JP2515744B2 - Heat resistant aromatic polyester - Google Patents
Heat resistant aromatic polyesterInfo
- Publication number
- JP2515744B2 JP2515744B2 JP61136127A JP13612786A JP2515744B2 JP 2515744 B2 JP2515744 B2 JP 2515744B2 JP 61136127 A JP61136127 A JP 61136127A JP 13612786 A JP13612786 A JP 13612786A JP 2515744 B2 JP2515744 B2 JP 2515744B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- iii
- aromatic polyester
- structural unit
- mol
- 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
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L23/00—Flanged joints
- F16L23/02—Flanged joints the flanges being connected by members tensioned axially
- F16L23/024—Flanged joints the flanges being connected by members tensioned axially characterised by how the flanges are joined to, or form an extension of, the pipes
- F16L23/028—Flanged joints the flanges being connected by members tensioned axially characterised by how the flanges are joined to, or form an extension of, the pipes the flanges being held against a shoulder
- F16L23/0286—Flanged joints the flanges being connected by members tensioned axially characterised by how the flanges are joined to, or form an extension of, the pipes the flanges being held against a shoulder the shoulder not being formed from the pipe
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は400℃以下で溶融成形可能で、ガラス転移温
度が140℃以上のすぐれた機械的性質と光学異方性を有
する成形品を与え得る新規な耐熱性芳香族ポリエステル
に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention provides a molded product that can be melt-molded at 400 ° C or lower and has excellent mechanical properties and optical anisotropy with a glass transition temperature of 140 ° C or higher. The present invention relates to a novel heat-resistant aromatic polyester obtained.
〈従来の技術〉 近年プラスチツクの高性能化に対する要求がますます
高まり、種々の新規性能を有するポリマが数多く開発さ
れ、市場に供されているが、なかでも特に分子鎖の平行
な配列を特徴とする光学異方性の液晶ポリマがすぐれた
機械的性質を有する点で注目されている。<Prior art> In recent years, the demand for higher performance of plastics has been increasing, and many polymers having various new properties have been developed and put on the market. A liquid crystal polymer having optical anisotropy has attracted attention because it has excellent mechanical properties.
この液晶ポリマとしては全芳香族ポリエステルが広く
知られており、例えばｐ−ヒドロキシ安息香酸のホモポ
リマおよびコポリマが知られている。しかしながらこの
ｐ−ヒドロキシ安息香酸ホモポリマおよびコポリマはそ
の融点があまりにも高すぎて溶融成形不可能であるた
め、ｐ−ヒドロキシ安息香酸に種々の成分を共重合し、
その融点を下げる方法が検討され、例えばｐ−ヒドロキ
シ安息香酸にフエニルハイドロキノン、テレフタル酸お
よび／または2,6−ナフタレンジカルボン酸を共重合す
る方法（公表特許公報昭55-500215号）、ｐ−ヒドロキ
シ安息香酸に2,6−ジヒドロキシナフタレンとテレフタ
ル酸を共重合する方法（特開昭54-50594号公報）および
ｐ−ヒドロキシ安息香酸に2,6−ジヒドロキシアンスラ
キノンとテレフタル酸を共重合する方法（米国特許第4,
224,433号）、ｐ−ヒドロキシ安息香酸に4,4′−ジヒド
ロキシビフエニルとテレフタル酸、イソフタル酸を共重
合する方法（特公昭57-24407、60-25046号公報）、テレ
フタル酸にフエニルハイドロキノンとｔ−ブチルハイド
ロキノンを共重合する方法（米国特許第4,238,600
号）、テレフタル酸に核置換フエニルハイドロキノンと
ハイドロキノンなどを共重合する方法（米国特許第4,15
3,779号）などが提案されている。As this liquid crystal polymer, a wholly aromatic polyester is widely known, for example, a homopolymer and a copolymer of p-hydroxybenzoic acid are known. However, since the melting point of the p-hydroxybenzoic acid homopolymer and copolymer is too high to be melt-molded, various components are copolymerized with p-hydroxybenzoic acid,
A method for lowering the melting point has been studied, for example, a method for copolymerizing phenylhydroquinone, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid with p-hydroxybenzoic acid (published patent publication No. 55-500215), p- Method for copolymerizing hydroxybenzoic acid with 2,6-dihydroxynaphthalene and terephthalic acid (JP-A-54-50594) and method for copolymerizing p-hydroxybenzoic acid with 2,6-dihydroxyanthraquinone and terephthalic acid (U.S. Patent No. 4,
224,433), a method of copolymerizing p-hydroxybenzoic acid with 4,4'-dihydroxybiphenyl and terephthalic acid and isophthalic acid (JP-B-57-24407, 60-25046), terephthalic acid with phenylhydroquinone Method for copolymerizing t-butyl hydroquinone (US Pat. No. 4,238,600
No.), a method of copolymerizing terephthalic acid with a nucleus-substituted phenylhydroquinone and hydroquinone (US Pat. No. 4,15
No. 3,779) has been proposed.
一方、ヒドロキシ安息香酸、ジヒドロキシベンゼン、
シクロヘキサンジカルボン酸からなるポリエステルにつ
いては特公昭59-31592号公報で知られているが、ジヒド
ロキシベンゼンとしてｔ−ブチルハイドロキノンを使用
することは明細書中にも全く記載されていない。On the other hand, hydroxybenzoic acid, dihydroxybenzene,
A polyester comprising cyclohexanedicarboxylic acid is known from Japanese Patent Publication No. 59-31592, but the use of t-butylhydroquinone as dihydroxybenzene is not described in the specification at all.
〈発明が解決しようとする問題点〉 しかるにこれらの方法で得られる芳香族ポリエステル
は多くのものが融点が400℃以下と比較的低い反面、そ
の紡出糸の弾性率はいまだに不十分であつたり、耐熱性
が不十分であつたり、流動性が不良であつたりしてより
一層の高弾性率化と高耐熱性化が望まれている。<Problems to be solved by the invention> However, although many of the aromatic polyesters obtained by these methods have relatively low melting points of 400 ° C or lower, the elastic modulus of the spun yarn is still insufficient. However, due to insufficient heat resistance or poor fluidity, further higher elastic modulus and higher heat resistance are desired.
そこで本発明者らは、耐熱性および流動性の優れた溶
融成形可能な芳香族ポリエステルの取得を目的として鋭
意検討した結果、ｐ−ヒドロキシ安息香酸、ｔ−ブチル
ハイドロキノン、テレフタル酸からなる芳香族ポリエス
テルのｔ−ブチルハイドロキノン及び／またはテレフタ
ル酸の一部をハイドロキノンなどの芳香族ヒドロキシ化
合物、イソフタル酸などの芳香族ジカルボン酸で置換す
ることにより、上記目的に好ましく合致した溶融成形可
能な芳香族ポリエステルが得られることを見出し、本発
明をなすに到つた。Therefore, as a result of intensive investigations by the present inventors for the purpose of obtaining a melt-moldable aromatic polyester having excellent heat resistance and fluidity, an aromatic polyester composed of p-hydroxybenzoic acid, t-butylhydroquinone, and terephthalic acid. By substituting a part of the t-butyl hydroquinone and / or terephthalic acid with an aromatic hydroxy compound such as hydroquinone or an aromatic dicarboxylic acid such as isophthalic acid, a melt-moldable aromatic polyester preferably satisfying the above object can be obtained. They have found that they can be obtained and have completed the present invention.
〈問題点を解決するための手段〉 すなわち、本発明は下記構造単位（Ｉ）〜（Ｖ）から
なり、構造単位（Ｉ）が〔（Ｉ）＋（II）＋（III）〕
の55〜80モル％、構造単位〔（II）＋（III）〕が
〔（Ｉ）＋（II）＋（III）〕の45〜20モル％を占め、
構造単位（II）／（III）のモル比が１〜５及び（IV）
／（Ｖ）のモル比が１〜５、〔（II）＋（III）〕と
〔（IV）＋（Ｖ）〕が実質的に等モルであり、4,4′−
ジフェニルジカルボニル単位を含まない、溶融粘度が
（液晶開始温度＋60℃）、ずり速度3,000（1/秒）の条
件下で10〜15,000ポイズであることを特徴とする耐熱性
芳香族ポリエステルを提供するものである。<Means for Solving Problems> That is, the present invention comprises the following structural units (I) to (V), wherein the structural unit (I) is [(I) + (II) + (III)].
Structural unit [(II) + (III)] accounts for 45-20 mol% of [(I) + (II) + (III)],
Structural unit (II) / (III) molar ratio 1-5 and (IV)
The molar ratio of / (V) is 1 to 5, [(II) + (III)] and [(IV) + (V)] are substantially equimolar, and 4,4'-
Provided is a heat-resistant aromatic polyester which does not contain a diphenyldicarbonyl unit and has a melt viscosity of (liquid crystal starting temperature + 60 ° C) and a shear rate of 3,000 (1 / sec) of 10 to 15,000 poise. It is a thing.
Ｏ−Ｘ−Ｏ …（III） （Ｘは から選ばれた１種以上の基を示し、Ｙは から選ばれた一種以上の基を示す。但しＸが から選ばれた１種以上の基の際にはＹが である組合せを除く） 本発明の芳香族ポリエステルにおいて上記構造単位
（Ｉ）はｐ−ヒドロキシ安息香酸から生成したポリエス
テルの構造単位を、上記構造単位（II）はｔ−ブチルハ
イドロキノンから生成した構造単位を、（III）はｔ−
ブチルハイドロキノン、ハイドロキノン、4,4′−ジヒ
ドロキシジフエニルエーテル、ビスフエノールＡ、ビス
フエノールＳ、3,3′,5,5′−テトラメチル−4,4′−ジ
ヒドロキシジフエニルなどの芳香族ジヒドロキシ化合物
から生成した構造単位を、（IV）はテレフタル酸から生
成した構造単位を、（Ｖ）はイソフタル酸、テレフタル
酸、ヘキサヒドロテレフタル酸、1,2−ビス（フエノキ
シ）エタン−4,4′−ジカルボン酸、1,2−ビス（２−ク
ロルフエノキシ）エタン−4,4′−ジカルボン酸、2,6−
ジカルボキシナフタレンなどのジカルボン酸から生成し
た構造単位を示す。 O-X-O (III) (X is Represents one or more groups selected from Represents one or more groups selected from Where X is In the case of one or more groups selected from In the aromatic polyester of the present invention, the structural unit (I) is the structural unit of the polyester produced from p-hydroxybenzoic acid, and the structural unit (II) is the structural unit produced from t-butylhydroquinone. (III) is t-
Aromatic dihydroxy compounds such as butyl hydroquinone, hydroquinone, 4,4'-dihydroxydiphenyl ether, bisphenol A, bisphenol S, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl (IV) is a structural unit produced from terephthalic acid, (V) is an isophthalic acid, terephthalic acid, hexahydroterephthalic acid, 1,2-bis (phenoxy) ethane-4,4'- Dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 2,6-
A structural unit formed from a dicarboxylic acid such as dicarboxynaphthalene is shown.
上記構造単位（Ｉ）が〔（Ｉ）＋（II）＋（III）〕
の80モル％を超えるか、45モル％未満では流動性が不良
で本発明の目的を達成することが不可能であり、最も好
ましい組成は構造単位（Ｉ）が〔（Ｉ）＋（II）＋（II
I）〕の60〜75モル％である。The structural unit (I) is [(I) + (II) + (III)]
If it exceeds 80 mol% or less than 45 mol%, the fluidity is poor and the object of the present invention cannot be achieved. The most preferable composition is structural unit (I) [(I) + (II) + (II
I)] is 60 to 75 mol%.
一方、上記構造単位（II）／（III）または（IV）／
（Ｖ）のモル比が１未満または５より大きい際にはやは
り流動性が不良で耐熱性の高弾性率成形品に得ることが
不可能であり、本発明のように（II）／（III）のモル
比が１〜５及び（IV）／（Ｖ）のモル比が１〜５である
場合にのみ、本発明の目的を達成することができる。こ
のうち最も好ましい組成は（II）／（III）のモル比が
１〜４及び（IV）／（Ｖ）のモル比が１〜４である。On the other hand, the structural unit (II) / (III) or (IV) /
When the molar ratio of (V) is less than 1 or more than 5, it is impossible to obtain a heat-resistant high-elasticity molded product due to poor fluidity, and (II) / (III) as in the present invention. The object of the present invention can be achieved only when the molar ratio of) is 1 to 5 and the molar ratio of (IV) / (V) is 1 to 5. Among them, the most preferable composition is a (II) / (III) molar ratio of 1 to 4 and a (IV) / (V) molar ratio of 1 to 4.
本発明の芳香族ポリエステルは従来のポリエステルの
重縮合法に準じて製造でき、製法については特に制限が
ないが、代表的な製法としては例えば次の（１）〜
（４）法が挙げられる。The aromatic polyester of the present invention can be produced according to a conventional polyester polycondensation method, and the production method is not particularly limited, but typical production methods include, for example, the following (1) to
(4) method.
（１） ｐ−アセトキシ安息香酸、ｔ−ブチルハイドロ
キノンジアセテートなどの芳香族ジヒドロキシ化合物と
テレフタル酸などのジカルボン酸から脱酢酸重縮合反応
によつて製造する方法。(1) A method for producing an aromatic dihydroxy compound such as p-acetoxybenzoic acid or t-butylhydroquinone diacetate and a dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction.
（２） ｐ−ヒドロキシ安息香酸、ｔ−ブチルハイドロ
キノンなどの芳香族ジヒドロキシ化合物とテレフタル酸
などのジカルボン酸および無水酢酸とから脱酢酸重縮合
反応によつて製造する方法。(2) A method of producing from an aromatic dihydroxy compound such as p-hydroxybenzoic acid or t-butylhydroquinone, a dicarboxylic acid such as terephthalic acid, and acetic anhydride by a deacetic acid polycondensation reaction.
（３） ｐ−ヒドロキシ安息香酸のフエニルエステルお
よびｔ−ブチルハイドロキノンなどの芳香族ジヒドロキ
シ化合物とテレフタル酸などのジカルボン酸のジフエニ
ルエステルから脱フエノール重縮合により製造する方
法。(3) A method for producing from a phenyl ester of p-hydroxybenzoic acid and an aromatic dihydroxy compound such as t-butylhydroquinone and a diphenyl ester of a dicarboxylic acid such as terephthalic acid by dephenol polycondensation.
（４） ｐ−ヒドロキシ安息香酸およびテレフタル酸な
どのジカルボン酸に所望量のジフエニルカーボネートを
反応させてそれぞれジフエニルエステルとした後、ｔ−
ブチルハイドロキノンなどの芳香族ジヒドロキシ化合物
を加え脱フエノール重縮合反応により製造する方法。(4) After dicarboxylic acid such as p-hydroxybenzoic acid and terephthalic acid is reacted with a desired amount of diphenyl carbonate to form each diphenyl ester, t-
A method for producing by a dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as butyl hydroquinone.
重縮合反応に使用する触媒としては酢酸第１錫、テト
ラブチルチタネート、酢酸鉛、三酸化アンチモン、マグ
ネシウム、酢酸ナトリウム、酢酸カリウムおよびリン酸
三ナトリウムなどの金属化合物が代表的であり、とりわ
け脱フエノール重縮合の際に有効である。Typical catalysts used in the polycondensation reaction are metal compounds such as stannous acetate, tetrabutyl titanate, lead acetate, antimony trioxide, magnesium, sodium acetate, potassium acetate and trisodium phosphate. Effective during polycondensation.
また、本発明の芳香族ポリエステルの溶融粘度は10〜
15,000ポイズが好ましく、特に20〜5,000ポイズがより
好ましい。The melt viscosity of the aromatic polyester of the present invention is 10 to
15,000 poise is preferable, and 20 to 5,000 poise is particularly preferable.
なお、この溶融粘度は（液晶開始温度＋60℃）でずり
速度3,000（1/秒）の条件下で高化式フローテスターに
よつて測定した値である。なお、液晶開始温度とは、偏
光顕微鏡下でずり応力を加えて乳白色を発する温度を示
す。The melt viscosity is a value measured by a Koka type flow tester under the condition of (liquid crystal starting temperature + 60 ° C) and shear rate of 3,000 (1 / sec). The liquid crystal onset temperature is the temperature at which shear stress is applied under a polarizing microscope to give a milky white color.
なお本発明の芳香族ポリエステルを重縮合する際には
上記（Ｉ）〜（Ｖ）を構成する成分以外に4,4′−ジヒ
ドロキシビフエニル、レゾルシン、クロルハイドロキノ
ン、メチルハイドロキノン、フエニルハイドロキノン、
2,6−ジヒドロキシナフタレン、2,7−ジヒドロキシナフ
タレンなどの芳香族ジヒドロキシ化合物、3,3′−ジフ
エニルジカルボン酸、3,4′−ジフエニルジカルボン
酸、2,2′−ジフエニルジカルボン酸などの芳香族ジカ
ルボン酸、ｍ−ヒドロキシ安息香酸、2,6−ヒドロキシ
ナフトエ酸などの芳香族ヒドロキシカルボン酸およびｐ
−アミノフエノール、ｐ−アミノ安息香酸などを本発明
の目的を損なわない程度の少割合の範囲でさらに共重合
せしめることができる。When polycondensing the aromatic polyester of the present invention, 4,4'-dihydroxybiphenyl, resorcin, chlorohydroquinone, methylhydroquinone, phenylhydroquinone, other than the components constituting the above (I) to (V),
Aromatic dihydroxy compounds such as 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, 3,3'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid Aromatic dicarboxylic acids, m-hydroxybenzoic acid, 2,6-hydroxynaphthoic acid and other aromatic hydroxycarboxylic acids and p
-Aminophenol, p-aminobenzoic acid and the like can be further copolymerized in a small proportion so long as the object of the present invention is not impaired.
かくしてなる本発明の芳香族ポリエステルは融点が40
0℃以下と低く、押出成形、射出成形、圧縮成形、ブロ
ー成形などの通常の溶融成形に供することができ、繊
維、フイルム、三次元成形品、容器、ホースなどに加工
することが可能である。The aromatic polyester thus obtained has a melting point of 40.
As low as 0 ° C or less, it can be used for ordinary melt molding such as extrusion molding, injection molding, compression molding, blow molding, and can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc. .
なお、成形時には本発明の芳香族ポリエステルに対
し、ガラス繊維、炭素繊維、アスベストなどの強化剤、
充填剤、核剤、顔料、酸化防止剤、安定剤、可塑剤、滑
剤、離型剤および難燃剤などの添加剤や他の熱可塑性樹
脂を添加して、成形品に所望の特性を付与することがで
きる。In addition, at the time of molding, the aromatic polyester of the present invention, glass fiber, carbon fiber, reinforcing agents such as asbestos,
Add additives such as fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents and flame retardants, and other thermoplastic resins to give desired properties to molded articles. be able to.
なお、このようにして得られた成形品は、熱処理によ
つて強度を増加させることができ、弾性率をも多くの場
合増加させることができる。The molded product thus obtained can have its strength increased by heat treatment, and its elastic modulus can also be increased in many cases.
この熱処理は、成形品を不活性雰囲気（例えば窒素、
アルゴン、ヘリウムまたは水蒸気）中または酸素含有雰
囲気（例えば空気）中でポリマの融点以下の温度で熱処
理することによつて行うことができる。この熱処理は緊
張下であつてもなくてもよく数分〜数日の間で行うこと
ができる。This heat treatment causes the molded article to be placed in an inert atmosphere (eg, nitrogen,
It can be carried out by heat treatment in argon, helium or water vapor) or in an oxygen-containing atmosphere (eg air) at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension and can be carried out for a few minutes to a few days.
本発明の新規な芳香族ポリエステルから得られる成形
品は、その平行な分子配列に起因して良好な光学異方性
を有し、耐熱性および機械的性質が極めて優れている。The molded product obtained from the novel aromatic polyester of the present invention has good optical anisotropy due to its parallel molecular arrangement, and has extremely excellent heat resistance and mechanical properties.
〈実施例〉 以下に実施例により本発明をさらに説明する。<Examples> The present invention will be further described below with reference to Examples.
実施例１ 重合用試験管にｐ−アセトキシ安息香酸24.1部（1.34
×10-1モル）、ｔ−ブチルハイドロキノンジアセテート
16.5部（0.66×10-1モル）、テレフタル酸7.3部（0.44
×10-1モル）、イソフタル酸3.65部（0.22×10-1モル）
を仕込み、次の条件で脱酢酸重合を行つた。Example 1 24.1 parts (1.34) of p-acetoxybenzoic acid was added to a polymerization test tube.
× 10 -1 mol), t-butyl hydroquinone diacetate
16.5 parts (0.66 × 10 -1 mol), terephthalic acid 7.3 parts (0.44
X 10 -1 mol), isophthalic acid 3.65 parts (0.22 x 10 -1 mol)
Was charged, and deacetic acid polymerization was carried out under the following conditions.
まず窒素ガス雰囲気下に250〜360℃で３時間反応させ
た後360℃で2.0mmHgに減圧し、更に0.6時間加熱し、重
縮合を完結させたところほぼ理論量の酢酸が留出し茶色
のポリマが得られた。First, after reacting in a nitrogen gas atmosphere at 250 to 360 ° C. for 3 hours, the pressure was reduced to 2.0 mmHg at 360 ° C. and further heated for 0.6 hours to complete the polycondensation. was gotten.
このポリマの理論構造式は次のとおりであり、そのポ
リエステルの元素分析結果は第１表のとおり理論値とよ
い一致を示した。The theoretical structural formula of this polymer is as follows, and the elemental analysis results of the polyester showed good agreement with the theoretical values as shown in Table 1.
1/m/n/o＝67/33/22/11 また、このポリエステルを偏光顕微鏡の試料台にのせ
シエアーをかけて光学異方性の確認を行つたところ、27
0℃以上で良好な光学異方性を示した。 1 / m / n / o = 67/33/22/11 In addition, when this polyester was placed on the sample stage of a polarizing microscope and the air anisotropy was applied to confirm it,
Good optical anisotropy was exhibited at 0 ° C or higher.
また、示差走査熱量計（パーキンエルマーII型）で熱
特性を測定したところガラス転移温度166℃であり良好
な耐熱性を有していることがわかつた。Further, the thermal characteristics were measured with a differential scanning calorimeter (Perkin Elmer II type), and it was found that the glass transition temperature was 166 ° C and that the glass had good heat resistance.
このポリエステルを高化式フローテスターに供し紡糸
温度330℃、口金孔径0.3mmφで紡糸を行い、17m/分で巻
き取り0.07mmφの紡出糸を得た。この紡出糸を東洋ボー
ルドウイン（株）社製レオバイブロンDDV-II-EAを用い
て周波数110Hz、昇温速度２℃／分、チヤツク間距離40m
mで弾性率を測定したところ30℃で57GPaであった。This polyester was applied to a Koka type flow tester and spun at a spinning temperature of 330 ° C. with a spinneret hole diameter of 0.3 mmφ and wound at 17 m / min to obtain a spun yarn of 0.07 mmφ. This spun yarn was manufactured using Toyo Baldwin Co., Ltd.'s Leovibron DDV-II-EA at a frequency of 110 Hz, a heating rate of 2 ° C./min, and a check distance of 40 m.
When the elastic modulus was measured at m, it was 57 GPa at 30 ° C.
なお、このポリマの溶融粘度は330℃、ずり速度3000
（1/秒）で900ポイズであつた。The melt viscosity of this polymer is 330 ° C and the shear rate is 3000.
(1 / sec) was 900 poise.
実施例２ 実施例１のイソフタル酸の代りにトランスシクロヘキ
サンジカルボン酸3.7部（0.22×10-1モル）を使用する
以外は全部同一仕込みで次の条件下で脱酢酸重合を行つ
た。Example 2 Deacetic acid polymerization was carried out under the following conditions except that 3.7 parts (0.22 × 10 -1 mol) of transcyclohexanedicarboxylic acid was used instead of isophthalic acid in Example 1.
まず窒素ガス雰囲気に250〜330℃で3.5時間反応させ
た後1.0mmHgに減圧し、330〜340℃で更に1.0時間加熱
し、重縮合を完結させたところほぼ理論量の酢酸が留出
し茶色のポリマが得られた。First, after reacting in a nitrogen gas atmosphere at 250 to 330 ° C for 3.5 hours, the pressure was reduced to 1.0 mmHg and further heated at 330 to 340 ° C for 1.0 hour to complete polycondensation. A polymer was obtained.
このポリマの理論構造式は次のとおりでありそのポリ
エステルの元素分析は第２表のとおり理論値とよい一致
を示した。The theoretical structural formula of this polymer is as follows, and the elemental analysis of the polyester showed good agreement with the theoretical values as shown in Table 2.
1/m/n/o＝67/33/22/11 また、このポリエステルを偏光顕微鏡の試料台にのせ
シエアーをかけて光学異方性の確認を行つたところ、25
0℃以上で良好な光学異方性を示した。 1 / m / n / o = 67/33/22/11 In addition, when this polyester was placed on the sample stage of a polarizing microscope and the air anisotropy was applied to confirm it,
Good optical anisotropy was exhibited at 0 ° C or higher.
また、示差走査熱量計（パーキンエルマーII型）で熱
特性を測定したところ、ガラス転移温度157℃であり良
好な耐熱性を有していることがわかつた。Further, the thermal characteristics were measured with a differential scanning calorimeter (Perkin Elmer II type), and it was found that the glass transition temperature was 157 ° C. and that the glass had good heat resistance.
このポリエステルを高化式フローテスターに供し紡糸
温度330℃、口金孔径0.3mmφで紡糸を行い49m/分で巻き
取り0.06mmφの紡出糸を得た。この紡出糸を東洋ボール
ドウイン（株）社製レオバイブロンDDV-II-EAを用いて
実施例１と同様に弾性率を測定したところ30℃で55GPa
であった。また動点損失のピーク温度は157℃と良好な
耐熱性を有していた。This polyester was applied to a Koka type flow tester and spun at a spinning temperature of 330 ° C. and a spinneret hole diameter of 0.3 mmφ, and wound at 49 m / min to obtain a spun yarn of 0.06 mmφ. The elastic modulus of this spun yarn was measured in the same manner as in Example 1 using Rheovibron DDV-II-EA manufactured by Toyo Baldwin Co., Ltd., and the elastic modulus was 55 GPa at 30 ° C.
Met. In addition, the peak temperature of the moving point loss was 157 ° C, indicating good heat resistance.
このポリマの溶融粘度は310℃、ずり速度3000（1/
秒）で970ポイズであつた。This polymer has a melt viscosity of 310 ° C and a shear rate of 3000 (1 /
970 poise in seconds).
実施例３〜14 ｐ−アセトキシ安息香酸（Ｉ）、ｔ−ブチルハイドロ
キノンジアセテート（II）、ハイドロキノンジアセテー
ト（III）、4,4′−ジアセトキシジフエニルエーテル
（IV）、ビスフエノールＡジアセテート（Ｖ）、ビスフ
エノールＳジアセテート（VI）、3,3′,5,5′−テトラ
メチル−4,4′−ジヒドロキシビフエニル（VII）、テレ
フタル酸（VIII）、イソフタル酸（IX）、1,4−トラン
スシクロヘキサンジカルボン酸（Ｘ）、1,2−ビス（フ
エノキシ）エタン−4,4′−ジカルボン酸（XI）、1,2−
ビス（２−クロルフエノキシ）エタン−4,4′−ジカル
ボン酸（XII）、2,6−ナフタレンジカルボン酸（XIII）
からなる原料を（II）〜（VII）成分と（VIII）〜（XII
I）の成分のモル数を同一にして重合用試験管に仕込み
実施例１、２と同様の条件で重縮合反応を行い液晶開始
温度および溶融粘度を測定した。Examples 3 to 14 p-acetoxybenzoic acid (I), t-butyl hydroquinone diacetate (II), hydroquinone diacetate (III), 4,4'-diacetoxy diphenyl ether (IV), bisphenol A diacetate. (V), bisphenol S diacetate (VI), 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl (VII), terephthalic acid (VIII), isophthalic acid (IX), 1,4-transcyclohexanedicarboxylic acid (X), 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid (XI), 1,2-
Bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid (XII), 2,6-naphthalenedicarboxylic acid (XIII)
(II) to (VII) components and (VIII) to (XII
The same number of moles of the component (I) was used, the mixture was charged into a polymerization test tube, and a polycondensation reaction was performed under the same conditions as in Examples 1 and 2 to measure the liquid crystal starting temperature and the melt viscosity.
第３表から本発明のポリエステル（実施例３〜14）は
剛直構造にもかかわらず液晶開始温度、溶融粘度が低
く、ガラス転移温度の高いことがわかる。It can be seen from Table 3 that the polyesters of the present invention (Examples 3 to 14) have a low liquid crystal initiation temperature, a low melt viscosity, and a high glass transition temperature despite the rigid structure.
比較実施例 ｐ−アセトキシ安息香酸24.1部（1.34×10-1モル）と
ｔ−ブチルハイドロキノンジアセテート16.5部（0.66×
10-1モル）およびテレフタル酸11.0部（0.66×10-1モ
ル）を重合用試験管に仕込み、窒素ガス雰囲気下に250
〜360℃で３時間反応させたところ流動性が不良で固化
して靱性のあるポリマが得られなかつた。 Comparative Example p-acetoxybenzoic acid 24.1 parts (1.34 x 10 -1 mol) and t-butyl hydroquinone diacetate 16.5 parts (0.66 x
10 -1 mol) and 11.0 parts of terephthalic acid (0.66 x 10 -1 mol) were charged into a polymerization test tube and placed under a nitrogen gas atmosphere at 250
When the reaction was carried out at ˜360 ° C. for 3 hours, the fluidity was poor and the polymer solidified and no tough polymer was obtained.
比較実施例２ ｐ−アセトキシ安息香酸24.1部（1.34×10-1モル）と
クロルハイドロキノンジアセテート10.1部（0.44×10-1
モル）、4,4′−ジアセトキシジフエニルエーテル6.3部
（0.22×10-1モル）およびテレフタル酸11.0部（0.66×
10-1モル）を重合用試験管に仕込み実施例１と同じよう
に重合した。Comparative Example 2 p-acetoxybenzoic acid 24.1 parts (1.34 × 10 -1 mol) and chlorohydroquinone diacetate 10.1 parts (0.44 × 10 -1)
Mol), 4,4′-diacetoxydiphenyl ether 6.3 parts (0.22 × 10 −1 mol) and terephthalic acid 11.0 parts (0.66 ×
10 -1 mol) was charged into a polymerization test tube and polymerized in the same manner as in Example 1.
得られたポリマの液晶開始温度は310℃であり実施例
１と同じように360℃で紡糸を行い、得られた紡出糸
（繊維径0.16mm）のレオバイブロンで動的損失のピーク
温度を測定したところ110℃と低い値であつた。The liquid crystal starting temperature of the obtained polymer was 310 ° C., spinning was carried out at 360 ° C. as in Example 1, and the peak temperature of the dynamic loss was measured with Rheovibron of the obtained spun yarn (fiber diameter 0.16 mm). As a result, it was a low value of 110 ° C.
〈本発明の効果〉 本発明の耐熱性芳香族ポリエステルは、溶融成形可能
であり、耐熱性が良好な成形品を得ることができるので
エンジニヤリングプラスチックなど種々の用途に使用す
ることができる。<Effects of the Present Invention> The heat-resistant aromatic polyester of the present invention can be melt-molded and a molded product having good heat resistance can be obtained, and thus can be used for various applications such as engineering plastics.
Claims (1)
造単位（Ｉ）が〔（Ｉ）＋（II）＋（III）〕の55〜80
モル％、構造単位〔（II）＋（III）〕が〔（Ｉ）＋（I
I）＋（III）〕の45〜20モル％を占め、構造単位（II）
／（III）のモル比が１〜５及び（IV）／（Ｖ）のモル
比が１〜５、〔（II）＋（III）〕と〔（IV）＋
（Ｖ）〕が実質的に等モルであり、4,4′−ジフェニル
ジカルボニル単位を含まない、溶融粘度が（液晶開始温
度＋60℃）、ずり速度3,000（1/秒）の条件下で10〜15,
000ポイズであることを特徴とする耐熱性芳香族ポリエ
ステル。 Ｏ−Ｘ−Ｏ …（III） （但し（III）式中Ｘは から選ばれた１種以上の基を、Ｙは から選ばれた１種以上の基を示す。但しＸが から選ばれた１種以上の基の際にはＹが である組合せを除く）1. The following structural units (I) to (V), wherein the structural unit (I) is [(I) + (II) + (III)] 55-80.
Mol%, structural unit [(II) + (III)] is [(I) + (I
I) + (III)] in the structural unit (II)
The molar ratio of / (III) is 1 to 5 and the molar ratio of (IV) / (V) is 1 to 5, [(II) + (III)] and [(IV) +
(V)] is substantially equimolar, does not contain 4,4′-diphenyldicarbonyl units, has a melt viscosity (liquid crystal starting temperature + 60 ° C.) and a shear rate of 3,000 (1 / sec). ~ 15,
A heat-resistant aromatic polyester characterized by being 000 poise. O-X-O (III) (However, in the formula (III), X is Y is one or more groups selected from And one or more groups selected from Where X is In the case of one or more groups selected from (Excluding combinations that are
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61136127A JP2515744B2 (en) | 1986-06-13 | 1986-06-13 | Heat resistant aromatic polyester |
| DE19873736606 DE3736606A1 (en) | 1986-06-13 | 1987-10-29 | ARRANGEMENT FOR ATTACHING ONE END OF A THIN-WALLED TUBE TO A FLANGE COUPLING |
| GB8725337A GB2211573B (en) | 1986-06-13 | 1987-10-29 | A pipe to flange coupling arrangement |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61136127A JP2515744B2 (en) | 1986-06-13 | 1986-06-13 | Heat resistant aromatic polyester |
| DE19873736606 DE3736606A1 (en) | 1986-06-13 | 1987-10-29 | ARRANGEMENT FOR ATTACHING ONE END OF A THIN-WALLED TUBE TO A FLANGE COUPLING |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62292832A JPS62292832A (en) | 1987-12-19 |
| JP2515744B2 true JP2515744B2 (en) | 1996-07-10 |
Family
ID=39529641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61136127A Expired - Lifetime JP2515744B2 (en) | 1986-06-13 | 1986-06-13 | Heat resistant aromatic polyester |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2515744B2 (en) |
| DE (1) | DE3736606A1 (en) |
| GB (1) | GB2211573B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6712154B2 (en) | 1998-11-16 | 2004-03-30 | Enventure Global Technology | Isolation of subterranean zones |
| US7357188B1 (en) | 1998-12-07 | 2008-04-15 | Shell Oil Company | Mono-diameter wellbore casing |
| US6823937B1 (en) | 1998-12-07 | 2004-11-30 | Shell Oil Company | Wellhead |
| US6745845B2 (en) | 1998-11-16 | 2004-06-08 | Shell Oil Company | Isolation of subterranean zones |
| US6634431B2 (en) | 1998-11-16 | 2003-10-21 | Robert Lance Cook | Isolation of subterranean zones |
| US6739392B2 (en) | 1998-12-07 | 2004-05-25 | Shell Oil Company | Forming a wellbore casing while simultaneously drilling a wellbore |
| AU770359B2 (en) * | 1999-02-26 | 2004-02-19 | Shell Internationale Research Maatschappij B.V. | Liner hanger |
| US6409175B1 (en) * | 1999-07-13 | 2002-06-25 | Grant Prideco, Inc. | Expandable joint connector |
| US6623048B2 (en) * | 2001-05-17 | 2003-09-23 | Delphi Technologies, Inc. | Apparatus and method of attaching a tube member to a housing of a vacuum brake booster |
| US7793721B2 (en) | 2003-03-11 | 2010-09-14 | Eventure Global Technology, Llc | Apparatus for radially expanding and plastically deforming a tubular member |
| AU2003230589A1 (en) | 2002-04-12 | 2003-10-27 | Enventure Global Technology | Protective sleeve for threaded connections for expandable liner hanger |
| EP1501645A4 (en) | 2002-04-15 | 2006-04-26 | Enventure Global Technology | Protective sleeve for threaded connections for expandable liner hanger |
| EP1552271A1 (en) | 2002-09-20 | 2005-07-13 | Enventure Global Technology | Pipe formability evaluation for expandable tubulars |
| US7886831B2 (en) | 2003-01-22 | 2011-02-15 | Enventure Global Technology, L.L.C. | Apparatus for radially expanding and plastically deforming a tubular member |
| CA2523862C (en) | 2003-04-17 | 2009-06-23 | Enventure Global Technology | Apparatus for radially expanding and plastically deforming a tubular member |
| US7712522B2 (en) | 2003-09-05 | 2010-05-11 | Enventure Global Technology, Llc | Expansion cone and system |
| CA2577083A1 (en) | 2004-08-13 | 2006-02-23 | Mark Shuster | Tubular member expansion apparatus |
| KR101654238B1 (en) * | 2015-11-23 | 2016-09-06 | 정우금속공업 주식회사 | Pipe Connecting Apparatus and Its Manufacturing Method |
| CN114479377B (en) * | 2022-02-11 | 2023-10-31 | 广东优巨先进新材料股份有限公司 | Polyester alloy material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US689455A (en) * | 1901-01-28 | 1901-12-24 | John H Bickford | Pipe-coupling. |
| GB759718A (en) * | 1954-09-20 | 1956-10-24 | Cecil Churchill Mackenzie Clou | Improvements in flanges for tubes |
| JPS6248722A (en) * | 1985-08-28 | 1987-03-03 | Agency Of Ind Science & Technol | Optically anisotropic polyester |
| JPH07696B2 (en) * | 1986-04-30 | 1995-01-11 | 三井石油化学工業株式会社 | Aromatic polyester |
-
1986
- 1986-06-13 JP JP61136127A patent/JP2515744B2/en not_active Expired - Lifetime
-
1987
- 1987-10-29 GB GB8725337A patent/GB2211573B/en not_active Expired - Lifetime
- 1987-10-29 DE DE19873736606 patent/DE3736606A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62292832A (en) | 1987-12-19 |
| GB8725337D0 (en) | 1987-12-02 |
| GB2211573A (en) | 1989-07-05 |
| DE3736606C2 (en) | 1992-02-20 |
| DE3736606A1 (en) | 1989-05-18 |
| GB2211573B (en) | 1991-08-28 |
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