JPS58118822A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPS58118822A JPS58118822A JP89282A JP89282A JPS58118822A JP S58118822 A JPS58118822 A JP S58118822A JP 89282 A JP89282 A JP 89282A JP 89282 A JP89282 A JP 89282A JP S58118822 A JPS58118822 A JP S58118822A
- Authority
- JP
- Japan
- Prior art keywords
- tank
- reaction
- compound
- esterification
- particles
- 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
Landscapes
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、テレフタル酸とエチレングリコールとを主な
出発原料とし、良好な光輝性、透明性を有し、且つ繊維
、フィルム等の成型体を得る際の工程通過性の良好なポ
リエチレンテレフタレートの製造方法１こ関するもので
ある。Detailed Description of the Invention The present invention uses terephthalic acid and ethylene glycol as main starting materials, and has good brightness and transparency, and process passability when obtaining molded products such as fibers and films. The present invention relates to a method for producing polyethylene terephthalate with good quality.
ポリエチレンテレフタレートは、その優れた物理特性に
基づき、Ｍ維、フィルム等広い用途に供されている。従
来、繊維及びフィルム等の成型加工時の工程通過性を高
めるため、ポリマ中に微細な粒子を含有させ、成型体と
金属及び／又は成型体同志の摩擦係数を低下せしめ、易
滑性を付与する試みが行なわれている。Polyethylene terephthalate is used in a wide range of applications such as M fibers and films based on its excellent physical properties. Conventionally, in order to improve process passability during the molding process of fibers, films, etc., fine particles were included in the polymer to lower the coefficient of friction between the molded object and the metal and/or between the molded objects, thereby imparting slipperiness. Attempts are being made to do so.
ポリマに易滑性を付与せしめる粒子としては。As particles that impart slipperiness to polymers.
従来、二酸化チタン、アルミナ等が使用されている。し
かしながら、成型体に光輝性、透明性が好まれる用途に
は、前記艶消し作用のある粒子は適当ではない。Conventionally, titanium dioxide, alumina, etc. have been used. However, the particles having a matting effect are not suitable for applications where glitter and transparency are preferred in the molded product.
この欠点を改良するため、艶消し作用が少なく、易滑性
を付与する粒子、例えばシリカ、タルク、酸化亜鉛等を
ポリエステルの製造工程で添加する方法が提案されてい
る。しかしながらこれらの粒子は、ポリエステルに対す
る分散性が悪く、ポリマ品質を低下せしめ、成型加工時
の工程通過性を損う欠点がある。In order to improve this drawback, a method has been proposed in which particles that have less matting effect and provide slipperiness, such as silica, talc, zinc oxide, etc., are added during the polyester manufacturing process. However, these particles have the drawback of poor dispersibility in polyester, lowering the quality of the polymer, and impairing process passability during molding.
一万、ポリエステルｅこ可溶な化合物を、ポリマ製造過
程で不溶性化合物ｔこ変化させ微細な粒子を形成させる
方法、いわゆる内部粒子を含有するポリマの製造方法が
提案されている。（例えば特公昭４７−１９８６６号公
報、同４９−１３２３４号公報など。）しかしながら、
この方法は、ポリマ中に形成させる粒子が粗大化したり
、またポリマ中の粒子の量を一定範囲内？こ再現性良く
コントロールすることが難しい等の欠点がある。A method has been proposed in which a soluble compound in polyester is converted into an insoluble compound during the polymer production process to form fine particles, a method for producing a polymer containing so-called internal particles. (For example, Japanese Patent Publication No. 47-19866, Japanese Patent Publication No. 49-13234, etc.) However,
This method does not cause the particles formed in the polymer to become coarse, or does it limit the amount of particles in the polymer to within a certain range? This method has drawbacks such as difficulty in controlling it with good reproducibility.
前記内部粒子は、主としてアルカリ金属化合物又はアル
カリ土類化合物とカルボキシル基との反応において形成
されるため１％にテレフタル酸を出発原料とする直接重
合法によるポリエチレンテレフタレートの製造方法ｔこ
おいては。Since the internal particles are mainly formed by the reaction of an alkali metal compound or an alkaline earth compound with a carboxyl group, the method for producing polyethylene terephthalate by a direct polymerization method using 1% terephthalic acid as a starting material.
テレフタル酸ジメチルを出発原料とする方法ｔこ比べ、
内部粒子の形成を適切にコントロールすることが困難で
あり、そのため内部粒子の凝集、粗大化のない高品位の
ポリマを再現性良く得ることができない。Comparing methods using dimethyl terephthalate as a starting material,
It is difficult to appropriately control the formation of internal particles, and therefore it is not possible to obtain high-quality polymers with good reproducibility without agglomeration or coarsening of internal particles.
すなわち１本発明はテレフタル酸とエチレングリコール
とを主な出発原料としてポリエステルを連続的ｔこ製造
するに際し、エステル化反応生成物にリン化合物を添加
した後、引き続きエステル化及び重縮合反応を行う任意
の段階で滞留時間が１．５時間以内の槽にＣａ及び／又
はＬｉ化合物を添加することを特徴とするポリエステル
の製造法である。In other words, the present invention provides an optional method for continuously producing polyester using terephthalic acid and ethylene glycol as the main starting materials, after adding a phosphorus compound to the esterification reaction product, followed by esterification and polycondensation reactions. This method for producing polyester is characterized in that Ca and/or Li compounds are added to a tank in which the residence time is within 1.5 hours at the step of step (1).
本発明の目的とするところは、繊維及びフィルム等の成
型加工時の工程通過性がＴｌＯ２含有ポリエステルと遜
色ないレベルであり、しかも良好な光輝性、透明性を有
する成型体を与えるポリエステルを製造する方法を提供
することにある。更？こ本発明の他の目的は、前記成型
特性に優れ、良好な光輝性、透明性を有する成型体を与
えるポリエステルを再現性良＜、シかも工業的に有利に
製造する方法を提供することにある。The purpose of the present invention is to produce a polyester that has process passability during molding of fibers, films, etc., at a level comparable to that of TlO2-containing polyester, and that provides molded products with good glitter and transparency. The purpose is to provide a method. Further? Another object of the present invention is to provide an industrially advantageous method for producing polyester with good reproducibility and which provides a molded article having excellent molding properties, good glitter and transparency. be.
本発明ｔこおけるポリエステルとはへテレフタル酸とエ
チレングリコールとを主たる構成成分とするが、その１
部を任意の共重合性第５成分１こ置き換えても良い。共
重合性第３成分の具体例としては、イソフタル酸、セパ
シン酸、アジピン酸、５−ナトリウムスルホイソフタル
酸。The main constituents of the polyester used in the present invention are heterephthalic acid and ethylene glycol.
One part of the fifth copolymerizable component may be replaced with one part of the optional fifth copolymerizable component. Specific examples of the copolymerizable third component include isophthalic acid, sepacic acid, adipic acid, and 5-sodium sulfoisophthalic acid.
２．６−ナフタリンジカルボン酸等のジカルボンヤ、ト
リメリット酸、トリメシン酸等の多価カルボン酸、プロ
ピレングリコール、１．４−ブタンジオール。１．４−
シクロヘキサンジメタツール、ネオペンチルグリコール
、ペンタエリスリトール等の多価アルコール及びこれら
の誘導体等がある。Dicarboxylic acids such as 2.6-naphthalene dicarboxylic acid, polyhydric carboxylic acids such as trimellitic acid and trimesic acid, propylene glycol, and 1,4-butanediol. 1.4-
Examples include polyhydric alcohols such as cyclohexane dimetatool, neopentyl glycol, and pentaerythritol, and derivatives thereof.
本発明で使用するリン化合物はリン酸、亜リン酸及びこ
れらのエステルである。リン酸、亜リン酸のエステルと
しては、モノエステル、ジエステル、トリエステルのい
ずれでも良く、エステル基としてはメチル、エチル、プ
ロピル。The phosphorus compounds used in the present invention are phosphoric acid, phosphorous acid, and esters thereof. The esters of phosphoric acid and phosphorous acid may be monoesters, diesters, or triesters, and the ester groups are methyl, ethyl, and propyl.
ブチルフェニル等である。本発明の実施に際しては、上
記リン化合物の１種又は２種以上の組み合わせを用いる
。butylphenyl, etc. In carrying out the present invention, one type or a combination of two or more of the above phosphorus compounds is used.
また本発明において使用するＣａ、Ｌｉのグリコール町
溶性塩とはアルキレングリコールの沸点における溶解度
が０．５重量％以上のもので１例えば有機カルボン酸塩
であり、更Ｐこ具体的には。Further, the glycol-soluble salts of Ca and Li used in the present invention are those having a solubility at the boiling point of alkylene glycol of 0.5% by weight or more, such as organic carboxylic acid salts.
酢酸カルシウム、プロピオン酸カルシウム、アジピン酸
カルシウム、酢酸リチウム、プロピオン酸リチウム、ア
ジピン酸リチウム等である。These include calcium acetate, calcium propionate, calcium adipate, lithium acetate, lithium propionate, lithium adipate, and the like.
特に好ましくは酢酸カルシウム、酢酸リチウムである。Particularly preferred are calcium acetate and lithium acetate.
ポリエステルの製造工程で（ａ及び／又はＬｌのダリコ
ール性可溶塩を添加せしめてＯａ及び／又はＬｌに由来
する内部粒子を生成せしめる際、その内部粒子のポリマ
中での分散状態に対して。In the polyester manufacturing process (when adding a dalichol soluble salt of a and/or Ll to generate internal particles derived from Oa and/or Ll, the state of dispersion of the internal particles in the polymer).
Ｏａ、Ｌｉ化合物の添加時の反応系の組成、添加する槽
の滞留時間、他の添加剤との添加タイミングが重要であ
ることを見い出した。すなわち。It has been found that the composition of the reaction system when adding Oa and Li compounds, the residence time in the tank where they are added, and the timing of addition with other additives are important. Namely.
本発明はエステル化反応生成物にリン化合物を添加せし
めた後、引き続きエステル化及び重縮合反応を行なう段
階でＣａ及び／又はＬｉ化合物を添加するものである。In the present invention, after a phosphorus compound is added to an esterification reaction product, Ca and/or Li compounds are added at a stage where esterification and polycondensation reactions are subsequently performed.
リン化合物の添加量は０、００５〜０．０５重量係の範
囲とすべきである。リン化合物の添加量が０．０ （：
Ｊ ３重量％以上の場合。The amount of phosphorus compound added should be in the range of 0.005 to 0.05 parts by weight. The amount of phosphorus compound added is 0.0 (:
J When it is 3% by weight or more.
得られるポリエステルの溶融時針熱性が悪化し、成型加
工時、悪影響がある。When the resulting polyester is melted, the heat resistance of the needle deteriorates, which has an adverse effect during molding.
一方、リン化合物が前記範囲より多くなると。On the other hand, if the amount of phosphorus compounds exceeds the above range.
重縮合反応性が低下すると同時に粗大なリン酸金属塩が
多量に生成し好ましくない。リン化合物の添加は、エス
テル反応の任意の段階で良いが、エステル化の初期に添
加するとジエチレングリコールの生成が促進され好まし
くない＠好ましいリン化合物の添加時期はエステル化反
応率が９０係以上の段階である。Ｃａ及び／又はＬｌ化
食物の添加は、滞留時間が１．５時間以内の槽とすべき
である。添加槽のエステル化反応生成物は、エステル化
反応率が９４係以上であることが特に好ましい。エステ
ル化反応率が９４係未満の場合、生成する内部粒子が充
分に微細化されず、しかも粗粒も多数存在するため、得
られたポリマの成型加工時の工程通過性が不良となる。Polycondensation reactivity decreases and at the same time a large amount of coarse metal phosphate is produced, which is undesirable. The phosphorus compound may be added at any stage of the ester reaction, but adding it early in the esterification will promote the formation of diethylene glycol, which is undesirable. The preferred time to add the phosphorus compound is when the esterification reaction rate is 90% or higher. be. Addition of Ca and/or Ll-formed food should be in a tank with a residence time of no more than 1.5 hours. It is particularly preferable that the esterification reaction product in the addition tank has an esterification reaction rate of 94 coefficients or higher. If the esterification reaction rate is less than 94 coefficients, the generated internal particles will not be sufficiently refined and many coarse particles will also be present, resulting in poor processability during molding of the obtained polymer.
一方、Ｃａ及び／又はＬ１化合物を添加する槽の平均滞
留時間が１，５時間を越えると、ポリマ中内部粒子中に
巨大な凝集粒子が生成し、好ましくない。更ｅこ好まし
くは平均滞留時間ｔ Ｏ〜０．１５時間である。この範
囲とすること１こより生成する内部粒子をより微細化で
き、しかも粒子径の分布が一層シャープになるとともｅ
こ添加金属化合物が内部粒子として一層有効に寄与する
。On the other hand, if the average residence time in the tank in which Ca and/or L1 compounds are added exceeds 1.5 hours, huge aggregated particles will be formed in the internal particles of the polymer, which is not preferable. The average residence time is preferably t0~0.15 hours. By choosing this range, the internal particles generated can be made finer, and the particle size distribution will become even sharper.
This added metal compound contributes more effectively as internal particles.
ここで生成する粒子の状態にＣａ及び／又はＬ１化合物
を添力ａする檜の滞留時間が影響を与える理由は、連続
プロセスの混合槽において、その槽から排出されるもの
の中ｔこは、滞留時間の短イモのから長いもの迄混在し
ている筈である。The reason why the residence time of the cypress in which Ca and/or L1 compounds are added affects the state of the particles generated here is that in the mixing tank of a continuous process, the amount of material discharged from the tank remains There should be a mixture of short and long lengths.
内部粒子を生成させるｔこは、その槽の状況にある一定
期間維持することが必要であるが、ＦＭ度Ｐこ長時間維
持されると、ａ粒にまで成長し逆に好ましくない。従っ
て、平均滞留時間を適切に選ぶことが必要となっている
と思われる。Ｃａ及び／Ｌ ｉ化合物の添加量は、得ら
れるポリエステルに対して０．０１５〜０．２０重量％
とすることが好ましい。添加量が０．２０重量％を越え
ると、ポリマ中の粒子量が多くなり過ぎる傾向にあり１
本発明で目的とする良好な光輝性、透明性を有する製品
を得ｔこぐい。一方、０．０１５１５重量％であると粒
子量が少なくなり過き゛る傾向ｐこあシ、本発明のポイ
ントである繊維及びフィルム等の成型加−工時の工程通
過性が低下してしまう。In order to generate internal particles, it is necessary to maintain the conditions in the tank for a certain period of time, but if the FM degree P is maintained for a long period of time, the particles will grow to a particle size, which is not desirable. Therefore, it seems necessary to appropriately select the average residence time. The amount of Ca and /Li compound added is 0.015 to 0.20% by weight based on the obtained polyester.
It is preferable that If the amount added exceeds 0.20% by weight, the amount of particles in the polymer tends to become too large.
A product having good glitter and transparency, which is the objective of the present invention, was obtained. On the other hand, if it is 0.01515% by weight, the particle amount tends to be too small and the process passability during molding of fibers, films, etc., which is the key point of the present invention, is reduced.
本発明で規定したカルボキシル基末端基量及び滞留時間
の２つの要件を満たす反応液の槽ｔこＣａ及び／又はＬ
１化合物を添加する際の添加形態は、グリコール、１価
アルコール、水等と共に溶液状態又はスラリ状態として
添加することが好ましく、更ｔこ好ましくはエチレング
リコールと水の両者併用系の溶液状態で添加する。A tank containing a reaction solution that satisfies the two requirements of the amount of carboxyl end groups and residence time specified in the present invention.
Regarding the addition form when adding one compound, it is preferable to add it in a solution state or slurry state together with glycol, monohydric alcohol, water, etc., and more preferably in a solution state of a combination system of both ethylene glycol and water. do.
Ｃａ、［、ｉ及び／又はリン化合物を添加するＷｌには
１通常ポリエステルの製造時に用いられる他の添加量す
１例えば重縮合触媒としてのアンチモン化合物、チタン
化合物、ゲルマニウム化合物。Addition of Ca, [, i and/or phosphorus compound to Wl includes 1. Other additives normally used in the production of polyester. 1. For example, antimony compounds, titanium compounds, germanium compounds as polycondensation catalysts.
青味付は剤としてのコバルト化合物、あるいは僅少量の
二酸化チタン、二酸化ケイ素等の顔料を添加しても良い
。A cobalt compound as an agent or a small amount of a pigment such as titanium dioxide or silicon dioxide may be added to impart blue color.
なお本発明を実施するに当り１通常使用される公知の軟
化点低下防止剤等をエステル化反応時ｅこ添加しても良
い。In carrying out the present invention, a commonly used and known softening point lowering inhibitor may be added during the esterification reaction.
更に内部粒子系ポリマを連続プロセスで製造する際１粒
子源化合物に由来するスケールが添加槽及びそれ以降の
反応槽内壁等に生長し、そのスケール脱落ｔこよる異物
混入が思念される場合しこは、触媒添加槽以降の段階で
酸性又はアルカリ性化合物を添加することが好ましい。Furthermore, when internal particle polymers are produced in a continuous process, scale derived from one particle source compound grows on the inner walls of the addition tank and subsequent reaction tanks, and the scale may fall off, causing contamination with foreign matter. It is preferable to add an acidic or alkaline compound at a stage after the catalyst addition tank.
具体的にはモノエタノールアミン、テトラエチルアンモ
ニウムヒドロキシド等のアミン化合物及び第４級アンモ
ニウム塩が挙げられる。Specific examples include amine compounds such as monoethanolamine and tetraethylammonium hydroxide, and quaternary ammonium salts.
次に本発明の好適な実施態様を図面に基づいて説明する
。第１図は本発明方法のフローシートの１例である。第
１エステル化度応槽１に予め所定モル比に調製したテレ
フタル酸−エチレングリコールスラリを連続的に供給し
、エステル化反応を行なう。反応生成物は、第１エステ
ル化槽１の滞留液量が常に一定ｔこなるように移送ポン
プ２より抜き出し第２エステル化槽５に導き、更ｔこエ
ステル化反応を行なった後、触媒添加槽４に移送する。Next, preferred embodiments of the present invention will be described based on the drawings. FIG. 1 is an example of a flow sheet of the method of the present invention. A terephthalic acid-ethylene glycol slurry prepared in advance at a predetermined molar ratio is continuously supplied to the first esterification degree reaction tank 1 to carry out an esterification reaction. The reaction product is extracted from the transfer pump 2 and guided to the second esterification tank 5 so that the amount of liquid remaining in the first esterification tank 1 is always constant. After further esterification reaction, a catalyst is added. Transfer to tank 4.
触媒添加槽４に所定の添加剤を加える。槽の滞留液量が
一定ｔこなるように反応液を移送ポンプ５を用いて抜き
出し、予備重合槽６ｔこ導く。予備重合槽６では１弱い
減圧下で重縮合反応を進行させその後、横型重合機７に
纒き、高真空度下にて重合反応を行ない所定重合度のポ
リマを得る。A predetermined additive is added to the catalyst addition tank 4. The reaction liquid is drawn out using a transfer pump 5 so that the amount of liquid remaining in the tank becomes constant t, and is led to a prepolymerization tank 6t. In the prepolymerization tank 6, the polycondensation reaction is allowed to proceed under a weakly reduced pressure of 1°C, and then the material is placed in a horizontal polymerization machine 7, where the polymerization reaction is carried out under a high degree of vacuum to obtain a polymer having a predetermined degree of polymerization.
更νこ、実施例を挙げて本発明を具体的に説明する。な
８．実施例中の各測定値は次の方法で行った。Next, the present invention will be specifically explained with reference to Examples. 8. Each measurement value in the examples was performed by the following method.
ホリエステル５．４ｇを精秤し、これにフェノール／四
塩化エタン（６７４重貴比）の混合溶媒を４００Ｃ加え
、１０２℃×２．０時間攪拌しつつポリマ部を溶解させ
る。溶解後１時間室温で放置、冷却した後１０ｍ１の石
英ガラスセルに入れ、日本精密光学株式会社製積分球式
Ｈ，Ｔ、ＲＭＥＴＥＲ５ＥＰ−Ｈ型ヘイズメーターを用
いＡＳＴＭ −１００３−５２に従って、溶液ヘイズを
測定するっ〔粒子状態〕
ポリマな熱板上で溶融プレスしてプレパラートを作成し
、４００倍位相差顕微鏡下で観察し。Accurately weigh 5.4 g of polyester, add a mixed solvent of phenol/tetrachloroethane (674 weight ratio) at 400C, and dissolve the polymer part while stirring at 102°C for 2.0 hours. After dissolution, the solution was left at room temperature for 1 hour, cooled, and then placed in a 10 m 1 quartz glass cell, and the solution haze was measured in accordance with ASTM-1003-52 using an integrating sphere H,T, RMETER5EP-H haze meter manufactured by Nippon Seimitsu Kogaku Co., Ltd. To measure [particle state] Prepare a preparation by melt-pressing it on a polymer hot plate and observe it under a 400x phase contrast microscope.
０、０５ ｗ１’視野１こ見られる全粒子の大きさを測
定〔フィッシュアイ〕
チップ１０ｇを３００℃の加熱プレスで厚さ約５０μの
膜状に成型し、これを１００１：雰囲気下で厚さ約５〜
７μに２軸延伸して得られたフィルムを直交する偏光板
内に置き光を透過させた時に見えるフィッシュアイの個
数をカウントする。この測定値をサンプル１ｇ当わに換
算した数値をフィッシュアイ数とする。0,05 w1' Measure the size of all particles seen in 1 field of view [Fisheye] 10g of the chip was molded into a film with a thickness of about 50μ using a hot press at 300℃, and this was made into a film with a thickness of about 50μ under a 1001: atmosphere. Approximately 5~
The film obtained by biaxial stretching to 7μ is placed in orthogonal polarizing plates, and the number of fish eyes visible when light is transmitted is counted. The value obtained by converting this measured value per gram of sample is defined as the fisheye number.
３６ホールの口金を用い２１ｇ／ｍｉｎの吐出速度でポ
」ツマ２００９を紡糸し、得られた未延伸糸を１００℃
の熱ビンを使用し、４６０ ｍ ／ｍｉｎの速度で３倍
ｔこ延伸した。紡糸時のドラムへの巻き付き、延伸時の
熱ビンへの巻き付きを糸切れ回数としてカウントした。Po'tsuma 2009 was spun at a discharge rate of 21 g/min using a 36-hole spinneret, and the resulting undrawn yarn was heated at 100°C.
The film was stretched 3 times at a speed of 460 m/min using a hot bottle. The number of yarn breakages was counted as the number of times the yarn was wrapped around a drum during spinning and around a heating bin during stretching.
Ａ、Ｃｏｎ１ｘの方法「Ｍａｋｒｏｍａｌ、 Ｃｈｅｍ
、 ２６，２２６（１９５８）Ｊｌこ従って測定し試料
Ｉ ＮＦ当りのＣ０ＯＨミリ自ｉｔ数として表示した値
である。A. Con1x method “Makromal, Chem
, 26, 226 (1958) Jl was measured and expressed as the number of C0OH milliliter per sample INF.
実施例１ 第１図の装置を用いて、以下の通り操作した。Example 1 The apparatus shown in FIG. 1 was operated as follows.
常圧下２４５℃に維持した第１エステル化槽１ｐこ予め
重合度が約２．３で０ＯＯＨ末端基が１２００ｍｅｑ／
１０５ｇの反応液６２７０重量部を滞留させておき、毎
時テレフタル酸８６５重量部、エチレンクリコール３８
７重量部の割合で混合したスラリを連続的に供給し、エ
ステル化反応を行なう。エステル化反応生成物は２４５
℃に維持した滞留時間１．５時間の第２エステル化槽３
に導き０．１重量部のリン酸を１５重量部のエチレング
リコールに混合して添加し、更にエステル化反応を行な
った後、触媒添加槽４に移送する。The first esterification tank 1p maintained at 245°C under normal pressure had a polymerization degree of about 2.3 and 0OOH end groups of 1200 meq/
6,270 parts by weight of 105 g of reaction solution was retained, and 865 parts by weight of terephthalic acid and 38 parts by weight of ethylene glycol were added per hour.
A slurry mixed at a ratio of 7 parts by weight is continuously fed to carry out an esterification reaction. The esterification reaction product is 245
Second esterification tank 3 with a residence time of 1.5 hours maintained at ℃
0.1 parts by weight of phosphoric acid was mixed with 15 parts by weight of ethylene glycol and added thereto, and after an esterification reaction was carried out, the mixture was transferred to the catalyst addition tank 4.
触媒添加槽４では、２４５ ℃、常圧下に維持し、−０
，７時間の滞留時間を終た後予備重合槽６に移送される
。触媒添加槽４では毎時０，２５重量部の酢酸カルシウ
ム、１水塩、０．３重量部の三酸化アンチモンを１０重
量部の水及び３０重量部のエチレングリコールに溶解し
て添加する。触媒添加槽ｔこ導く反応液及び取り出した
反応液のエステル化反応率はそれぞれ９３．０，９６．
５％である。予備重合槽６では、毎時０．２重量部のテ
トラエチルアンモニウムヒドロキシドを、０．８重量部
の水、１５重量部のエチレングリコールと共ｔこ添加す
る。予備重合槽６は２６５℃１００ｔｏｒｒに維持され
、０．７時間の滞留時間となる様液面を調整する。その
後重合機７で高真空度下で重縮合反応を行ない、ポリエ
チレンテレフタレートを得た。得られたポリマの固有粘
度は０、６５８でポリマ中粒子は微細粒子が主体で、数
平均径が０．８５μ、３μ〜５μの粒子数が８ケ。In the catalyst addition tank 4, the temperature was maintained at 245 °C and under normal pressure, and -0
After a residence time of 7 hours, the polymer is transferred to a prepolymerization tank 6. In the catalyst addition tank 4, 0.25 parts by weight of calcium acetate, monohydrate, and 0.3 parts by weight of antimony trioxide are dissolved and added in 10 parts by weight of water and 30 parts by weight of ethylene glycol. The esterification reaction rates of the reaction liquid introduced into the catalyst addition tank and the reaction liquid taken out were 93.0 and 96.9, respectively.
It is 5%. In the prepolymerization tank 6, 0.2 parts by weight of tetraethylammonium hydroxide is added per hour together with 0.8 parts by weight of water and 15 parts by weight of ethylene glycol. The prepolymerization tank 6 is maintained at 265° C. and 100 torr, and the liquid level is adjusted so that the residence time is 0.7 hours. Thereafter, a polycondensation reaction was carried out in a polymerizer 7 under high vacuum to obtain polyethylene terephthalate. The intrinsic viscosity of the obtained polymer was 0.658, and the particles in the polymer were mainly fine particles, with a number average diameter of 0.85 μ and 8 particles with a size of 3 μ to 5 μ.
６μ以上の粒子は全くなかった。ポリマの溶液ヘイズは
１４％、フィッシュ・アイハラ個／ｇであった。該ポリ
マを乾燥後、製糸したところ紡糸及び延伸時の糸切れ等
欠点は全くなかった。There were no particles larger than 6μ. The solution haze of the polymer was 14%, Fish Aihara pieces/g. After drying the polymer, yarn was spun, and there were no defects such as yarn breakage during spinning and stretching.
実施例２〜４．比較実施例１
実施例１１こおける第２エステル化槽及び触媒添加槽の
条件の一部を変更した他、全く同様に行なった。その結
果を表１に示す。Examples 2-4. Comparative Example 1 The same procedure as in Example 11 was carried out except that the conditions of the second esterification tank and the catalyst addition tank were partially changed. The results are shown in Table 1.
第１図は本発明方法を説明するだめのフローシートであ
る。
１：第１エステル化反応槽
２．５：移送ポンプ
５：第２エステル化反応槽
４：触媒添加槽
６：予備重合槽
７：重合機
特許出願人 東し株式会社FIG. 1 is a flow sheet illustrating the method of the present invention. 1: First esterification reaction tank 2.5: Transfer pump 5: Second esterification reaction tank 4: Catalyst addition tank 6: Prepolymerization tank 7: Polymerization machine Patent applicant Toshi Co., Ltd.
Claims (1)
してポリエステルを連続的に製造す応を行う任意の段階
で滞留時間が１．５時間以内の槽ｅこＣａ及び／又はＬ
１化合物を添加することを特徴とするポリエステルの製
造法。Continuous production of polyester using terephthalic acid and ethylene glycol as main starting materials.
A method for producing polyester, characterized by adding one compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP89282A JPS58118822A (en) | 1982-01-08 | 1982-01-08 | Production of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP89282A JPS58118822A (en) | 1982-01-08 | 1982-01-08 | Production of polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58118822A true JPS58118822A (en) | 1983-07-15 |
| JPH0359925B2 JPH0359925B2 (en) | 1991-09-12 |
Family
ID=11486325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP89282A Granted JPS58118822A (en) | 1982-01-08 | 1982-01-08 | Production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58118822A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS626906A (en) * | 1985-07-03 | 1987-01-13 | Toray Ind Inc | Production of polyester fiber |
| JP2004107624A (en) * | 2002-07-22 | 2004-04-08 | Mitsubishi Chemicals Corp | Polyester resin and film consisting of the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490397A (en) * | 1977-12-28 | 1979-07-18 | Daiafoil | Preparation of polyester for film forming |
-
1982
- 1982-01-08 JP JP89282A patent/JPS58118822A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490397A (en) * | 1977-12-28 | 1979-07-18 | Daiafoil | Preparation of polyester for film forming |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS626906A (en) * | 1985-07-03 | 1987-01-13 | Toray Ind Inc | Production of polyester fiber |
| JP2004107624A (en) * | 2002-07-22 | 2004-04-08 | Mitsubishi Chemicals Corp | Polyester resin and film consisting of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0359925B2 (en) | 1991-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1110988B1 (en) | Catalyst for polyester production and process for producing polyester with the same | |
| JP2003238673A (en) | Method for producing polyester | |
| JPH08311177A (en) | Thermoplastic polyester resin | |
| JP7251260B2 (en) | Cationic dyeable polyester and method for producing the same | |
| JP2004183143A (en) | Polyester fiber and method for producing the same | |
| JP2004067924A (en) | Polyester, manufacturing process therefor and fiber thereof | |
| JP2005187556A (en) | Polyester and manufacturing method of polyester | |
| JPS58118822A (en) | Production of polyester | |
| JPH0551611B2 (en) | ||
| JPS58129020A (en) | Preparation of polyester | |
| JPS58118820A (en) | Continuous production of polyester | |
| JPH02302432A (en) | Production of polyester | |
| JPS58157817A (en) | Preparation of polyester | |
| JPS6025047B2 (en) | Manufacturing method of modified polyester | |
| JP2000204145A (en) | Production of high molecular weight polyethylene terephthalate | |
| JPS5946256B2 (en) | Polyester manufacturing method | |
| JPH06509386A (en) | Method of manufacturing polyester and its use | |
| JPS63530B2 (en) | ||
| JP2004124004A (en) | Manufacturing method of polyester, polyester and fiber | |
| JPS6237652B2 (en) | ||
| JP2003096169A (en) | Copolyester | |
| JPH0114249B2 (en) | ||
| JPH03192118A (en) | Production of polyester | |
| JPS6256894B2 (en) | ||
| JPH041224A (en) | Production of polyester |