JP2003192731A - Method for producing polytetrafluoroethylene - Google Patents
Method for producing polytetrafluoroethyleneInfo
- Publication number
- JP2003192731A JP2003192731A JP2001395012A JP2001395012A JP2003192731A JP 2003192731 A JP2003192731 A JP 2003192731A JP 2001395012 A JP2001395012 A JP 2001395012A JP 2001395012 A JP2001395012 A JP 2001395012A JP 2003192731 A JP2003192731 A JP 2003192731A
- Authority
- JP
- Japan
- Prior art keywords
- ptfe
- monomer
- reaction system
- polytetrafluoroethylene
- producing
- 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 49
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 49
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 230000001737 promoting effect Effects 0.000 claims abstract description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 9
- 239000000155 melt Substances 0.000 abstract description 5
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000009778 extrusion testing Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】
【課題】融点以上において、成型に適した溶融粘度特性
を示すＰＴＦＥの製造方法を提供する。
【解決手段】分子中に遊離し易いフッ素原子を有するパ
ーフルオロビニルモノマーを分岐促進コモノマーとして
含み、連鎖移動剤を分岐長さの調節のための分子量調節
剤として含む反応系において、テトラフルオロエチレン
モノマーを重合することによって分岐状のポリテトラフ
ルオロエチレンを生成させる。(57) [Problem] To provide a method for producing PTFE exhibiting a melt viscosity characteristic suitable for molding at a melting point or higher. A reaction system comprising a perfluorovinyl monomer having a fluorine atom which is easily liberated in a molecule as a branching promoting comonomer and a chain transfer agent as a molecular weight regulator for controlling the branch length, comprising a tetrafluoroethylene monomer. Is polymerized to produce a branched polytetrafluoroethylene.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリテトラフルオ
ロエチレン（以下、ＰＴＦＥという）の製造方法に関
し、特に、融点以上において、成型に適した溶融粘度特
性を示すＰＴＦＥの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polytetrafluoroethylene (hereinafter referred to as PTFE), and more particularly to a method for producing PTFE showing melt viscosity characteristics suitable for molding at a melting point or higher.
【０００２】[0002]
【従来の技術】ＰＴＦＥは、繰り返し単位を規則正しく
並べた鎖状の分子構成を有し、これによる高い結晶性を
備える点においてポリエチレンと共通するところがある
が、骨格炭素原子に結合するフッ素原子がポリエチレン
分子における水素原子より大きく、従って、分子の自由
回転性に大きな制約があることと、これにより分子鎖が
剛直性を帯びている点においては、ポリエチレンと大き
く異なっている。2. Description of the Related Art PTFE has a molecular structure in a chain structure in which repeating units are regularly arranged and has a high crystallinity, which is common with polyethylene, but a fluorine atom bonded to a skeletal carbon atom is a polyethylene. It differs greatly from polyethylene in that it is larger than a hydrogen atom in a molecule, and thus has a large restriction on the free rotation of the molecule, and that the molecular chain is rigid due to this.
【０００３】また、ＰＴＦＥは、骨格炭素原子の表面が
フッ素原子でほとんど埋め尽くされているために、その
分子鎖から炭化水素の性質が失われていること、従っ
て、フッ素を主体とした構成物特有の極度に低い摩擦係
数を備えており、さらに、低屈折率による優れた光学的
特性を有している点においても、ポリエチレンとは異な
るところがある。Further, PTFE has a structure in which fluorine is the main constituent, because the surface of the skeletal carbon atoms is almost completely filled with fluorine atoms, so that the molecular chain loses the property of hydrocarbons. It is different from polyethylene in that it has a peculiar extremely low coefficient of friction and has excellent optical properties due to a low refractive index.
【０００４】また、分子鎖を構成する骨格炭素原子とフ
ッ素原子の間の共有結合エネルギーが、水素原子や塩素
原子結合のものよりも大きく、従って、このことによる
プラスティックス中最高の耐熱性を備えていることも、
この重合体の大きな特色であり、さらには、高周波特性
および耐化学薬品性等に優れていることも、この重合体
の大きな利点として挙げることができる。Further, the covalent bond energy between the skeletal carbon atom and the fluorine atom constituting the molecular chain is larger than that of the hydrogen atom or chlorine atom bond, and therefore, this provides the highest heat resistance in plastics. That
It is a great feature of this polymer that it is a major feature of this polymer and that it is also excellent in high frequency characteristics and chemical resistance.
【０００５】以上のように優れた特性を有するＰＴＦＥ
は、絶縁材料、機械部品材料あるいは電子部品材料等多
くの用途に活用されており、特に、光通信、半導体およ
び先端医療の分野においては、他のプラスティックス類
では代替えすることのできない特殊な材料として、揺る
ぎない地位を占めている。PTFE having excellent properties as described above
Is used in many applications such as insulating materials, mechanical parts materials, electronic parts materials, etc. In particular, in the fields of optical communication, semiconductors and advanced medicine, special materials that cannot be replaced by other plastics. As such, it occupies an unwavering position.
【０００６】[0006]
【発明が解決しようとする課題】しかし、従来のＰＴＦ
Ｅによると、加工性に著しく劣る性質を有するため、そ
の成型に際しては、ペースト状押出あるいは金型加工等
の非効率的な方法に依存せざるを得ず、このため、生産
性の面において大きな不利益性を有している。[Problems to be Solved by the Invention] However, conventional PTF
According to E, since it has a property of being extremely inferior in workability, it has no choice but to rely on an inefficient method such as paste-like extrusion or die processing in its molding. It has a disadvantage.
【０００７】即ち、従来のＰＴＦＥの溶融粘度は、３８
０℃で約１０11ポイズと極めて高く、従って、ゲルのよ
うな流動性を示さないことから、通常の押出機等による
溶融成型は望めない。このため、乳化重合より得られる
ファインパウダーの場合には、主としてペースト状押出
加工が採られ、一方、懸濁重合より得られるモールディ
ンググレード品の場合には、金型による成型か普通とな
るが、これらの方法は、非効率的であり、低い生産性を
余儀なくされる。That is, the melt viscosity of conventional PTFE is 38
Since it is extremely high at about 10 11 poise at 0 ° C. and therefore does not show fluidity like gel, it cannot be expected to be melt-molded by an ordinary extruder or the like. Therefore, in the case of fine powder obtained by emulsion polymerization, mainly paste-like extrusion processing is adopted, while in the case of molding grade products obtained by suspension polymerization, molding by a mold is common, These methods are inefficient and force low productivity.
【０００８】この融点以上の温度において極度に高い溶
融粘度を示す原因は、いまだ充分に解明されてはおら
ず、さらに、ＰＴＦＥを溶解させるのに適した溶剤がな
いために、その溶液粘度あるいは分子量を特定するため
の精密測定すら、不可能な状態にあるのが実情である。The cause of the extremely high melt viscosity at temperatures above this melting point has not yet been fully clarified, and since there is no suitable solvent for dissolving PTFE, its solution viscosity or molecular weight is The reality is that even precise measurements for identification are impossible.
【０００９】分子量については、溶融粘度やクリープ測
定の結果より、ポリエチレンよりも大きな、およそ数百
万程度の高水準にあるものと推定されているが、これを
成型性確保のために数十万程度に下げる場合には、なぜ
か実用上の機械的特性が得られなくなる特質を有してお
り、このように従来のＰＴＦＥには、成型性を改良する
うえにおいて、多くの未解明事項ないしは問題点が内在
している。Regarding the molecular weight, it is estimated from the results of melt viscosity and creep measurement that it is at a high level of about several million, which is larger than that of polyethylene. When it is lowered to a certain degree, it has a characteristic that mechanical properties for practical use cannot be obtained for some reason. Thus, in the conventional PTFE, there are many unclear points or problems in improving the moldability. The dot is inherent.
【００１０】従って、本発明の目的は、融点以上におい
て、成型に適した溶融粘度特性を示す新規タイプのＰＴ
ＦＥの製造方法を提供することにある。Therefore, an object of the present invention is to provide a novel type of PT which exhibits a melt viscosity characteristic suitable for molding at a melting point or higher.
It is to provide a manufacturing method of FE.
【００１１】[0011]
【課題を解決するための手段】本発明は、上記の目的を
達成するため、融点以上において流動性を示し、前記流
動性に基づく良好な成型性を有するＰＴＦＥの製造方法
において、遊離し易いフッ素原子を分子中に含むパーフ
ルオロビニルモノマーを分岐促進コモノマーとして含
み、連鎖移動剤を分岐長さの調節のための分子量調節剤
として含む反応系において、テトラフルオロエチレンモ
ノマーを重合することによって前記反応系に分岐状の分
子構成を有するＰＴＦＥを生成させることを特徴とする
ＰＴＦＥの製造方法を提供するものである。[Means for Solving the Problems] In order to achieve the above-mentioned object, the present invention shows a flowable substance at a melting point or higher, and a fluorine which is easily liberated in a method for producing PTFE having good moldability based on the fluidity. In a reaction system containing a perfluorovinyl monomer containing an atom in the molecule as a branching-promoting comonomer and a chain transfer agent as a molecular weight controlling agent for controlling the branch length, the reaction system by polymerizing a tetrafluoroethylene monomer. The present invention provides a method for producing PTFE, characterized in that PTFE having a branched molecular structure is produced.
【００１２】本発明は、実用上における充分な機械的特
性と、融点以上での低い溶融粘度特性を両立させること
に基盤をおくもので、従来のＰＴＦＥがほぼ線状の分子
構成を有していることの確認と、これとは異質の多数の
長分岐を有するＰＴＦＥが、融点以上において良好な流
動性を示すことの発見により成立しているものである。The present invention is based on achieving both sufficient mechanical properties for practical use and low melt viscosity properties above the melting point, and conventional PTFE has an almost linear molecular structure. It has been confirmed by the confirmation that it is present and that PTFE having a large number of long branches, which are different from each other, exhibits good fluidity at the melting point or higher.
【００１３】また、これに加え、分岐は比較的長いもの
であること、末端と分岐の間の分子鎖が従来の線状のＰ
ＴＦＥより短いこと、および分岐状ＰＴＦＥの分子１個
の平均の数平均分子量が従来の線状ＰＴＦＥのそれとほ
ぼ同等であることが、実用的な機械的特性を得るための
前提となることを見出したものである。In addition to this, the branch is relatively long, and the molecular chain between the end and the branch is a conventional linear P
It was found that it is shorter than TFE and that the average number average molecular weight of one molecule of branched PTFE is almost the same as that of conventional linear PTFE, which is a prerequisite for obtaining practical mechanical properties. It is a thing.
【００１４】そして、その基本的な考え方は、連鎖反応
により生成する重合体の分子構造をして、分岐促進コモ
ノマーの存在により成長しつつある鎖状ラジカルへフッ
素原子を移動させ易い構造とし、これにより鎖状ラジカ
ルの成長を停止させることによって重合体の分子を再活
性化させ、この再活性化した重合体にモノマーを付加し
て成長させるか、あるいは他の成長鎖状ラジカルと結合
させて分岐状ＰＴＦＥを生成させることにある。The basic idea is that the molecular structure of the polymer formed by the chain reaction is set to a structure in which the fluorine atom is easily transferred to the growing chain radical due to the presence of the branch promoting comonomer. To reactivate the molecule of the polymer by stopping the growth of the chain radical by adding a monomer to this reactivated polymer to grow it, or to combine it with another growing chain radical to branch it. The purpose is to generate PTFE.
【００１５】但し、これらの反応を繰り返し継続して行
わせるためには、適度な長さに制御された鎖状ラジカル
が多数存在していることが必要であり、これは、分子量
を調節することによって達成される。本発明における連
鎖移動剤は、この意味において重要な存在であり、従っ
て、本発明が目的とする分岐状のＰＴＦＥを生成させる
ためには、前述した分岐促進コモノマーと同じく、連鎖
移動剤も重要な要素となる。However, in order to carry out these reactions repeatedly and continuously, it is necessary that a large number of chain radicals controlled to have an appropriate length be present, which is to control the molecular weight. Achieved by The chain transfer agent in the present invention is important in this sense, and therefore, in order to produce the branched PTFE targeted by the present invention, the chain transfer agent is also important in the same manner as the above-mentioned branch promoting comonomer. It becomes an element.
【００１６】本発明における分岐促進コモノマーの量
は、このコモノマーとテトラフルオロエチレンモノマー
との合計量のうちの０．５〜３．０重量％（以下、単に
％という）を占めるように設定することが好ましく、ま
た、連鎖移動剤の量は、分岐促進コモノマーおよびテト
ラフルオロエチレンモノマーを含む反応系１００重量部
（以下、単に部という）に対して、０．００２〜０．０
２部となるように設定することが好ましい。The amount of the branch promoting comonomer in the present invention is set so as to account for 0.5 to 3.0% by weight (hereinafter, simply referred to as%) of the total amount of the comonomer and the tetrafluoroethylene monomer. The amount of the chain transfer agent is preferably 0.002 to 0.0 with respect to 100 parts by weight of the reaction system containing the branching promoting comonomer and the tetrafluoroethylene monomer (hereinafter simply referred to as "parts").
It is preferable to set the number of copies to be two.
【００１７】前者の数値範囲における下限値は、得られ
るＰＴＦＥに良好な成型性を与えるうえでの守るべき最
低水準であり、一方、上限値は、ＰＴＦＥとしての特質
を維持するのに守るべき限界値となる。また、後者の数
値範囲における下限値は、有効な分子量調節効果を得る
ための好ましい最低値であり、一方、上限値は、反応の
進行を阻害しないようにするために守るべき最大値とな
る。The lower limit in the numerical range of the former is the minimum level that should be observed in order to give the obtained PTFE good moldability, while the upper limit is the limit that should be observed in order to maintain the characteristics of PTFE. It becomes a value. In addition, the lower limit of the latter numerical range is a preferable minimum for obtaining an effective molecular weight adjusting effect, while the upper limit is a maximum that should be observed so as not to hinder the progress of the reaction.
【００１８】分岐促進コモノマーを構成するパーフルオ
ロビニルモノマーは、遊離し易いフッ素原子を有するこ
とによって特徴づけられるものであり、具体的には、ヘ
キサフルオロプロピレンあるいはフルオロアルキルビニ
ルエーテル等が好適な例として挙げられる。一方、分子
量調節剤の例としては、たとえば、ｎ−フルオロブチル
メルカプタン、ｎ−フルオロドデシルメルカプタンある
いはｔ−フルオロブチルメルカプタン等が挙げられる。The perfluorovinyl monomer which constitutes the branching-promoting comonomer is characterized by having a fluorine atom which is easily released, and specific examples thereof include hexafluoropropylene and fluoroalkyl vinyl ether. To be On the other hand, examples of the molecular weight modifier include n-fluorobutyl mercaptan, n-fluorododecyl mercaptan, t-fluorobutyl mercaptan and the like.
【００１９】なお、本発明による製造方法は、従来と同
じく乳化重合あるいは懸濁重合に基づいて行われる。従
って、反応遂行のためには、当然、開始剤が必要であ
り、これには、ハイドロパーオキサイド類、脂肪族系ア
ゾビスニトリル類；あるいは水溶性有機過酸化物、過酸
化加里、過酸化水素または第１鉄イオン等の水溶性開始
剤などが使用される。反応開始剤の代わりに各種の放射
線を使用することは可能である。The production method according to the present invention is carried out on the basis of emulsion polymerization or suspension polymerization as in the conventional case. Therefore, in order to carry out the reaction, of course, an initiator is required, which includes hydroperoxides, aliphatic azobisnitriles; or water-soluble organic peroxides, potassium peroxide, hydrogen peroxide. Alternatively, a water-soluble initiator such as ferrous ion is used. It is possible to use various radiations instead of the initiator.
【００２０】[0020]
【発明の実施の形態】次に、本発明によるＰＴＦＥの製
造方法の実施の形態を説明する。BEST MODE FOR CARRYING OUT THE INVENTION Next, an embodiment of the method for producing PTFE according to the present invention will be described.
【実施例１】水６４部に脂肪酸石けん０．７部と過酸化
加里０．０４部を加えて攪拌することにより水媒体を調
合し、この水媒体に連鎖移動剤としてｎ−フルオロブチ
ルメルカプタン０．０１部を加えて攪拌した後、この閉
じられた反応系の温度を６０℃に加熱昇温させ、これ
に、テトラフルオロエチレン９７％とヘキサフルオロプ
ロピレン（分岐促進コモノマー）３％の混合ガス３６部
を封入して３０分間攪拌反応させた。Example 1 An aqueous medium was prepared by adding 0.7 part of fatty acid soap and 0.04 part of potassium peroxide to 64 parts of water and stirring, and n-fluorobutyl mercaptan 0 as a chain transfer agent was added to this aqueous medium. After adding 0.01 part and stirring, the temperature of the closed reaction system was raised to 60 ° C. and heated to a mixed gas 36 of tetrafluoroethylene 97% and hexafluoropropylene (branching promoting comonomer) 3%. The part was sealed and the reaction was carried out with stirring for 30 minutes.
【００２１】反応終了後、得られた乳化液を破壊・分離
させることによって液中に生成した重合体を採取および
精製し、これにより、分岐状の分子構成を有する所定の
ＰＴＦＥ（厳密には、ヘキサフルオロプロピレンとの共
重合体）を得た。After completion of the reaction, the resulting emulsion is destroyed and separated to collect and purify the polymer produced in the emulsion, whereby a predetermined PTFE having a branched molecular structure (strictly speaking, A copolymer with hexafluoropropylene) was obtained.
【００２２】次に、このＰＴＦＥを加熱プレスによって
成形したところ、４００℃×３０分の条件下において、
０．５ｍｍの厚さにシート化することができた。得られ
たシートは、透明であり、浮沈比重法による密度は、
２．１０５ｇ／ｃｍ3を示した。Next, when this PTFE was molded by a hot press, under the condition of 400 ° C. × 30 minutes,
It could be formed into a sheet having a thickness of 0.5 mm. The obtained sheet is transparent, and the density by the float-sink specific gravity method is
It showed 2.105 g / cm 3 .
【００２３】一方、このシートを使用して動的粘弾性の
温度分散を測定したところ、測定周波数が１Ｈｚにおい
て、従来のＰＴＦＥ（線状ＰＴＦＥ）より値が若干低い
ものの、３１０℃以上４００℃までプラトーモジュラス
を示した。On the other hand, when the temperature dispersion of dynamic viscoelasticity was measured using this sheet, the value was slightly lower than that of conventional PTFE (linear PTFE) at a measurement frequency of 1 Hz, but from 310 ° C to 400 ° C. The plateau modulus was shown.
【００２４】また、測定周波数を１／１０の０．１Ｈｚ
に下げ、同じく動的粘弾性の温度分散を測定したとこ
ろ、モジュラスは、３１０℃以上において急激な低下を
示し、さらに、測定後のシートサンプルの外観状態も、
構成重合体が溶解し、流動した痕跡を明確に残してい
た。The measurement frequency is 1/10, 0.1 Hz.
When the temperature dispersion of the dynamic viscoelasticity was similarly measured, the modulus showed a sharp decrease at 310 ° C. or higher, and the appearance state of the sheet sample after the measurement was also
The constituent polymer dissolved, leaving a clear trace of fluidization.
【００２５】なお、この実施例で得られたシートの引張
強度を温度２４℃および引張速度５０ｍｍ／ｍｉｎの条
件下に測定したところ、１．６ｋｇｆ／ｍｍ2と、充分
な特性を示した。また、ＤＳＣ融点を昇温速度１０℃／
ｍｉｎのもとに測定したところ、３１２℃を示し、さら
に、４００℃のフローテスターによる押出テストを実施
した結果、成型するのに充分な良好な押出加工性を示し
た。The tensile strength of the sheet obtained in this example was measured under the conditions of a temperature of 24 ° C. and a pulling speed of 50 mm / min. As a result, it showed 1.6 kgf / mm 2 and sufficient characteristics. In addition, the DSC melting point is set to a temperature rising rate of 10 ° C /
When measured under min, it showed 312 ° C. Further, as a result of carrying out an extrusion test with a flow tester at 400 ° C., good extrusion processability sufficient for molding was shown.
【００２６】[0026]
【実施例２】実施例１において、連鎖移動剤および開始
剤として、それぞれｔ−フルオロブチルメルカプタン
０．０１８部および過酸化水素０．１８部を使用し、さ
らに、封入する混合ガスの組成をテトラフルオロエチレ
ン９９％およびフルオロアルキルビニルエーテル１％に
設定するとともに、反応系の温度を７０℃に設定するこ
とにより、所定の分岐状ＰＴＦＥを製造した。Example 2 In Example 1, 0.018 parts of t-fluorobutyl mercaptan and 0.18 part of hydrogen peroxide were used as the chain transfer agent and the initiator, respectively, and the composition of the mixed gas to be sealed was changed to tetra. Fluoroethylene 99% and fluoroalkyl vinyl ether 1% were set, and the temperature of the reaction system was set to 70 ° C. to produce a predetermined branched PTFE.
【００２７】得られたＰＴＦＥを加熱プレスによりシー
ト化したところ、実施例１と同様に成型可能であり、４
００℃×３０分の条件で容易にシート化することができ
た。また、得られたシートの密度は２．２０ｇ／ｃｍ3
を示し、さらに、実施例１と同じ条件によりＤＳＣ融点
および引張強度を測定したところ、それぞれ３１８℃お
よび１．８ｋｇｆ／ｍｍ2の結果が得られた。When the obtained PTFE was formed into a sheet by a hot press, it could be molded in the same manner as in Example 1, and 4
A sheet could be easily formed under the condition of 00 ° C x 30 minutes. The density of the obtained sheet is 2.20 g / cm 3.
Furthermore, when the DSC melting point and the tensile strength were measured under the same conditions as in Example 1, the results of 318 ° C. and 1.8 kgf / mm 2 were obtained, respectively.
【００２８】また、このシートを使用して動的粘弾性の
温度分散を測定したところ、測定周波数によって大きな
違いを示し、およそ３２０℃以上では、１Ｈｚでプラト
ーモジュラスを示す一方、０．１Ｈｚになると、大きく
緩和する傾向を示した。なお、４００℃のフローテスタ
ーによる押出テストでは、充分に良好な押出加工性を示
した。When the temperature dispersion of dynamic viscoelasticity was measured using this sheet, a large difference was observed depending on the measurement frequency. At about 320 ° C. or higher, the plateau modulus was shown at 1 Hz, while it was 0.1 Hz. , Showed a tendency to greatly ease. In the extrusion test using a flow tester at 400 ° C., sufficiently good extrusion processability was exhibited.
【００２９】[0029]
【参考例１】実施例１において、分岐促進コモノマーを
使用せず、他を同じ条件に設定することによりＰＴＦＥ
の重合を実施したところ、得られた重合体の加熱プレス
による成型は可能であったが、動的粘弾性の測定は、測
定中に試料が破断したため、実施不可能であった。[Reference Example 1] In Example 1, a PTFE was obtained by using the same conditions except that the branching promoting comonomer was not used.
When the polymerization was carried out, the obtained polymer could be molded by hot pressing, but the dynamic viscoelasticity could not be measured because the sample broke during the measurement.
【００３０】[0030]
【参考例２】実施例１において、連鎖移動剤を使用せ
ず、他を同一条件に設定することによりＰＴＦＥの重合
を実施したところ、生成重合体は融点以上で流動せず、
加熱プレスによる成形が不可能であった。また、この重
合体を圧縮成型し、これより切り出したシートを使用し
て動的粘弾性の測定を実施した結果、測定周波数１Ｈｚ
および０．１Ｈｚのいずれにおいても堅固なプラトーモ
ジュラスを示し、緩和の傾向を全く示さなかった。Reference Example 2 The polymerization of PTFE was carried out in the same manner as in Example 1 except that the chain transfer agent was not used and the other conditions were set to the same conditions.
Molding by hot pressing was impossible. In addition, the polymer was compression molded and the sheet cut out therefrom was used to measure the dynamic viscoelasticity.
At 0.1 Hz and 0.1 Hz, a firm plateau modulus was exhibited and no tendency of relaxation was shown.
【００３１】[0031]
【参考例３】実施例１において、ヘキサフルオロプロピ
レンのテトラフルオロエチレンに対する混合比を４〜１
０％の範囲内において数例設定するとともに、他を同一
条件に設定することによりそれぞれＰＴＦＥの重合を実
施したところ、結果は、いずれも、参考例２と同じであ
った。[Reference Example 3] In Example 1, the mixing ratio of hexafluoropropylene to tetrafluoroethylene was 4 to 1
When several cases were set in the range of 0% and the polymerization of PTFE was carried out by setting the other conditions under the same conditions, the results were all the same as in Reference Example 2.
【００３２】[0032]
【参考例４】実施例１において、連鎖移動剤の量を０．
０３５部に設定するとともに、他を同一条件に設定する
ことによりＰＴＦＥの重合反応を実施したところ、得ら
れた生成物の加熱プレスによる成形は不可能であった。
この例および参考例３の結果より、本発明の実施に際し
ては、連鎖移動剤および分岐促進コモノマーの量に対し
て、充分な配慮を行うべきである。Reference Example 4 In Example 1, the amount of the chain transfer agent was adjusted to 0.
When the polymerization reaction of PTFE was carried out by setting the amount to 035 parts and the other conditions to the same, it was impossible to mold the obtained product by hot pressing.
From the results of this Example and Reference Example 3, sufficient consideration should be given to the amounts of the chain transfer agent and the branching promoting comonomer when carrying out the present invention.
【００３３】なお、以上に述べた実施例１および２にお
ける融点以上での引張モジュラスモードによる動的粘弾
性の温度分散の測定において、周波数１Ｈｚでプラトー
領域を示しながら、０．１Ｈｚで非プラトー化し、緩和
する挙動は、分子中に長い分岐を有するＰＴＦＥの特有
の性質といえる。In the measurement of the temperature dispersion of the dynamic viscoelasticity by the tensile modulus mode above the melting point in Examples 1 and 2 described above, a plateau region was shown at a frequency of 1 Hz, and a non-plateau was obtained at 0.1 Hz. The relaxation behavior can be said to be a characteristic property of PTFE having a long branch in the molecule.
【００３４】従って、１０11ポイズもの溶融粘度を有す
る従来の線状ＰＴＦＥとは全く異質の、３７０〜４４０
℃における良好な流動性が確認されているが、本発明に
よるＰＴＦＥは、この優位性以外に、卓越した摩耗抵抗
性を有することによっても特徴づけられる。Therefore, 370 to 440 which is completely different from the conventional linear PTFE having a melt viscosity of 10 11 poises.
Although good flowability at 0 ° C has been confirmed, the PTFE according to the present invention is also characterized not only by this advantage, but also by having excellent abrasion resistance.
【００３５】即ち、実施例１および２により得られたエ
マルジョンより粉状のＰＴＦＥを採取し、これを濃度２
０％となるように線状ＰＴＦＥ粉にブレンドしたものを
圧力３０ＭＰａで１時間圧縮成型し、これにより縦横５
０ｍｍおよび厚さ１０ｍｍのブロックを得た後、その比
摩耗量をＪＩＳ Ｋ７２１８に基づいて従来の線状ＰＴ
ＦＥとの対比において測定したところ、従来の線状ＰＴ
ＦＥ単独によるものが１０5×１０-8ｍｍ3／Ｎ・ｍ3 を
示したのに比べ、実施例１のＰＴＦＥを混入したものが
５０×１０-8ｍｍ3／Ｎ・ｍｍ3 、および実施例２のＰ
ＴＦＥを混入したものが３０×１０-8ｍｍ3／Ｎ・ｍ
3と、著しく低い結果を示した。That is, powdery PTFE was collected from the emulsions obtained in Examples 1 and 2, and the powdery PTFE was collected at a concentration of 2
A linear PTFE powder blended so as to be 0% was compression molded at a pressure of 30 MPa for 1 hour.
After obtaining a block with a thickness of 0 mm and a thickness of 10 mm, the specific wear amount was determined according to JIS K7218 and the conventional linear PT
When measured in comparison with FE, conventional linear PT
The FE alone showed 10 5 × 10 -8 mm 3 / N · m 3 , whereas the FE alone mixed with PTFE was 50 × 10 -8 mm 3 / N · mm 3 , and P in example 2
Those containing TFE are 30 × 10 -8 mm 3 / N ・ m
3, which was a remarkably low result.
【００３６】この理由についての解明は、充分に行われ
ていないが、恐らく、摩損のメカニズムのなか、融点以
上の領域において、分子鎖が線状ＰＴＦＥよりも容易に
緩和して外力による損傷を受けにくいこと、および流動
できることが関係しているものと推定される。この性質
は、ＰＴＦＥの活用範囲を広げるうえにおいて、明らか
に有益な特質となる。Although the reason for this has not been sufficiently clarified, it is conceivable that the molecular chains are more easily relaxed and damaged by external force than the linear PTFE in the region above the melting point in the mechanism of abrasion. It is presumed that difficulty and fluidity are involved. This property is an apparently useful property in expanding the range of use of PTFE.
【００３７】[0037]
【発明の効果】以上説明したように、本発明によるＰＴ
ＦＥの製造方法によれば、分子中に遊離し易いフッ素原
子を有するパーフルオロビニルモノマーを分岐促進コモ
ノマーとして含み、連鎖移動剤を分岐長さの調節のため
の分子量調節剤として含む反応系において、テトラフル
オロエチレンモノマーを重合することによってＰＴＦＥ
を製造するため、分岐状の分子構成を有し、従って、溶
融押出等による成型に適した溶融粘度特性を備えるＰＴ
ＦＥを提供することができる。As described above, the PT according to the present invention
According to the method for producing FE, in a reaction system containing a perfluorovinyl monomer having a fluorine atom which is easily released in the molecule as a branching promoting comonomer, and a chain transfer agent as a molecular weight controlling agent for controlling the branch length, PTFE by polymerizing tetrafluoroethylene monomer
Has a branched molecular structure and therefore has a melt viscosity characteristic suitable for molding by melt extrusion or the like.
FE can be provided.
Claims (3)
性に基づく良好な成型性を有するポリテトラフルオロエ
チレンの製造方法において、 遊離し易いフッ素原子を分子中に有するパーフルオロビ
ニルモノマーを分岐促進コモノマーとして含み、連鎖移
動剤を分岐長さの調節のための分子量調節剤として含む
反応系において、テトラフルオロエチレンモノマーを重
合することによって前記反応系に分岐状の分子構成を有
するポリテトラフルオロエチレンを生成させることを特
徴とするポリテトラフルオロエチレンの製造方法。1. A method for producing polytetrafluoroethylene which exhibits fluidity at a temperature equal to or higher than a melting point and has good moldability based on the fluidity, which promotes branching of a perfluorovinyl monomer having a fluorine atom which is easily liberated in the molecule. In a reaction system containing a comonomer and a chain transfer agent as a molecular weight modifier for adjusting the branch length, polytetrafluoroethylene having a branched molecular structure is polymerized in the reaction system by polymerizing a tetrafluoroethylene monomer. A method for producing polytetrafluoroethylene, which comprises producing the polytetrafluoroethylene.
合するステップは、前記反応系が、前記分岐促進コモノ
マーを前記テトラフルオロエチレンモノマーとの合計量
のうちの０．５〜３．０重量％を占めるように含むとと
もに、前記連鎖移動剤を当該反応系１００重量部当たり
０．００２〜０．０２重量部含む条件下において行われ
ることを特徴とする請求項１項記載のポリテトラフルオ
ロエチレンの製造方法。2. The step of polymerizing the tetrafluoroethylene monomer so that the reaction system accounts for 0.5 to 3.0% by weight of the total amount of the branch promoting comonomer and the tetrafluoroethylene monomer. And a chain transfer agent in an amount of 0.002 to 0.02 part by weight per 100 parts by weight of the reaction system.
合するステップは、前記分岐促進コモノマーとして、ヘ
キサフルオロプロピレンモノマーあるいはフルオロアル
キルビニルエーテルモノマーを含む前記反応系において
行われることを特徴とする請求項１項記載のポリテトラ
フルオロエチレンの製造方法。3. The step of polymerizing the tetrafluoroethylene monomer is performed in the reaction system containing a hexafluoropropylene monomer or a fluoroalkyl vinyl ether monomer as the branch promoting comonomer. Method for producing polytetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001395012A JP2003192731A (en) | 2001-12-26 | 2001-12-26 | Method for producing polytetrafluoroethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001395012A JP2003192731A (en) | 2001-12-26 | 2001-12-26 | Method for producing polytetrafluoroethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003192731A true JP2003192731A (en) | 2003-07-09 |
Family
ID=27601567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001395012A Pending JP2003192731A (en) | 2001-12-26 | 2001-12-26 | Method for producing polytetrafluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003192731A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052015A1 (en) * | 2003-11-26 | 2005-06-09 | Daikin Industries, Ltd. | Fluororesin and coated electric wire |
-
2001
- 2001-12-26 JP JP2001395012A patent/JP2003192731A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052015A1 (en) * | 2003-11-26 | 2005-06-09 | Daikin Industries, Ltd. | Fluororesin and coated electric wire |
| US7638588B2 (en) | 2003-11-26 | 2009-12-29 | Daikin Industries, Ltd. | Fluororesin and coated electric wire |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4792622B2 (en) | Tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer and method for producing the same | |
| JP5066096B2 (en) | Fluoropolymer composition | |
| JPS584728B2 (en) | Method for producing fluorine-containing multi-segmented polymer | |
| WO2007061914A1 (en) | Core/shell polymer | |
| CN108495891A (en) | Process for producing ASA graft copolymer, process for producing thermoplastic ASA resin composition comprising same, and process for producing ASA molded article | |
| JP2002138210A (en) | Multiple polymer additive system | |
| TWI372167B (en) | Polymer latex suitable for the preparation of dip-molded articles | |
| JP6573933B2 (en) | Acrylic processing aid and vinyl chloride resin composition containing the same | |
| EP0931798A1 (en) | Process for preparing modified PTFE | |
| CN101611090B (en) | Improved heat aged perfluoropolymer | |
| EP0111342B1 (en) | Non-melt-fabricable granular modified terafluoroethylene polymer | |
| JPS61266459A (en) | Sulfur-containing poly(arylether ketone) composition | |
| JP2003192731A (en) | Method for producing polytetrafluoroethylene | |
| CN112574347B (en) | Fluorine-containing vinyl chloride copolymer, method for producing same, composition comprising same, and resin article made from same | |
| JPS6149327B2 (en) | ||
| KR20080026971A (en) | Acrylic copolymer for processing aid of vinyl chloride-based resin composition, method for preparing the same, and vinyl chloride-based resin composition comprising the same | |
| CN117820535A (en) | Soft vinyl chloride copolymer, process for producing the same, vinyl chloride resin composition, and resin product | |
| Haba et al. | Development and characterization of reactively extruded PVC/polystyrene blends | |
| Abreu et al. | Reversible deactivation radical polymerization of vinyl chloride | |
| CN117801151A (en) | Rigid vinyl chloride copolymer and preparation method thereof, vinyl chloride resin composition and resin product | |
| WO2004056887A1 (en) | Tetrafluoroethylene copolymer | |
| CN111253512A (en) | Tetrafluoroethylene-alkyl acrylate-perfluoroalkyl vinyl ether dispersion resin and microporous membrane prepared from same | |
| CN112574349B (en) | Rigid polyvinyl chloride-based copolymer, method for producing same, composition comprising same, and resin product made from composition | |
| JP3791223B2 (en) | Ethylene / tetrafluoroethylene copolymer composition | |
| Chakrabarti et al. | Studies on engineering properties of PVC–PMMA semi‐interpenetrating polymer networks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040123 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050401 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20050712 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20051206 |