JPH03234753A - Production of fluororesin having high elastic modulus - Google Patents
Production of fluororesin having high elastic modulusInfo
- Publication number
- JPH03234753A JPH03234753A JP2820490A JP2820490A JPH03234753A JP H03234753 A JPH03234753 A JP H03234753A JP 2820490 A JP2820490 A JP 2820490A JP 2820490 A JP2820490 A JP 2820490A JP H03234753 A JPH03234753 A JP H03234753A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- fluorine
- fluororesin
- polymerization
- units
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 6
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 125000000962 organic group Chemical class 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 239000000178 monomer Substances 0.000 abstract description 9
- 239000000155 melt Substances 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DVMSVWIURPPRBC-UHFFFAOYSA-N 2,3,3-trifluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C(F)F DVMSVWIURPPRBC-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical group FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は高弾性率を有するフッ素樹脂の製造法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a fluororesin having a high modulus of elasticity.
［従来の技術］ フッ素樹脂はその優れた耐熱性、耐薬品性。[Conventional technology] Fluororesin has excellent heat resistance and chemical resistance.
表面特性により、さまざまな分野で利用されているが、
その欠点の一つとして弾性率の低いことがあげられる。It is used in various fields due to its surface characteristics, but
One of its drawbacks is its low elastic modulus.
またポリテトラフルオロエチレン（ＰＴＦＥ）以外のフ
ッ素樹脂は融点以上に加熱すると流動して形が保てない
ことも欠点としてあげられる。ＰＴＦＥは融点以上に加
熱しても流動しないが、逆に溶融成形できないという欠
点がある。かくして高弾性率で溶融成形ができてしかも
融点以上に加熱しても流動しないフッ素樹脂の開発が望
まれていた。Another drawback of fluororesins other than polytetrafluoroethylene (PTFE) is that they flow and cannot maintain their shape when heated above their melting point. PTFE does not flow even when heated above its melting point, but it has the disadvantage that it cannot be melt-molded. Thus, it has been desired to develop a fluororesin that can be melt-molded with a high modulus of elasticity and that does not flow even when heated above its melting point.
フッ素樹脂を成形後架橋させることによりこれらの要求
特性を満たすことが考えられ、いままで様々な架橋方法
が考案されている。例えば特公昭６２−２３７７２では
フッ素樹脂に電子線を照射して架橋させている。しかし
この方法はハイドロカーボン樹脂には有効でもパーフル
オロ樹脂には適応できない。また特開昭６１−１５５４
１０ではフッ素樹脂にトリアリルシアヌレートなどの架
橋剤を添加して電子線架橋を行っている。しかしこの方
法で得られた樹脂は架橋剤の存在により耐薬品性、耐熱
性が劣る。また特開昭６３６８６０４やυＳＰ ４，２
０４，９２７ではフッ素樹脂に光反応性基を付加し光架
橋を行っている。しかしこれらの方法でも得られた樹脂
は耐薬品性、副動性に劣る。また、特公昭５５−２３５
６７にはテトラフルオロエチレンとパーフルオロアクリ
ル酸（誘導体〉との共重合体に熱を加えることにより架
橋することが記述されている。しかし、架橋したポリマ
ーについての物性の詳しい記述はない。It is thought that these required characteristics can be met by crosslinking the fluororesin after molding, and various crosslinking methods have been devised so far. For example, in Japanese Patent Publication No. 62-23772, a fluororesin is crosslinked by irradiating it with an electron beam. However, although this method is effective for hydrocarbon resins, it cannot be applied to perfluoro resins. Also, JP-A-61-1554
In No. 10, electron beam crosslinking is performed by adding a crosslinking agent such as triallyl cyanurate to a fluororesin. However, the resin obtained by this method has poor chemical resistance and heat resistance due to the presence of a crosslinking agent. Also, JP-A-6368604 and υSP 4,2
In No. 04,927, a photoreactive group is added to a fluororesin and photocrosslinking is performed. However, the resins obtained by these methods are inferior in chemical resistance and side movement properties. In addition, special public service 55-235
67 describes that a copolymer of tetrafluoroethylene and perfluoroacrylic acid (derivative) is crosslinked by applying heat. However, there is no detailed description of the physical properties of the crosslinked polymer.
［発明の解決しようとする課題］
本発明は、従来知られていなかった高弾性フッ素樹脂を
与える製造法を新規に提供することを目的とするもので
ある。[Problems to be Solved by the Invention] An object of the present invention is to provide a novel manufacturing method for producing a high-elastic fluororesin, which has not been previously known.
Ｃ課題を解決するための手段］
本発明は、前述の問題点を解決すべくなされたものであ
り、式（１） イＣＦ、−ＣＦＸチ（ただしＸはフッ
素または塩素である）で表わされる単し、Ｒ２は２価の
フッ素置換有機基、Ｙはカルボン酸基またはカルボン酸
誘導体である）で表わされる単位が０．１〜２０モル％
、式（３）（ＣＦ、−ＣＦＺ ） （たタシ、２は１価
ノフッ素置換有機基である）で表わされる単位がＯまた
は１０モル％以下の割合である含フツ素重合体を２００
℃以上該含フッ素重合体の融点以下の温度で熱処理する
ことを特徴とする高弾性率フッ素樹脂の製造法を提供す
るものである。Means for Solving Problem C] The present invention has been made to solve the above-mentioned problems, and is represented by the formula (1) ACF, -CFXC (where X is fluorine or chlorine). R2 is a divalent fluorine-substituted organic group, Y is a carboxylic acid group or a carboxylic acid derivative) 0.1 to 20 mol%
, a fluorine-containing polymer in which the units represented by the formula (3) (CF, -CFZ) (where 2 is a monovalent fluorine-substituted organic group) is O or a proportion of 10 mol% or less is
The present invention provides a method for producing a high modulus fluororesin, which is characterized by heat treatment at a temperature of 0.degree. C. or higher and lower than the melting point of the fluoropolymer.
本発明の製造法において用いる含フツ素重合体は、式ｍ
（ＣＦ、−ＣＦＸ ） （ただしＸはフッ素または
塩素である）で表わされる単位がＲ，は２価のフッ素置
換有機基、Ｙはカルボン酸基またはカルボン酸誘導体基
である）で表わされる単位が０．１〜２０モル％、式（
３）（ＣＦ、−ＣＦＺ ） （ただし２は１価のフッ素
置換有機基である）で表わされる単位が０または１０モ
ル％以下である含フツ素重合体である。The fluorine-containing polymer used in the production method of the present invention has the formula m
(CF, -CFX) (where X is fluorine or chlorine), R is a divalent fluorine-substituted organic group, Y is a carboxylic acid group or carboxylic acid derivative group 0.1-20 mol%, formula (
3) A fluorine-containing polymer in which the unit represented by (CF, -CFZ) (where 2 is a monovalent fluorine-substituted organic group) is 0 or 10 mol% or less.
かかる含フツ素重合体において、式（１）のＸはフッ素
であるものの方が耐薬品性などの面からより好ましい。In such a fluorine-containing polymer, it is more preferable that X in formula (1) is fluorine from the viewpoint of chemical resistance.
式（２）におけるＲｔは２価のフッ素置換有機基である
。例えば（ＣＦｚ）。Rt in formula (2) is a divalent fluorine-substituted organic group. For example (CFz).
（ＣＦ、 ）−、、（ＯＣＦｚ（：ＦＪ□４ ＣＦｉＣ
ＦＯ） −４ＣＦ２） 。(CF, )-,, (OCFz(:FJ□4 CFiC
FO) -4CF2).
昆 ＋″ＣＦａＣＦＯ） −（ＣＦａ：） 。Kon +″CFaCFO) −(CFa:).
などの基が例示される。特にパーフルオロ基であるもの
が好ましい。また、Ｙはカルボン酸基またはカルボン酸
誘導体基である。具体的には−ＣＯＯＡ （Ａは水素
、炭素数１〜３程度のアルキル基あるいはフルオロアル
キル基、アルカリ金属、またはアンモニウム塩基、ある
いは置換アンモニウム塩基）または−ＣＯＢ（Ｂはフッ
素または塩素）が例示される。本発明では、含フツ素重
合体が上記Ｙで表わされる基を有するため、後述の方法
により高弾性率を有するフッ素樹脂を製造することが可
能である。Examples include groups such as Particularly preferred are perfluoro groups. Moreover, Y is a carboxylic acid group or a carboxylic acid derivative group. Specifically, -COOA (A is hydrogen, an alkyl group or fluoroalkyl group having about 1 to 3 carbon atoms, an alkali metal, an ammonium base, or a substituted ammonium base) or -COB (B is fluorine or chlorine) are exemplified. Ru. In the present invention, since the fluorine-containing polymer has the group represented by Y, it is possible to produce a fluororesin having a high elastic modulus by the method described below.
本発明の方法において用いられる含フツ素重合体は上述
の単位を、式（１）の単位７０〜９９．９モル％５式（
２）の単位を０．１〜２０％の割合で含有する。式（２
）で表わされる単位が少なすぎると後述の方法により処
理しても高弾性率を有するフッ素樹脂が得られ難くなる
ので好ましくない。また、多すぎると含フツ素重合体の
融点が低下し熱処理時に形状を保つことが難しくなるた
め精密成形が困難になる。熱処理時に内部歪が生じ易く
クラックが発生し易くなる。また重合体がエラストマー
性となり成形性が低下する、などの欠点が生じるため好
ましくない。The fluorine-containing polymer used in the method of the present invention contains 70 to 99.9 mol% of the units of formula (1).
Contains units of 2) in a proportion of 0.1 to 20%. Formula (2
) If the number of units represented by ) is too small, it becomes difficult to obtain a fluororesin having a high modulus of elasticity even when processed by the method described below, which is not preferable. On the other hand, if the amount is too large, the melting point of the fluorine-containing polymer decreases and it becomes difficult to maintain the shape during heat treatment, making precision molding difficult. Internal strain is likely to occur during heat treatment and cracks are likely to occur. In addition, the polymer becomes elastomeric, resulting in reduced moldability, which is undesirable.
また、本発明の方法において用いられる含フツ素重合体
は、上述の式（１）および式（２）の単位から構成され
るものであってもよいし、式（３）４ＣＦ、−ＣＦＺ
）−（ただし２は１価のフッ素置換有機基である）で表
わされる単位を含むものであってもよい。式（３）で表
わされる単位が含まれていると、溶融成形性の向上、熱
処理後のフッ素樹脂の耐衝撃性９強靭性などの物性向上
といった利点がある。ただし、過剰に式（３）で表わさ
れる単位を含むとエラストマー性となるため好ましくな
い。式（３）で表わされる単位は１０モル％以下である
ことが好ましい。Further, the fluorine-containing polymer used in the method of the present invention may be composed of units of the above formula (1) and formula (2), or may be composed of units of formula (3) 4CF, -CFZ
)-(wherein 2 is a monovalent fluorine-substituted organic group). When the unit represented by formula (3) is included, there are advantages such as improved melt moldability and improved physical properties such as impact resistance 9 toughness of the fluororesin after heat treatment. However, it is not preferable to contain an excessive amount of the unit represented by formula (3) because it becomes elastomeric. The unit represented by formula (3) is preferably 10 mol% or less.
また、かかる含フツ素重合体は、式（１°）ＣＦ、＝Ｃ
ＦＸ （Ｘは前述と同シ）、式（２°）ヨリ式（３’
） ＣＦ、ＣＦＺ （Ｚは前述と同じ）で表わされる
単量体を重合開始源の存在下に共重合することによって
得られる。重合開始源としては、電離性放射線や、有機
パーオキサイド系重合開始剤、酸化還元系重合開始剤な
どの重合開始剤などが採用可能である。また、重合方法
としては、懸濁重合、乳化重合、溶液重合、塊状重合な
ど従来公知の重合方法が採用される。Moreover, such a fluorine-containing polymer has the formula (1°) CF, =C
FX (X is the same as above), formula (2°) and formula (3'
) It can be obtained by copolymerizing monomers represented by CF and CFZ (Z is the same as above) in the presence of a polymerization initiator. As the polymerization initiation source, ionizing radiation, a polymerization initiator such as an organic peroxide polymerization initiator, a redox polymerization initiator, etc. can be employed. Further, as the polymerization method, conventionally known polymerization methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are employed.
ここで重合開始剤としては遊離ラジカル重合開始剤が好
ましく、例えばジ（フルオロアシル）パーオキシド類、
ジ（クロロフルオロアシル）パーオキシド類、ジアルキ
ルパーオキシジカーボエート類、ジアシルパーオキシド
類、パーオキシエステル類、過硫酸塩類などが挙げられ
る。Here, the polymerization initiator is preferably a free radical polymerization initiator, such as di(fluoroacyl) peroxides,
Examples include di(chlorofluoroacyl) peroxides, dialkyl peroxy dicarboates, diacyl peroxides, peroxy esters, persulfates, and the like.
重合媒体としては、溶液重合ではフロン１１゜フロン１
１３などのフロン類、ターシャリブタノールなどが挙げ
られ、懸濁重合、乳化重合では水または水と他の溶媒と
の混合媒体が用いられる。In solution polymerization, the polymerization medium is CFC 11° CFC 1
Examples include chlorofluorocarbons such as No. 13, tertiary butanol, and the like. In suspension polymerization and emulsion polymerization, water or a mixed medium of water and other solvents is used.
重合温度は０〜１００℃、重合圧力は０．５〜３０ｋｇ
／ｃｍ”Ｇの範囲から選択することができる。Polymerization temperature is 0~100℃, polymerization pressure is 0.5~30kg
/cm”G range.
重合反応は、例えば撹拌機つきオートクレーブに重合媒
体と単量体（２”）、および必要により単量体（３“）
９分子量論節剤をまず仕込み、必要量の単量体（ｌｏ）
を圧入し、重合開始剤を加えて重合を開始する。The polymerization reaction is carried out by placing the polymerization medium and the monomer (2"), and if necessary, the monomer (3") in an autoclave equipped with a stirrer, for example.
9 Molecular weight moderating agent is first added, and the required amount of monomer (lo) is added.
is press-fitted, and a polymerization initiator is added to start polymerization.
重合の進行と共に圧力が低下するので、圧力の低下を補
うように化合物（Ａ）を圧入し、目的量の重合体が生成
するまで重合を続ける。重合終了後は未反応モノマーを
放出後、重合体を洗浄、乾燥する。得られた重合体は、
重合体の融点以上に加熱することにより溶融成形が可能
である。また成形物を２００℃以上融点以下の温度で５
時間以上処理を行うことにより架橋剤の添加なしに架橋
させることができ、高弾性率で融点以上でも流動しない
成形物が得られる。Since the pressure decreases as the polymerization progresses, compound (A) is injected under pressure to compensate for the decrease in pressure, and the polymerization is continued until the desired amount of polymer is produced. After the polymerization is completed, unreacted monomers are released, and then the polymer is washed and dried. The obtained polymer is
Melt molding is possible by heating the polymer to a temperature higher than its melting point. In addition, the molded product is heated at a temperature of 200℃ or higher and lower than the melting point for 5 minutes.
By carrying out the treatment for a longer period of time, crosslinking can be carried out without adding a crosslinking agent, and a molded article having a high elastic modulus and not flowing even above the melting point can be obtained.
本発明において、含フツ素重合体はメルトフローレート
が０．０１−１００のものが好ましい。メルトフローレ
ートとは含フツ素重合体の融点以上の温度で測定される
押出速度（ｇ／分）であり、具体的には次に示す方法で
測定した。In the present invention, the fluorine-containing polymer preferably has a melt flow rate of 0.01-100. The melt flow rate is the extrusion rate (g/min) measured at a temperature equal to or higher than the melting point of the fluorine-containing polymer, and specifically, it was measured by the method shown below.
メルトインデクサ−を用い、含フツ素重合体を内径９．
５ＩＩＩＩ１１のシリンダーに装填し３８０℃で５分間
保持した後、その温度で５ ｋｇのピストン荷重下に内
径２．１ ｍｍ 、長さ８．０ｍｍのオリフィスを通し
て押出し、このときの押出し速度（ｇ／分）をメルトフ
ローレートとした。Using a melt indexer, measure the fluorine-containing polymer to an inner diameter of 9.
After loading it into a cylinder of 5III11 and holding it at 380°C for 5 minutes, it was extruded at that temperature under a piston load of 5 kg through an orifice with an inner diameter of 2.1 mm and a length of 8.0 mm. ) was taken as the melt flow rate.
また融点は真空理工製分析機（ＤＴＡ）を用いて行った
。試料１０ ｍｇをアルミニウムカップに入れ、室温よ
り毎分ｌＯ℃で昇温し、融解吸熱ピーク温度を融点とし
た。メルトフローレートが極めて小さい、すなわち超高
分子量のものは、成形性が極めて低下し、成形材料とし
て適さなくなり、また、メルトフローレートが極めて大
きい、すなわち、低分子量のものは、機械的強度が著し
く低下し、好ましくない。Further, the melting point was determined using a vacuum-Riko analyzer (DTA). 10 mg of the sample was placed in an aluminum cup, and the temperature was raised from room temperature at 10°C per minute, and the melting endothermic peak temperature was taken as the melting point. A material with an extremely low melt flow rate, that is, an ultra-high molecular weight, has extremely low moldability and is no longer suitable as a molding material.A material with an extremely high melt flow rate, that is, a material with a low molecular weight, has extremely low mechanical strength. lowered and unfavorable.
本発明は、上述の含フツ素重合体を２００℃以上含フツ
素重合体の融点以下の温度で熱処理することが重要であ
る。かかる熱処理を行うことにより高弾性率フッ素樹脂
が得られる。熱処理は所望の形状に成形した後に行うこ
とが好ましい。熱処理温度が低すぎると充分な高弾性率
変化が達成されず、またあまりに高温で行うと熱処理時
に形状保持のための手段が必要となり、作業が煩雑にな
るため好ましくない。また、熱処理は５時間以上行うこ
とが好ましい。In the present invention, it is important to heat-treat the above-mentioned fluorine-containing polymer at a temperature of 200° C. or higher and lower than the melting point of the fluorine-containing polymer. By performing such heat treatment, a high elastic modulus fluororesin can be obtained. It is preferable that the heat treatment is performed after molding into a desired shape. If the heat treatment temperature is too low, a sufficiently high change in the elastic modulus will not be achieved, and if the heat treatment temperature is too high, a means to maintain the shape will be required during the heat treatment, which will complicate the work, which is not preferable. Moreover, it is preferable to carry out the heat treatment for 5 hours or more.
熱処理時間が短いと充分な高弾性変化が難しい。また、
熱処理は窒素ガスなどのイナートガス中で行ってもよい
し、空気中で行ってもよい。作業性の面からは空気中で
行うことが好ましい。If the heat treatment time is short, it is difficult to achieve a sufficiently high elasticity change. Also,
The heat treatment may be performed in an inert gas such as nitrogen gas or in air. From the viewpoint of workability, it is preferable to carry out the process in air.
［実施例］
合成例１
内容積１２００ｃｃの撹拌機つきオートクレーブに、フ
ロン１１３を１４７４ｇ 、ＣＦ２＝ＣＦＯ（ＣＦ２）
３ｃＯＯｃ）１Ｂを４１．７ｇ 、メタノールを０．８
３ｇ仕込み、内部空間を窒素ガスで１分置換した後これ
を排気し、これにテトラフルオロエチレン（ＴＦＥ）６
０ｇ圧入し、温度を５０℃にし、撹拌を行う。これに重
合開始剤としてジ（ヘプタフルオロプロパノイル）パー
オキサイドを１重量％フロン１１３に溶解させたものを
５．５ｃｃ加えて重合を開始させる。反応中、圧力の降
下に応じてＴＦＥを逐次追加し、一定圧力を保つように
する。ＴＦＥの逐次追加量が７４ｇになったところで冷
却、モノマーバージを行なった。得られたスラリー溶７
夜をフロン１１３で洗浄して、１２０℃１２時間乾燥し
、重合体を得た。[Example] Synthesis Example 1 In an autoclave with an internal volume of 1200 cc and equipped with a stirrer, 1474 g of Freon 113 was added, CF2=CFO (CF2)
3cOOc) 41.7g of 1B, 0.8g of methanol
After charging 3g and replacing the internal space with nitrogen gas for 1 minute, it was evacuated, and tetrafluoroethylene (TFE) 6
0 g was introduced under pressure, the temperature was raised to 50°C, and the mixture was stirred. To this, 5.5 cc of di(heptafluoropropanoyl) peroxide dissolved in 1% by weight Freon 113 as a polymerization initiator is added to initiate polymerization. During the reaction, TFE is added sequentially as the pressure decreases to maintain a constant pressure. When the amount of TFE added sequentially reached 74 g, cooling and monomer purge were performed. Obtained slurry solution 7
The polymer was washed with Freon 113 and dried at 120°C for 12 hours to obtain a polymer.
重合体の物性の測定は次の方法によって行った。The physical properties of the polymer were measured by the following method.
メルトフローレート
メルトインデクサ−により測定したもので、重合体を内
径９．５ｍｍのシリンダーに装填し３８０℃で５分間保
持した後、その温度で５ｋｇのピストン荷重下に内径２
．１ｍｍ 、長さ８ｍｍのオリフィスを通して押出し、
このときの押出速度（ｇ／分）をメルトフローレートと
した。Melt flow rate was measured using a melt indexer. After the polymer was loaded into a cylinder with an inner diameter of 9.5 mm and held at 380°C for 5 minutes, the inner diameter was 2.
．． Extruded through an orifice of 1 mm and 8 mm long,
The extrusion speed (g/min) at this time was defined as the melt flow rate.
ＣＦ、＝ＣＦＯ（ＣＦ、）ａｃＯＯｃＨ，含有量粉体の
試料的０．８ｇを秤量し、０．３５ＮのＮａＯＨ−メタ
ノール溶液に浸漬し、密封して６０℃で２日間放置した
後、メタノール溶液中の未反応のＮａＯＨをＯ，ＩＮの
ＭＣＩ水溶液で滴定することにより求めた。CF,=CFO(CF,)acOOcH, Content: 0.8 g of powder sample was weighed, immersed in 0.35N NaOH-methanol solution, sealed and left at 60°C for 2 days, then diluted with methanol solution. The unreacted NaOH in the solution was determined by titration with an aqueous MCI solution of O and IN.
融点（”Ｃ） 融点は真空理工製熱分析機（ＤＴＡ）を用いて行った。Melting point ("C) The melting point was determined using a thermal analyzer (DTA) manufactured by Shinku Riko.
試料１０ｍｇをアルミニウムカップに入れ、室温より毎
分１０℃で昇温し、融解吸熱ピーク温度を融点とした。10 mg of the sample was placed in an aluminum cup, and the temperature was raised from room temperature at a rate of 10°C per minute, and the melting endothermic peak temperature was taken as the melting point.
合成例２
ＣＦｚ：ＣＦＯｆＣＦｚ）ａｃＯＯｃＨｓを２５．０ｇ
を仕込みメタノールを１．１３ｇ仕込む以外は合成例１
と同等の方法により重合体を得た。Synthesis Example 2 25.0 g of CFz:CFOfCFz)acOOcHs
Synthesis Example 1 except that 1.13g of methanol was charged.
A polymer was obtained by the same method as above.
合成例３
合成例１のＣＦｚ：ＣＦＯ（ＣＦａ）３ＣＯＯＣＨｚの
かわりにＣＦ２：ＣＦＯＣＦｚＣＦ（ＣＦ３）０（Ｃｈ
）ｉｃＯＯｃＨｓを６４．３ｇ仕込みメタノールを０．
６４ｇ仕込む以外は合成例１と同等の方法により重合体
を得た。Synthesis Example 3 Instead of CFz:CFO(CFa)3COOCHz in Synthesis Example 1, CF2:CFOCFzCF(CF3)0(Ch
) 64.3g of icOOcHs and 0.0g of methanol.
A polymer was obtained in the same manner as in Synthesis Example 1 except that 64 g was charged.
合成例４
合成例１のＣＦ２＝ＣＦＯｆＣＦ、１３ＣＯＯＣ）１．
のかわりにＣＦ２＝ＣＦＯｆＣＦり３ＣＯＯＨ４１，８
ｇ仕込みメタノールを０．４５ｇ仕込む以外は合成例１
と同等の方法により重合体を得た。Synthesis Example 4 CF2 of Synthesis Example 1=CFOfCF, 13COOC)1.
Instead, CF2=CFOfCFri3COOH41,8
Synthesis Example 1 except that 0.45g of methanol was charged.
A polymer was obtained by the same method as above.
合成例５
合成例１のｃｐａ＝ｃｐｏ （ＣＦ、） 、Ｃ００ＣＲ
，のかわりにＣＦ、＝ＣＦＯ（ＣＦｔ）、ＣＯＦ ４２
．１ｇ仕込みメタノールを０、７８ｇ仕込む以外は合成
例１と同等の方法により重合体を得た。Synthesis Example 5 cpa of Synthesis Example 1 = cpo (CF,), C00CR
, instead of CF, =CFO(CFt), COF 42
．． A polymer was obtained in the same manner as in Synthesis Example 1 except that 0.78 g of methanol was charged.
合成例６
ＣＦ、＝ＣＦＯ（ＣＦ、）、Ｃ００ＣＨｓ ２５．Ｄｇ
、 ＣＦ、＝ＣＦＯＣＦＩＣＦ、ＣＦｚ ２１．７ｇ
仕込みメタノール０．９５ｇ仕込む以外は合成例１と同
等の方法により重合体を得た。Synthesis Example 6 CF,=CFO(CF,), C00CHs 25. Dg
, CF,=CFOCFICF, CFz 21.7g
A polymer was obtained in the same manner as in Synthesis Example 1 except that 0.95 g of methanol was charged.
表１に重合結果を示す。Table 1 shows the polymerization results.
実施例１〜６．比較例１，２゜
表２に各合成例の含フツ素重合体、ＰＦＡ樹脂およびＰ
ＴＦＥ樹脂の熱処理前後の物性を示す。Examples 1-6. Comparative Examples 1 and 2 Table 2 shows the fluorine-containing polymer, PFA resin, and P of each synthesis example.
The physical properties of TFE resin before and after heat treatment are shown.
熱処理を行うことにより、高弾性率で、融点以上に加熱
しても流動せず、耐熱性、耐薬品性の優れた成形物を得
ることができた。By performing the heat treatment, it was possible to obtain a molded product that had a high elastic modulus, did not flow even when heated above the melting point, and had excellent heat resistance and chemical resistance.
［発明の効果］
本発明の方法は高弾性率で融点以上に加熱しても流動せ
ず、耐熱、耐薬品性が良好であるという優れた効果を有
するフッ素樹脂を与えることができるものである。[Effects of the Invention] The method of the present invention can provide a fluororesin having excellent effects such as a high modulus of elasticity, no flow even when heated above the melting point, and good heat resistance and chemical resistance. .
Claims (2)
だしＸはフッ素 または塩素である）で表わされる単位が７０〜９９．９
モル％、式（２）▲数式、化学式、表等があります▼（
ただし、Ｒ＿ｆは２価のフッ素置換有機基、Ｙはカルボ
ン酸基またはカルボン酸誘導体である）で表わされる単
位が０．１〜２０モル％、式（３）▲数式、化学式、表
等があります▼（ただし、Ｚは１価のフッ素置 換有機基である）で表わされる単位が０または１０モル
％以下の割合である含フッ素重合体を２００℃以上該含
フッ素重合体の融点以下の温度で熱処理することを特徴
とする高弾性率フッ素樹脂の製造法。(1) Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where X is fluorine or chlorine) The unit represented by is 70 to 99.9
Mol%, formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (
However, R_f is a divalent fluorine-substituted organic group, and Y is a carboxylic acid group or carboxylic acid derivative. ▼ (However, Z is a monovalent fluorine-substituted organic group) A fluoropolymer containing 0 or 10 mol% or less of units is heated at a temperature of 200°C or higher and below the melting point of the fluoropolymer. A method for producing a high modulus fluororesin, which is characterized by heat treatment.
。(2) The manufacturing method according to claim 1, wherein the heat treatment is performed for at least 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2820490A JP3210000B2 (en) | 1990-02-09 | 1990-02-09 | Manufacturing method of high modulus fluororesin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2820490A JP3210000B2 (en) | 1990-02-09 | 1990-02-09 | Manufacturing method of high modulus fluororesin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03234753A true JPH03234753A (en) | 1991-10-18 |
| JP3210000B2 JP3210000B2 (en) | 2001-09-17 |
Family
ID=12242137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2820490A Expired - Fee Related JP3210000B2 (en) | 1990-02-09 | 1990-02-09 | Manufacturing method of high modulus fluororesin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3210000B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015623A1 (en) * | 1995-10-27 | 1997-05-01 | Daikin Industries, Ltd. | Resin composition, molding produced using the same, and process for producing the same |
| JP2002265522A (en) * | 2001-03-09 | 2002-09-18 | Kurabo Ind Ltd | Method of improving pra resin |
| US6479161B1 (en) | 1997-06-06 | 2002-11-12 | Daikin Industries, Ltd. | Fluorine-containing adhesive and adhesive film and laminated article made by using the same |
| JP2007153960A (en) * | 2005-12-01 | 2007-06-21 | Yunimatekku Kk | Fluorine-containing copolymer and article on which thin film thereof is formed |
| EP2527397A1 (en) | 2005-10-31 | 2012-11-28 | Daikin Industries, Ltd. | Method for molding polytetrafluoroethylene, polytetrafluoroethylene molded body, crosslinkable polytetrafluoroethylene, powdered polytetrafluoroethylene crosslinked body, resin blend composition of matter and resin blend molded body |
| JP2015096572A (en) * | 2013-11-15 | 2015-05-21 | 旭硝子株式会社 | Manufacturing method of fluorine-containing copolymer molded article, wire coating material and slide member |
| CN105814120A (en) * | 2013-09-19 | 2016-07-27 | 泰尔茂株式会社 | Polymer particles |
| CN105849159A (en) * | 2013-12-26 | 2016-08-10 | 旭硝子株式会社 | Method for manufacturing fluorine-containing cross-linked product and use thereof |
| JP2017516903A (en) * | 2014-06-05 | 2017-06-22 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Melt-processable perfluoropolymer with improved thermal and mechanical properties after heat treatment |
-
1990
- 1990-02-09 JP JP2820490A patent/JP3210000B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015623A1 (en) * | 1995-10-27 | 1997-05-01 | Daikin Industries, Ltd. | Resin composition, molding produced using the same, and process for producing the same |
| US6479578B2 (en) | 1995-10-27 | 2002-11-12 | Daikin Industries, Ltd. | Resin composition |
| US6479161B1 (en) | 1997-06-06 | 2002-11-12 | Daikin Industries, Ltd. | Fluorine-containing adhesive and adhesive film and laminated article made by using the same |
| US6599997B2 (en) | 1997-06-06 | 2003-07-29 | Daikin Industries, Ltd. | Fluorine-containing adhesive and adhesive film and laminated article made by using same |
| JP2002265522A (en) * | 2001-03-09 | 2002-09-18 | Kurabo Ind Ltd | Method of improving pra resin |
| EP2527397A1 (en) | 2005-10-31 | 2012-11-28 | Daikin Industries, Ltd. | Method for molding polytetrafluoroethylene, polytetrafluoroethylene molded body, crosslinkable polytetrafluoroethylene, powdered polytetrafluoroethylene crosslinked body, resin blend composition of matter and resin blend molded body |
| EP2641936A1 (en) * | 2005-10-31 | 2013-09-25 | Daikin Industries, Ltd. | Method for molding polytetrafluoroethylene, polytetrafluoroethylene molded body, crosslinkable polytetrafluoroethylene, powered polytetrafluoroethylene crosslinked body, resin blend composition of matter and resin blend molded body |
| JP2007153960A (en) * | 2005-12-01 | 2007-06-21 | Yunimatekku Kk | Fluorine-containing copolymer and article on which thin film thereof is formed |
| CN105814120A (en) * | 2013-09-19 | 2016-07-27 | 泰尔茂株式会社 | Polymer particles |
| JP2015096572A (en) * | 2013-11-15 | 2015-05-21 | 旭硝子株式会社 | Manufacturing method of fluorine-containing copolymer molded article, wire coating material and slide member |
| CN105849159A (en) * | 2013-12-26 | 2016-08-10 | 旭硝子株式会社 | Method for manufacturing fluorine-containing cross-linked product and use thereof |
| JP2017516903A (en) * | 2014-06-05 | 2017-06-22 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Melt-processable perfluoropolymer with improved thermal and mechanical properties after heat treatment |
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|---|---|
| JP3210000B2 (en) | 2001-09-17 |
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