JPH0649775B2 - Method for producing polyazole molded article - Google Patents
Method for producing polyazole molded articleInfo
- Publication number
- JPH0649775B2 JPH0649775B2 JP18213787A JP18213787A JPH0649775B2 JP H0649775 B2 JPH0649775 B2 JP H0649775B2 JP 18213787 A JP18213787 A JP 18213787A JP 18213787 A JP18213787 A JP 18213787A JP H0649775 B2 JPH0649775 B2 JP H0649775B2
- Authority
- JP
- Japan
- Prior art keywords
- polyazole
- metal
- producing
- polyphosphoric acid
- poly
- 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.)
- Expired - Lifetime
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- Artificial Filaments (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、高い耐熱性と優れた弾性率を有するポリアゾ
ール成形体を提供する方法に関する。TECHNICAL FIELD The present invention relates to a method for providing a polyazole molded article having high heat resistance and an excellent elastic modulus.
＜従来の技術＞ ポリアゾールは通常ポリリン酸溶液中で重合生成され
る。重合反応液であるポリアゾールポリリン酸溶液を、
目的に応じて種々の形状のノズルから押し出し凝固溶中
に浸漬することにより、繊維状成形体やフイルム・シー
ト状成形体が得られ、またミキサー攪拌下に凝固浴中で
沈澱させると粒子状成形体が得られる。<Prior Art> Polyazoles are usually produced by polymerization in a polyphosphoric acid solution. Polyazole polyphosphoric acid solution, which is a polymerization reaction solution,
Depending on the purpose, it can be extruded from nozzles of various shapes and immersed in the coagulation melt to obtain fibrous moldings or film / sheet-shaped moldings. In addition, if it is precipitated in a coagulation bath while stirring with a mixer, it can be molded into particles. The body is obtained.
しかしながら従来の成形体にあっては種々の問題点があ
った。However, there are various problems in the conventional molded body.
即ち、繊維状やフイルム・シート状の成形体の如く高配
向化したものはフィブリル化しやすく、また粒子状に沈
澱させたものは加圧成形しても粒子相互が十分に融着し
ないという問題点があった。That is, a highly oriented product such as a fibrous or film / sheet shaped product is likely to be fibrillated, and a particle-precipitated product is not sufficiently fused with each other even when pressure-molded. was there.
本発明者らは、これら成形体の問題点は、ポリアゾール
にリン酸金属塩をミクロに介在させることにより解消さ
れることを見出し、かかるリン酸金属塩がミクロに介在
したポリアゾール成形体を得る方法につき鋭意検討し本
発明に到達した。The inventors of the present invention have found that the problems of these molded products can be solved by microscopically interposing a metal phosphate in polyazole, and a method for obtaining a polyazole molded product in which such a metal phosphate is microscopically present. Therefore, the present invention has been achieved.
＜問題点を解決する具体的な方法＞ 本発明はポリアゾールのポリリン酸溶液から、金属酸化
物，金属水酸化物及び／又は金属塩化物の存在下にポリ
アゾールを凝固せしめるポリアゾール成形体の製造方法
である。<Specific Method for Solving Problems> The present invention is a method for producing a polyazole molded product, which comprises coagulating polyazole from a polyphosphoric acid solution of polyazole in the presence of a metal oxide, a metal hydroxide and / or a metal chloride. is there.
本発明に用いられるポリアゾールとしては、ポリ−p −
フェニレンベンゾビスチアゾール，ポリ−p −フェニレ
ンベンゾビスオキサゾール或いはこれらのコポリマー又
はこれらのポリマーに核置換基をつけたものが挙げられ
る。The polyazole used in the present invention includes poly-p-
Examples thereof include phenylene benzobis thiazole, poly-p-phenylene benzobisoxazole, copolymers thereof, and those polymers having a nuclear substituent.
これらのポリマーの重合度は、その目安となる固有粘度
（［η］）で表わして２以上が好ましい。成形体を高強
度にするためには重合度の大きい方が好ましく、［η］
が10以上になるとさらに好ましい。The degree of polymerization of these polymers is preferably 2 or more in terms of the intrinsic viscosity ([η]) which is a standard. In order to increase the strength of the molded body, it is preferable that the degree of polymerization is large.
Is more preferably 10 or more.
金属酸化物，金属水酸化物又は金属塩化物を構成する金
属としては、Ｌi ，Ｎa ，Ｋ，Ｍg ，Ｃa ，Ｂa ，Ａl
，Ｔi ，Ｎi ，Ｚn ，Ｂa ，Ｆe 等が用いられる。Examples of the metal constituting the metal oxide, metal hydroxide or metal chloride are Li, Na, K, Mg, Ca, Ba and Al.
, Ti, Ni, Zn, Ba, Fe, etc. are used.
金属酸化物としては、Ｌi 2 Ｏ，Ｎa 2 Ｏ，Ｍg Ｏ，Ｃ
a Ｏ，Ｂa Ｏ，Ａl 2 Ｏ3 ，Ｔi Ｏ4 ，Ｎi Ｏ，Ｚn ，
Ｃu Ｏ，Ｆe Ｏ，Ｆe 2 Ｏ3 等が挙げられ、金属水酸化
物としては、Ｌi ＯＨ，Ｎa ＯＨ，Ｍg （ＯＨ）2 ，Ｃ
a （ＯＨ）2 ，Ｂa （ＯＨ）2 ，Ａl （ＯＨ）3 ，Ｎi
（ＯＨ）2 ，Ｚn （ＯＨ）2 ，Ｃu （ＯＨ）2 ，Ｆe
（ＯＨ）2 ，Ｆe （ＯＨ）3 等が挙げられ、金属塩化物
としては、Ｌi Cl，Ｎa Cl，Ｍg Cl2 ，Ｃa Cl2 ，Ｂa
Cl2 ，Ａl Cl3 ，Ｚn Cl2 ，Ｃu Cl2 ，Ｆe Cl2 ，Ｆe
Cl3 等が挙げられる。As the metal oxide, Li 2 O, Na 2 O, Mg O, C
a O, Ba O, Al 2 O 3 , Ti O 4 , Ni O, Zn,
Cu O, Fe O, Fe 2 O 3 and the like can be mentioned, and as the metal hydroxide, Li OH, Na OH, Mg (OH) 2 , C
a (OH) 2 , Ba (OH) 2 , Al (OH) 3 , Ni
(OH) 2 , Zn (OH) 2 , Cu (OH) 2 , Fe
(OH) 2, Fe (OH ) 3 and the like, and metal chloride, Li Cl, Na Cl, Mg Cl 2, Ca Cl 2, Ba
Cl 2, Al Cl 3, Zn Cl 2, Cu Cl 2, Fe Cl 2, Fe
Examples include Cl 3 and the like.
これら金属酸化物，金属水酸化物，金属塩化物は混合し
て用いてもよい。These metal oxides, metal hydroxides and metal chlorides may be mixed and used.
これらはポリアゾールのポリリン酸溶液と接触せしめら
れるとポリリン酸中に少くとも一部が溶解して行き、そ
の金属のリン酸塩となってポリアゾールと混合し、又は
その金属のリン酸塩を金属酸化物，金属水酸化物及び／
又は金属塩化物の表面に形成してポリアゾールと混合す
るため、これらの金属酸化物，金属水酸化物又は金属塩
化物が存在する状態でポリアゾールポリリン酸溶液から
ポリアゾールを凝固させると、凝固ポリアゾール中にリ
ン酸塩及び／又はリン酸塩を表面に形成した金属酸化物
や金属水酸化物又は金属塩化物がミクロに混入すること
になる。When these are brought into contact with a polyphosphoric acid solution of polyazole, at least a part of them will be dissolved in polyphosphoric acid to form the metal phosphate, which is mixed with polyazole, or the metal phosphate is oxidized with metal. Thing, metal hydroxide and /
Or, since it is formed on the surface of the metal chloride and mixed with the polyazole, when the polyazole is coagulated from the polyazole polyphosphoric acid solution in the presence of these metal oxides, metal hydroxides or metal chlorides, the coagulated polyazole The phosphate and / or the metal oxide, the metal hydroxide or the metal chloride having the phosphate formed on the surface thereof are microscopically mixed.
金属酸化物や金属水酸化物又は金属塩化物は直接ポリア
ゾールポリリン酸溶液中に添加しても良く、また凝固浴
中に添加しておいてもよい。The metal oxide, metal hydroxide or metal chloride may be added directly to the polyazole polyphosphoric acid solution or may be added to the coagulation bath.
ポリアゾール成形体中に混入せしめる量としては、成形
体がフイルム，テープや繊維状のものである場合は、金
属に換算して10wt％以下が好ましく、成形体が粒子状で
ある場合は融着性発現の上で20wt％以上であることが好
ましい。The amount to be mixed in the polyazole molded product is preferably 10 wt% or less in terms of metal when the molded product is a film, tape or fibrous product, and when the molded product is in a particulate form, the fusion property In terms of expression, it is preferably 20 wt% or more.
ポリアゾールのポリリン酸溶液からこれらの成形体を形
成せしめる方法は従来公知の方法が用いられ、凝固浴に
接触させる前の押し出しノズルの形状を種々かえること
により、繊維状，フイルム状，テープ状のものが得ら
れ、ミキサー攪拌下に凝固せしめると粒子状，粉末状の
ものが得られる。Conventionally known methods are used to form these molded products from a polyphosphoric acid solution of polyazole, and fibrous, film-shaped, and tape-shaped ones can be obtained by changing the shape of the extrusion nozzle before contacting with the coagulation bath. Is obtained and solidified under stirring with a mixer to obtain particles or powder.
本発明においてはポリアゾールポリリン酸溶液を、前記
金属酸化物，金属水酸化物及び／又は金属塩化物を含有
する水系凝固浴中に押し出し、又は投入攪拌する方法
が、凝固ポリアゾール中の金属含有量をコントロールす
る上で好ましい。In the present invention, a method of extruding a polyazole polyphosphoric acid solution into an aqueous coagulation bath containing the metal oxide, the metal hydroxide and / or the metal chloride, or adding and stirring the metal content in the coagulated polyazole. It is preferable for controlling
この際、高められた温度で接触させると金属の含有量が
高くなるので、粒子状成形体を得るときはこの方が好ま
しい。At this time, the content of the metal is increased when the particles are contacted at an elevated temperature, and therefore, this is preferable when a particulate molded body is obtained.
かくして得られた成形体、特に粒子状（粉末状）成形体
はさらに熱圧成形することもできる。例えば 200℃以上
600℃以下の温度， 100〜5000Kg／cm2，好ましくは１
０００Kg／cm2以上の圧力で熱圧成形すると緻密・強靭
な成形体が得られる。The molded product thus obtained, particularly a particulate (powdered) molded product, can be further subjected to thermocompression molding. For example, above 200 ℃
Temperature below 600 ℃, 100-5000Kg / cm 2 , preferably 1
Dense and tough compacts can be obtained by thermocompression molding at a pressure of 000 kg / cm 2 or more.
この熱圧成形時の雰囲気は、窒素ガス，ヘリウムガス，
アルゴンガス等の不活性ガス下又は空気下であってよい
が、脱気しながら行うことが好ましい。The atmosphere during this hot-press forming is nitrogen gas, helium gas,
It may be carried out under an inert gas such as argon gas or under air, but it is preferably carried out while degassing.
＜発明の効果＞ 本発明により得られた成形体は、フイルム状，テープ状
や繊維状のものは耐フィブリル性が向上し、粒子・粉末
状のものはそれを熱圧成形することにより耐熱性の高い
高モジュラス成形体を与える原料として有用である。<Effects of the Invention> The molded product obtained according to the present invention has improved fibril resistance in the form of film, tape or fiber, and heat resistance in the form of particles / powder by thermocompression molding. It is useful as a raw material for providing a high-modulus molded product having a high viscosity.
（ポリアゾールの固有粘度測定法） ポリアゾールをメタンスルホン酸溶液に溶解し、ポリマ
ー濃度 0.05 ， 0.2wt％とする。この溶液をウベロード
型粘度計で測定しηsp／c を求め、これをゼロ濃度に外
挿することで固有粘度（［η］）を求める。(Method for measuring intrinsic viscosity of polyazole) Polyazole is dissolved in a methanesulfonic acid solution to make polymer concentrations of 0.05 and 0.2 wt%. This solution is measured with an Ubbelohde viscometer to obtain ηsp / c, and the intrinsic viscosity ([η]) is obtained by extrapolating this to zero concentration.
実施例１ ポリ−p −フェニレンベンゾビスチアゾールのポリリン
酸溶液は、以下のごとく作成した。Example 1 A polyphosphoric acid solution of poly-p-phenylenebenzobisthiazole was prepared as follows.
即ち 2−， 5−ジアミノ− 1−， 4−ベンゼンジチオー
ル塩酸塩55.39 ｇをアルゴンガス雰囲気下で採取し、充
分に脱気したポリリン酸 438ｇの入ったフラスコ中に添
加し、アルゴンガス雰囲気下で60℃で約24時間攪拌を続
けて塩化水素ガスを除去した。次いで等量のテレフター
ル酸を添加し、さらに脱気したポリリン酸を 560ｇ追加
して90− 100℃で５時間攪拌し、次いで 150℃で昇温し
て12時間攪拌し、さらに 180− 200℃で24時間攪拌し
た。最終的に固有粘度21のポリ−p −フェニレンベンゾ
ビスチアゾールのポリリン酸溶液を得た。That is, 55.39 g of 2-, 5-diamino-1-, 4-benzenedithiol hydrochloride was collected in an argon gas atmosphere, added to a flask containing 438 g of sufficiently degassed polyphosphoric acid, and then added in an argon gas atmosphere. Hydrogen chloride gas was removed by continuing stirring at 60 ° C. for about 24 hours. Then, an equal amount of terephthalic acid was added, and 560 g of degassed polyphosphoric acid was added and stirred at 90-100 ° C for 5 hours, then heated at 150 ° C and stirred for 12 hours, and further at 180-200 ° C. It was stirred for 24 hours. Finally, a polyphosphoric acid solution of poly-p-phenylenebenzobisthiazole having an intrinsic viscosity of 21 was obtained.
該ポリ−p −フェニレンベンゾビスチアゾールのポリリ
ン酸溶液に酸化アルミニウムを、Ｐ／Ａｌが３：１にな
るように添加し、 200℃で加熱して混合した。Aluminum oxide was added to the polyphosphoric acid solution of poly-p-phenylenebenzobisthiazole so that P / Al was 3: 1, and the mixture was heated at 200 ° C. and mixed.
さらにこれをメタノール中にて粉砕し、粒子化して 350
℃の温度で熱処理した。これを温水洗浄し、未反応のポ
リリン酸を溶出し、乾燥してポリ−p −フェニレンベン
ゾビスチアゾールリン酸アルミニウム金属塩を得た。該
金属塩を金型に入れ真空ポンプで脱気しながら 200まで
昇温した。荷重2000Kg／cm2を加え、さらに脱気しなが
ら 430℃で12時間熱圧成形した。本サンプルの曲げモジ
ュラスは15.9ＧＰa で強度は67ＭＰa であった。Furthermore, it was crushed in methanol and made into particles.
Heat treatment was performed at a temperature of ° C. This was washed with warm water, unreacted polyphosphoric acid was eluted, and dried to obtain aluminum metal poly-p-phenylenebenzobisthiazolephosphate. The metal salt was placed in a mold and heated up to 200 while degassing with a vacuum pump. A load of 2000 kg / cm 2 was applied, and while further degassing, thermocompression molding was performed at 430 ° C. for 12 hours. The bending modulus of this sample was 15.9 GPa and the strength was 67 MPa.
同様に 450℃で12時間の熱圧成型したものは曲げモジュ
ラス24.9ＧＰa で強度は72ＭＰa であった。良好な成形
体が得られた。密度から推定されたポリ−p −フェニレ
ンベンゾビスチアゾールの含有量は39％であった。Similarly, the product obtained by thermocompression molding at 450 ° C. for 12 hours had a bending modulus of 24.9 GPa and a strength of 72 MPa. A good molded product was obtained. The content of poly-p-phenylenebenzobisthiazole estimated from the density was 39%.
比較例１ 実施例１において、ポリ−p −フェニレンベンゾビスチ
アゾールが溶解していないポリリン酸のみからなる溶液
を用いる以外は、まったく同じ操作でリン酸アルミニウ
ム金属塩粒子を得、金型に入れて熱圧成形した。熱圧条
件 430℃×12時間， 450℃×12時間の2000Kg／cm2の圧
力下で成形したものは、いずれも粒子間の付着力がな
く、くだけてしまった。Comparative Example 1 Aluminum phosphate metal salt particles were obtained by the same procedure as in Example 1 except that a solution consisting of polyphosphoric acid in which poly-p-phenylenebenzobisthiazole was not dissolved was used, and the particles were placed in a mold. It was hot pressed. Hot-pressing conditions 430 ° C. × 12 hours, 450 ° C. × 12 hours under a pressure of 2000 Kg / cm 2 , all had no adhesion between particles and were worn out.
ポリ−p −フェニレンベンゾビスチアゾールが存在する
場合は、リン酸アルミニウム金属塩がバインダーとして
有効に働くが、ポリ−p −フェニレンベンゾビスチアゾ
ールがない場合には、バインダーとして働かないことが
わかった。It has been found that when poly-p-phenylenebenzobisthiazole is present, the aluminum metal phosphate serves effectively as a binder, but in the absence of poly-p-phenylenebenzobisthiazole it does not.
比較例２ ポリ−p −フェニレンベンゾビスチアゾールのみからな
る粒子を実施例１の記載の方法とまったく同く条件で熱
圧成形を試みたが、粒子の付着がなく成形体を得るまで
に至らなかった。Comparative Example 2 Particles consisting only of poly-p-phenylenebenzobisthiazole were subjected to thermocompression molding under exactly the same conditions as in the method described in Example 1, but no particles adhered to obtain a molded body. It was
実施例２及び比較例３ 実施例１で得られたポリ−p −フェニレンベンゾビスチ
アゾールポリリン酸溶液を 0.3φの１ホールのノズルか
ら線速度30ｍ／min で押し出し、20cmの空気層を介して
凝固浴に浸漬した。凝固浴は、水酸化ナトリウムと塩化
アルミニウムをそれぞれ 0.05 モルづつ水に溶解したも
のを用いた。Example 2 and Comparative Example 3 The poly-p-phenylene benzobisthiazole polyphosphoric acid solution obtained in Example 1 was extruded at a linear velocity of 30 m / min from a 1-hole nozzle of 0.3φ and coagulated through an air layer of 20 cm. Immersed in a bath. The coagulation bath was prepared by dissolving 0.05 mol of sodium hydroxide and 0.05 mol of aluminum chloride in water.
凝固浴からでてきた未延伸糸は、軽く水洗後、温水で緊
張延伸後乾燥した。ついで 470℃で延伸した。The unstretched yarn coming out of the coagulation bath was lightly washed with water, stretched under warm water under tension and then dried. Then, it was stretched at 470 ° C.
熱延伸された繊維中には、Ａｌへの換算で約 3.2％含有
していた。繊維のモジュラスは 280ＧＰa で、強度は
2.1ＧＰa であった。The heat-drawn fiber contained about 3.2% in terms of Al. The fiber modulus is 280 GPa and the strength is
It was 2.1 GPa.
この繊維を20回程丸棒の上で左右に摩擦した。フィブリ
ル状のものが発生するが、その長さは短く、その量は少
なかった。This fiber was rubbed left and right on the round bar about 20 times. Fibrils were generated, but the length was short and the amount was small.
これに対し、凝固浴に水のみを用いて同じ条件で紡糸
し、後処理した繊維は、モジュラスが 280ＧＰa と同程
度のものでも丸棒の上での摩擦試験ではフィブリルの長
さが大きく、繊維自身が分割されるようにフィブリル化
した。On the other hand, the fiber which was spun under the same conditions using only water in the coagulation bath and post-treated had a large fibril length in the friction test on the round bar even if the modulus was about 280 GPa, and I fibrillated myself so that I could be divided.
Claims (5)
酸化物，金属水酸化物及び／又は金属塩化物の存在下
に、ポリアゾールを凝固せしめることを特徴とするポリ
アゾール成形体の製造方法。1. A method for producing a polyazole molded article, which comprises solidifying polyazole from a polyphosphoric acid solution of polyazole in the presence of a metal oxide, a metal hydroxide and / or a metal chloride.
ベンゾビスチアゾール及び／又はポリ−ｐ−フェニレン
ベンゾビスオキサゾールである特許請求の範囲第１項記
載のポリアゾール成形体の製造方法。2. The method for producing a polyazole molded article according to claim 1, wherein the polyazole is poly-p-phenylenebenzobisthiazole and / or poly-p-phenylenebenzobisoxazole.
化物がＣａ，Ｚｎ，Ａｌ，及びＮａ酸化物，水酸化物及
び塩化物から選ばれるものである特許請求の範囲第１項
記載のポリアゾール成形体の製造方法。3. The method according to claim 1, wherein the metal oxide, metal hydroxide and metal chloride are selected from Ca, Zn, Al and Na oxides, hydroxides and chlorides. A method for producing a polyazole molded body according to claim 1.
求の範囲第１項記載のポリアゾール成形体の製造方法。4. The method for producing a polyazole molded article according to claim 1, wherein the solidification is performed at 250 to 600 ° C.
ルム状又は粒子状である特許請求の範囲第１項記載のポ
リアゾール成形体の製造方法。5. The method for producing a polyazole molded product according to claim 1, wherein the polyazole molded product is in the form of fibers, films or particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18213787A JPH0649775B2 (en) | 1987-07-23 | 1987-07-23 | Method for producing polyazole molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18213787A JPH0649775B2 (en) | 1987-07-23 | 1987-07-23 | Method for producing polyazole molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6426646A JPS6426646A (en) | 1989-01-27 |
| JPH0649775B2 true JPH0649775B2 (en) | 1994-06-29 |
Family
ID=16112988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18213787A Expired - Lifetime JPH0649775B2 (en) | 1987-07-23 | 1987-07-23 | Method for producing polyazole molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0649775B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3631539A1 (en) * | 1986-09-17 | 1988-03-24 | Bayer Ag | AGING RESISTANT THERMOPLASTIC MOLDS WITH GOOD TOUGHNESS |
| US5302334A (en) * | 1992-05-21 | 1994-04-12 | The Dow Chemical Company | Process for coagulating and washing lyotropic polybenzazole films |
| WO1994025256A1 (en) * | 1993-04-30 | 1994-11-10 | The Dow Chemical Company | Three-dimensional polybenzazole structures |
-
1987
- 1987-07-23 JP JP18213787A patent/JPH0649775B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6426646A (en) | 1989-01-27 |
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| EXPY | Cancellation because of completion of term |