JPH09291141A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPH09291141A JPH09291141A JP13090996A JP13090996A JPH09291141A JP H09291141 A JPH09291141 A JP H09291141A JP 13090996 A JP13090996 A JP 13090996A JP 13090996 A JP13090996 A JP 13090996A JP H09291141 A JPH09291141 A JP H09291141A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- antimony trioxide
- producing
- sodium
- atoms
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、色調の良好なポリ
エステルを安定して製造することのできるポリエステル
の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a polyester capable of stably producing a polyester having a good color tone.
【０００２】[0002]
【従来の技術】ポリエチレンテレフタレート（ＰＥＴ）
は、機械的特性及び化学的特性に優れており、衣料用や
産業用の繊維のほか、包装用、磁気テープ用、写真用、
コンデンサー用等のフイルム、ボトル等の成形物として
広く用いられている。2. Description of the Related Art Polyethylene terephthalate (PET)
Has excellent mechanical and chemical properties, as well as clothing and industrial fibers, as well as packaging, magnetic tape, photographic,
It is widely used as molded products such as films for condensers and bottles.
【０００３】ＰＥＴは、工業的にはテレフタル酸又はジ
メチルテレフタレートとエチレングリコールとからエス
テル化もしくはエステル交換によりビス（β−ヒドロキ
シエチル）テレフタレート（その低重合体を含む）を
得、これを重縮合触媒の存在下、高温、高減圧下で重縮
合する方法により製造されている。PET is industrially used to obtain bis (β-hydroxyethyl) terephthalate (including its low polymer) from terephthalic acid or dimethyl terephthalate and ethylene glycol by esterification or transesterification, and this is used as a polycondensation catalyst. It is produced by a method of polycondensation under high temperature and high reduced pressure in the presence of.
【０００４】ＰＥＴを製造する際の重縮合触媒として
は、三酸化アンチモンが安価で、かつ触媒活性が優れて
いるため最も広く用いられている。しかしながら、三酸
化アンチモンを重縮合触媒として用いると、得られるポ
リエステルの透明性が悪化し、黒ずんだ灰緑色の色調と
なり易いという欠点を有している。As a polycondensation catalyst for producing PET, antimony trioxide is most widely used because it is inexpensive and has excellent catalytic activity. However, when antimony trioxide is used as a polycondensation catalyst, it has a drawback that the transparency of the obtained polyester is deteriorated and a dark grayish green color tone is easily obtained.
【０００５】この欠点を解消する方法として、特開昭50
− 53495号公報には、エチレングリコール中で加熱した
際に検出される特定の不純物の量が一定量以下である三
酸化アンチモンを使用する方法が提案されている。この
ような三酸化アンチモンを使用することによりポリエス
テルの色調はある程度改良されるものの、ポリエステル
中に未溶解のアンチモン金属等が含まれているためか、
ポリエステルを溶融成形する際、特に溶融紡糸し、延伸
する際に糸切れが発生し、操業性が低下するという問題
があった。As a method for solving this drawback, Japanese Patent Laid-Open No.
-53495 proposes a method of using antimony trioxide in which the amount of specific impurities detected when heated in ethylene glycol is a certain amount or less. Although the color tone of the polyester is improved to some extent by using such antimony trioxide, it may be because undissolved antimony metal or the like is contained in the polyester.
There has been a problem that yarn breakage occurs when melt-forming polyester, particularly when melt-spinning and stretching, and the operability is deteriorated.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、重縮合触媒
として三酸化アンチモンを使用して、色調の良好なポリ
エステルを安定して製造することのできるポリエステル
の製造方法を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention is intended to provide a method for producing a polyester by using antimony trioxide as a polycondensation catalyst, which makes it possible to stably produce a polyester having a good color tone. is there.
【０００７】[0007]
【課題を解決するための手段】本発明らは、上記の課題
を解決するもので、その要旨は、テレフタル酸又はこれ
を主体とする酸成分とエチレングリコール又はこれを主
体とするグリコールとからポリエステルを製造するに際
し、重縮合触媒として、ナトリウム及び鉄の酸化物をナ
トリウム原子及び鉄原子の合計量で15〜80ppm 含有する
三酸化アンチモンを使用することを特徴とするポリエス
テルの製造方法にある。Means for Solving the Problems The present invention is to solve the above-mentioned problems, and the gist thereof is to provide a polyester from terephthalic acid or an acid component mainly containing this and ethylene glycol or glycol mainly containing this. The method for producing polyester is characterized by using antimony trioxide containing sodium and iron oxides in an amount of 15 to 80 ppm as the total amount of sodium and iron atoms as a polycondensation catalyst.
【０００８】[0008]
【発明の実施の形態】以下、本発明について詳細に説明
する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
【０００９】本発明の方法は、主としてテレフタル酸成
分とエチレングリコール成分とからＰＥＴを製造する際
に適用されるが、少量の共重合成分を含有させてもよ
い。共重合成分としては、イソフタル酸、無水フタル
酸、２，６−ナフタレンジカルボン酸、５−ナトリウム
スルホイソフタル酸、アジピン酸、コハク酸等のジカル
ボン酸成分や1,４−ブタンジオール、1,３−プロパンジ
オール、ジエチレングリコール、ポリエチレングリコー
ル等のグリコール成分が挙げられる。The method of the present invention is mainly applied to the production of PET from a terephthalic acid component and an ethylene glycol component, but it may contain a small amount of a copolymerization component. Examples of the copolymerization component include diphthalic acid components such as isophthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid and succinic acid, 1,4-butanediol, 1,3- Examples include glycol components such as propanediol, diethylene glycol, and polyethylene glycol.
【００１０】本発明においては、重縮合触媒として、ナ
トリウム及び鉄の酸化物をナトリウム原子及び鉄原子の
合計量で15〜80ppm 含有する三酸化アンチモンを使用す
る。ナトリウム及び鉄の酸化物の含有量が多すぎると、
異物の含有量が多いポリエステルとなり、製糸する場
合、糸切れが発生し易くなったり、色調の劣ったポリエ
ステルとなったりする。一方、ナトリウム及び鉄の酸化
物の含有量が少なすぎると色調を向上させる効果が乏し
い。なお、ナトリウム原子の含有量を５〜70ppm 、鉄原
子の含有量を10〜75ppm とし、合計で15〜80ppm となる
ようにすることが望ましい。In the present invention, as the polycondensation catalyst, antimony trioxide containing sodium and iron oxides in an amount of 15 to 80 ppm as the total amount of sodium and iron atoms is used. If the content of sodium and iron oxides is too high,
Polyester has a large amount of foreign matter, and when yarn is produced, yarn breakage easily occurs, or the polyester has a poor color tone. On the other hand, if the content of the oxides of sodium and iron is too small, the effect of improving the color tone is poor. It is desirable that the sodium atom content is 5 to 70 ppm and the iron atom content is 10 to 75 ppm, so that the total is 15 to 80 ppm.
【００１１】本発明で使用する三酸化アンチモンは、ア
ンチモン鉱石を焼成して得られる三酸化アンチモンを精
製することにより得ることができ、精製の度合いによっ
て、ナトリウム及び鉄の酸化物の含有量を調整すること
ができる。なお、従来ポリエステルの重縮合触媒として
用いる三酸化アンチモンは、高純度のものが好ましいと
考えられており、ナトリウム原子及び鉄原子の合計含有
量が10ppm 未満のものが一般に使用されていた。The antimony trioxide used in the present invention can be obtained by refining antimony trioxide obtained by firing antimony ore, and the contents of sodium and iron oxides can be adjusted depending on the degree of refining. can do. It is considered that high-purity antimony trioxide used as a polycondensation catalyst for conventional polyesters is preferable, and those having a total content of sodium atoms and iron atoms of less than 10 ppm have been generally used.
【００１２】本発明の方法は、通常のＰＥＴの製造方法
に準じて実施することができ、例えば、テレフタル酸と
エチレングリコールとをエステル化反応させ、次いで反
応生成物を重縮合させて所定の極限粘度のポリエステル
とする方法で行うことができる。The method of the present invention can be carried out in accordance with a conventional method for producing PET. For example, terephthalic acid and ethylene glycol are subjected to an esterification reaction, and then the reaction product is polycondensed to a predetermined limit. It can be carried out by a method of forming a polyester having a viscosity.
【００１３】具体的には、ビス (β−ヒドロキシエチ
ル）テレフタレート及び／又はその低重合体の存在する
エステル化反応缶にテレフタル酸とエチレングリコール
とのモル比１／1.6 程度のスラリーを連続的に供給し、
温度 220〜260 ℃、圧力0.02〜1.50MPa で、５〜７時間
エステル化反応を行い、エステル化反応率90〜95％のエ
ステル化反応物を得る。次いで、エステル化反応物を重
縮合反応缶に移送し、重縮合触媒である三酸化アンチモ
ンを添加し、13 hPa以下の減圧下、 260〜280 ℃の温度
で、高重合度のポリエステルが得られるまで重縮合反応
を行う。Specifically, a slurry having a molar ratio of terephthalic acid and ethylene glycol of about 1 / 1.6 is continuously added to an esterification reaction vessel containing bis (β-hydroxyethyl) terephthalate and / or its low polymer. Supply,
The esterification reaction is carried out at a temperature of 220 to 260 ° C. and a pressure of 0.02 to 1.50 MPa for 5 to 7 hours to obtain an esterification reaction product having an esterification reaction rate of 90 to 95%. Next, the esterification reaction product is transferred to a polycondensation reaction vessel, polycondensation catalyst antimony trioxide is added, and a polyester having a high degree of polymerization is obtained at a temperature of 260 to 280 ° C under a reduced pressure of 13 hPa or less. Perform polycondensation reaction until.
【００１４】重縮合触媒の添加時期は、エステル化反応
終了後、重縮合反応開始前が好ましいが、重縮合反応の
初期までであればよい。また、三酸化アンチモンは、エ
チレングリコール溶液として反応系に添加するのが好ま
しい。The polycondensation catalyst is preferably added after the esterification reaction and before the polycondensation reaction is started, but may be added until the initial stage of the polycondensation reaction. Further, antimony trioxide is preferably added to the reaction system as an ethylene glycol solution.
【００１５】重縮合触媒としての三酸化アンチモンは、
通常、酸成分１モルに対して、４×10-5〜４×10-3モル
の範囲で添加される。Antimony trioxide as a polycondensation catalyst is
Usually, it is added in the range of 4 × 10 −5 to 4 × 10 −3 mol with respect to 1 mol of the acid component.
【００１６】[0016]
【作用】本発明の方法によると、重縮合触媒として三酸
化アンチモンを用いているにもかかわらず、得られるポ
リマーは優れた色調を示す。これは、本発明で使用する
三酸化アンチモンは、適量のナトリウム及び鉄の酸化物
を含有しているため、三酸化アンチモンの還元が抑制さ
れ、くすみの原因となる金属アンチモンの析出が抑制さ
れるためと認められる。According to the method of the present invention, the obtained polymer shows an excellent color tone despite the use of antimony trioxide as the polycondensation catalyst. This is because the antimony trioxide used in the present invention contains an appropriate amount of sodium and iron oxides, the reduction of antimony trioxide is suppressed, and the precipitation of metallic antimony that causes dullness is suppressed. Recognized as a reason.
【００１７】[0017]
【実施例】次に、実施例をあげて本発明を具体的に説明
する。なお、実施例においてポリエステルの特性値は次
のようにして測定した。 (a) 極限粘度〔η〕 フェノールと四塩化エタンとの等重量混合物を溶媒とし
て、温度20.0℃で測定した。 (b) 色調（ｂ値） 日本電色工業社製の色差計ND−Σ80型を用いて測定し
た。ｂ値は黄−青系の色相（＋は黄味、−は青味）を表
わし、ポリマーの色調として極端に小さくならない限り
ｂ値が小さいほど良好である。 (c) ナトリウム原子及び鉄原子の含有量 リガク社製蛍光Ｘ線分析装置 3270-E1型を用いて測定し
た。 (d) 昇圧速度 小型エクストルーダーの先端に、2000メッシュと 600メ
ッシュの金網フイルターを装着し、 285℃で溶融したポ
リマーを押し出し、12時間の間の昇圧度を測定して求め
た。Next, the present invention will be described specifically with reference to examples. In the examples, the characteristic values of polyester were measured as follows. (a) Intrinsic viscosity [η] Measured at a temperature of 20.0 ° C. using an equal weight mixture of phenol and ethane tetrachloride as a solvent. (b) Color tone (b value) It was measured using a color difference meter ND-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. The b value indicates a yellow-blue hue (+ indicates yellowish,-indicates bluish). Unless the color tone of the polymer becomes extremely small, the smaller the b value is, the better. (c) Content of sodium atom and iron atom It was measured using a fluorescent X-ray analyzer 3270-E1 manufactured by Rigaku Corporation. (d) Pressurization rate A 2000 mesh and 600 mesh wire mesh filter was attached to the tip of a small extruder, the polymer melted at 285 ° C was extruded, and the pressurization degree was measured for 12 hours.
【００１８】実施例１ ビス（β−ヒドロキシエチル）テレフタレート及びその
低重合体の存在するエステル化反応缶に、テレフタル酸
とエチレングリコールとのモル比１／1.6 のスラリーを
連続的に供給し、温度 260℃、圧力 0.04MPa、滞留時間
６時間の条件で反応させ、エステル化反応率95％のエス
テル化生成物を連続的に得た。このエステル化生成物60
kgを重縮合反応缶に仕込み、重縮合触媒として、ナトリ
ウム及び鉄の酸化物を、ナトリウム原子６ppm 及び鉄原
子13ppm の含有量で含有する三酸化アンチモン２×10-4
モル／酸成分モルをエチレングリコール溶液として添加
し、温度 280℃で徐々に減圧し、最終的に 1.3hPa と
し、２時間重縮合反応を行った。得られたポリマーの特
性値を表１に示す。Example 1 A slurry of terephthalic acid and ethylene glycol in a molar ratio of 1 / 1.6 was continuously fed to an esterification reaction vessel containing bis (β-hydroxyethyl) terephthalate and its low polymer, and the temperature was raised. The reaction was carried out under the conditions of 260 ° C., pressure of 0.04 MPa and residence time of 6 hours to continuously obtain an esterification product having an esterification reaction rate of 95%. This esterification product 60
charged kg to a polycondensation reactor, as a polycondensation catalyst, sodium and iron oxides, sodium atom 6ppm and iron atoms contained in a content of 13ppm antimony trioxide 2 × 10 -4
Mol / mol of acid component was added as an ethylene glycol solution, and the pressure was gradually reduced at a temperature of 280 ° C. to finally set to 1.3 hPa, and a polycondensation reaction was carried out for 2 hours. The characteristic values of the obtained polymer are shown in Table 1.
【００１９】実施例２〜７及び比較例１〜５ 三酸化アンチモンのナトリウム及び鉄の酸化物の含有量
を変えた以外は、実施例１と同様にしてポリエステルを
製造した。得られたポリマーの特性値を表１に示す。Examples 2 to 7 and Comparative Examples 1 to 5 Polyesters were produced in the same manner as in Example 1 except that the contents of sodium and iron oxides of antimony trioxide were changed. The characteristic values of the obtained polymer are shown in Table 1.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【発明の効果】本発明によれば、重縮合触媒として三酸
化アンチモンを使用して、色調の良好なポリエステルを
安定して製造することができる。According to the present invention, polyester having a good color tone can be stably produced by using antimony trioxide as a polycondensation catalyst.
Claims (2)
分とエチレングリコール又はこれを主体とするグリコー
ルとからポリエステルを製造するに際し、重縮合触媒と
して、ナトリウム及び鉄の酸化物をナトリウム原子及び
鉄原子の合計量で15〜80ppm 含有する三酸化アンチモン
を使用することを特徴とするポリエステルの製造方法。1. A method for producing a polyester from terephthalic acid or an acid component containing mainly terephthalic acid and ethylene glycol or glycol containing mainly this, a polycondensation catalyst containing sodium and iron oxides of sodium and iron oxides. A method for producing a polyester, which comprises using antimony trioxide in a total amount of 15 to 80 ppm.
５〜70ppm 、鉄原子を10〜75ppm 、合計で15〜80ppm 含
有するものである請求項１記載のポリエステルの製造方
法。2. The method for producing a polyester according to claim 1, wherein the antimony trioxide contains sodium atoms in an amount of 5 to 70 ppm, iron atoms in an amount of 10 to 75 ppm, and a total of 15 to 80 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13090996A JPH09291141A (en) | 1996-04-25 | 1996-04-25 | Production of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13090996A JPH09291141A (en) | 1996-04-25 | 1996-04-25 | Production of polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09291141A true JPH09291141A (en) | 1997-11-11 |
Family
ID=15045577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13090996A Pending JPH09291141A (en) | 1996-04-25 | 1996-04-25 | Production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09291141A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
| WO2007035250A2 (en) | 2005-09-16 | 2007-03-29 | Eastman Chemical Company | Polyester composition containing aluminum and lithium catalysts and titanium nitride particles and having improved reheat |
| US7199212B2 (en) | 2000-01-05 | 2007-04-03 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyesters produced with the same and process for producing polyesters |
| US7208565B1 (en) | 1999-08-24 | 2007-04-24 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester |
| WO2009025312A1 (en) | 2007-08-20 | 2009-02-26 | Sakai Chemical Industry Co., Ltd. | Polycondensation catalyst for production of polyester, process for production of the catalyst, and process for production of polyester |
| WO2011034156A1 (en) | 2009-09-15 | 2011-03-24 | 堺化学工業株式会社 | Polycondensation catalyst for the production of polyesters, and polyester production method using same |
| WO2014021206A1 (en) | 2012-07-31 | 2014-02-06 | 堺化学工業株式会社 | Polycondensation catalyst for polyester production and production of polyester using polycondensation catalyst for polyester production |
| US9289749B2 (en) | 2012-07-31 | 2016-03-22 | Sakai Chemical Industry Co., Ltd. | Polycondensation catalyst for producing polyester and production of polyester using the polycondensation catalyst |
| WO2019124166A1 (en) | 2017-12-22 | 2019-06-27 | 堺化学工業株式会社 | Polycondensation catalyst for polyester production and polyester production using same |
-
1996
- 1996-04-25 JP JP13090996A patent/JPH09291141A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8293862B2 (en) | 1999-08-24 | 2012-10-23 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and a process for producing polyester |
| US7208565B1 (en) | 1999-08-24 | 2007-04-24 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester |
| US7199212B2 (en) | 2000-01-05 | 2007-04-03 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyesters produced with the same and process for producing polyesters |
| US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
| US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
| WO2007035250A2 (en) | 2005-09-16 | 2007-03-29 | Eastman Chemical Company | Polyester composition containing aluminum and lithium catalysts and titanium nitride particles and having improved reheat |
| WO2009025312A1 (en) | 2007-08-20 | 2009-02-26 | Sakai Chemical Industry Co., Ltd. | Polycondensation catalyst for production of polyester, process for production of the catalyst, and process for production of polyester |
| WO2011034156A1 (en) | 2009-09-15 | 2011-03-24 | 堺化学工業株式会社 | Polycondensation catalyst for the production of polyesters, and polyester production method using same |
| WO2014021206A1 (en) | 2012-07-31 | 2014-02-06 | 堺化学工業株式会社 | Polycondensation catalyst for polyester production and production of polyester using polycondensation catalyst for polyester production |
| KR20150040855A (en) | 2012-07-31 | 2015-04-15 | 사까이가가꾸고오교가부시끼가이샤 | Polycondensation catalyst for producing polyester and production of polyester using the polycondensation catalyst |
| US9289749B2 (en) | 2012-07-31 | 2016-03-22 | Sakai Chemical Industry Co., Ltd. | Polycondensation catalyst for producing polyester and production of polyester using the polycondensation catalyst |
| WO2019124166A1 (en) | 2017-12-22 | 2019-06-27 | 堺化学工業株式会社 | Polycondensation catalyst for polyester production and polyester production using same |
| KR20200101368A (en) | 2017-12-22 | 2020-08-27 | 사까이가가꾸고오교가부시끼가이샤 | Polycondensation catalyst for polyester production and production of polyester using the same |
| US11612882B2 (en) | 2017-12-22 | 2023-03-28 | Sakai Chemical Industry Co., Ltd. | Polycondensation catalyst for producing polyester and production of polyester using the same |
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