JPS5817453B2 - Continuous esterification method of terephthalic acid - Google Patents
Continuous esterification method of terephthalic acidInfo
- Publication number
- JPS5817453B2 JPS5817453B2 JP9898677A JP9898677A JPS5817453B2 JP S5817453 B2 JPS5817453 B2 JP S5817453B2 JP 9898677 A JP9898677 A JP 9898677A JP 9898677 A JP9898677 A JP 9898677A JP S5817453 B2 JPS5817453 B2 JP S5817453B2
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- Prior art keywords
- reaction
- mixing tank
- esterification
- amount
- terephthalic acid
- Prior art date
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Description
【発明の詳細な説明】
本発明はテレフタル酸をエチレングリコール(以下BG
と略す)によって連続的にエステル化する改良された方
法に関するものであり、その目的とするところはエステ
ル化反応系に補給するEGの量を過不足なく最少量に保
ち、かつ均一な品質のエステル化物を得ることにある。DETAILED DESCRIPTION OF THE INVENTION The present invention combines terephthalic acid with ethylene glycol (hereinafter referred to as BG).
The purpose of this method is to keep the amount of EG supplied to the esterification reaction system at the minimum amount, and to produce ester of uniform quality. It's about getting monsters.
衣料用、産業資材用として有用なポリエチレンテレフタ
レートはテレフタル酸をEGによってエステル化し、さ
らに高温減圧下に重縮合を行なって製造される。Polyethylene terephthalate, which is useful for clothing and industrial materials, is produced by esterifying terephthalic acid with EG and then polycondensing it at high temperature and reduced pressure.
ここで、通常エステル化反応はテレフタル酸とEGを混
合して240〜270℃に加熱することによって行なわ
れるのである75− EGの常圧における沸点が反応温
度よりも低い為に、従来、反応は2〜5kg/cyAG
の加圧下に行なわれていた。Here, the esterification reaction is usually carried out by mixing terephthalic acid and EG and heating it to 240 to 270°C.75- Because the boiling point of EG at normal pressure is lower than the reaction temperature, the reaction has conventionally been carried out. 2~5kg/cyAG
It was carried out under pressure.
この場合EGはI/1とんど反応液中に溶存し反応によ
って生成する水を除去することにより安定して反応を行
なわせることが出来る。In this case, EG is dissolved in the reaction solution at most of I/1, and the reaction can be carried out stably by removing water produced by the reaction.
しかし、反応液中の水酸基濃度が高くなり、エーテル結
合の生成が起こりやすく、ポリマーの軟化点を低下させ
たり、またエーテル結合生成抑制剤として、添加するア
ミン類によってポリマーが着色する等の欠点を有する。However, the concentration of hydroxyl groups in the reaction solution increases, which tends to cause the formation of ether bonds, which lowers the softening point of the polymer.Also, when used as an ether bond formation inhibitor, the amines added may color the polymer. have
この欠点は反応圧力を下けて2kVc4G以下とするこ
とによって除くことが出来る。This drawback can be eliminated by lowering the reaction pressure to 2 kVc4G or less.
すなわち反応圧力が低い為に反応液中のEG溶存量が少
7<fi!;+、つまり、反応液中の水酸基濃度が低く
なり、エーテル結合の生成量は極めて少なくなる。In other words, since the reaction pressure is low, the amount of EG dissolved in the reaction solution is small7<fi! ;+, that is, the concentration of hydroxyl groups in the reaction solution becomes low, and the amount of ether bonds produced becomes extremely small.
このことは逆に供給したEGの多くがエステル化反応器
外に排出されることを意味する。This means that much of the supplied EG is discharged outside the esterification reactor.
従ってエステル化反応圧力を下げる場合には、EGの再
利用システムを確立しておく必要がある。Therefore, when lowering the esterification reaction pressure, it is necessary to establish an EG reuse system.
この方法として、エステル化反応器から発生する蒸気を
蒸留操作によって脱水精製して得られたEGを直接スラ
リー混合槽に循環し、系外からEGを一定量ずつ補給す
る方法が考えられる。As a method for this, a method can be considered in which EG obtained by dehydrating and purifying the steam generated from the esterification reactor by a distillation operation is directly circulated to the slurry mixing tank, and a fixed amount of EG is replenished from outside the system.
ところがこの方法を実施し続けると、循環EG量が絶え
ず変動しているだめ、スラリー混合槽内でのテレフタル
酸に対するEGの割合が一定にならず、反応率が変動し
、その結果エステル化物の品質が均一にならない。However, if this method is continued, the amount of circulating EG is constantly changing, so the ratio of EG to terephthalic acid in the slurry mixing tank is not constant, and the reaction rate fluctuates, resulting in poor quality of the esterified product. is not uniform.
また前記方法では蒸留塔および反応器内のEGのホール
ドアツプ量の増加によって循iEG量が減少した時を考
慮して、補給するEG量を多い目にし7ておくことが必
要となるので、過剰のEGを絶えず抜き出さねばならず
、EGの無駄な消費量が多くなる。In addition, in the above method, it is necessary to increase the amount of EG to be replenished, taking into consideration the case where the amount of circulating iEG decreases due to an increase in the amount of EG held up in the distillation column and reactor. EG must be constantly extracted, resulting in a large amount of wasted EG consumption.
など実際操作する際支障が多く連続操業は好ましくない
。Continuous operation is not recommended as there are many problems during actual operation.
そこで、本発明者らは系外より補給するEG量を過不足
なく最少量に保ち、かつ均一な品質のエステル化物を得
るために、鋭意研究、検討した結果、遂に本発明を完成
するに至った。Therefore, the present inventors have conducted intensive research and examination in order to maintain the amount of EG supplied from outside the system to the minimum amount without excess or deficiency, and to obtain an esterified product of uniform quality, and as a result, they have finally completed the present invention. Ta.
すなわち、本発明はテレフタル酸とエチレングリコール
ラスラリ−混合槽にて混合しスラリー状となし、該スラ
リーを連続的にO〜2に&/cniGの圧力に保たれた
エステル化反応器に供給してエステル化反応を行なわせ
るに際し、前記エステル化反応器より発生する蒸気より
エチレングリコールを回収して、エチレングリコール調
合槽に導ひき、該調合槽の貯留量が一定となるように、
反応系外から反応によって消費された量のエチレングリ
コールを補給し、混合した後計量して前記スラリー混合
槽または/およびエステル化反応器へ循環することを特
徴とするテレフタル酸の連続エステル化方法である。That is, in the present invention, terephthalic acid and ethylene glycol slurry are mixed in a slurry mixing tank to form a slurry, and the slurry is continuously supplied to an esterification reactor maintained at a pressure of O~2 &/cniG. When carrying out the esterification reaction, ethylene glycol is recovered from the steam generated from the esterification reactor and introduced into an ethylene glycol mixing tank, so that the amount stored in the mixing tank is constant.
A method for continuous esterification of terephthalic acid, characterized in that the amount of ethylene glycol consumed by the reaction is replenished from outside the reaction system, mixed, measured, and circulated to the slurry mixing tank or/and esterification reactor. be.
本発明において、エステル化反応器から発生する蒸気中
にはEG以外に、エステル化反応によって生成した多量
の水、少量のアルデヒド類、オリゴマーなどが含まれて
おり、蒸留操作によって脱水精製される。In the present invention, the steam generated from the esterification reactor contains, in addition to EG, a large amount of water produced by the esterification reaction, small amounts of aldehydes, oligomers, etc., and is dehydrated and purified by a distillation operation.
蒸留操作は蒸留塔の塔頂から水分および少量のアルデヒ
ド類が、一方塔底からは若干の水とオリゴマーを含むE
Gが取出される。In the distillation operation, water and a small amount of aldehydes are released from the top of the distillation column, while E containing some water and oligomers is released from the bottom of the column.
G is taken out.
この取出されたBG中の水分は10重量%以下に保つこ
とが好ましい。It is preferable to keep the water content in the extracted BG at 10% by weight or less.
これより水分が多い場合には循環再使用するBG中の水
分が多くなり、エステル化反応器にかかる熱負荷が多く
なるのみならず加水分解反応が起こり、エステル化率が
低下したり、またスラリー混合槽においてテレフタル酸
と混合する際に水蒸気によりテレフタル酸の供給管を閉
塞させる等の弊害があるので好ましくない。If the water content is higher than this, there will be more water in the BG to be recycled and reused, which will not only increase the heat load on the esterification reactor but also cause a hydrolysis reaction, resulting in a decrease in the esterification rate and a reduction in the slurry. When mixed with terephthalic acid in a mixing tank, water vapor causes problems such as clogging of the terephthalic acid supply pipe, which is not preferable.
前記水分率10重量%以下になって塔底より取出された
BGは、次にEG調合槽に供給する。The BG taken out from the bottom of the tower with a moisture content of 10% by weight or less is then supplied to an EG mixing tank.
一方EG調合槽には、反応によシ消費された量のEGを
補給するが、これは上記EG調合槽の貯留量が一定にな
るように制御しながら補給する。On the other hand, the EG mixing tank is replenished with the amount of EG consumed by the reaction, and this is controlled so that the amount stored in the EG mixing tank remains constant.
貯留量を一定になるように制御する方法としては、たと
えば一般に市販されている気泡吹込み型、またはダイヤ
フラム型等の液面計をEG調合槽に設置し反応系外から
補給されるEG配管にとりつけだコントロール弁と連動
させる事によって該EG調合槽内のEG滞留量を一定量
に保持するなど種々の方法を採用することができる。As a method of controlling the storage amount to be constant, for example, a generally commercially available bubble blowing type or diaphragm type liquid level gauge is installed in the EG mixing tank and connected to the EG piping that is supplied from outside the reaction system. Various methods can be adopted, such as maintaining the amount of EG retained in the EG mixing tank at a constant amount by interlocking with an attached control valve.
なお本発明において、EG調合槽の容量は反応系のEG
のホールドアツプの2〜5倍が好ましい。In the present invention, the capacity of the EG mixing tank is the same as the EG in the reaction system.
2 to 5 times the hold up is preferable.
これは、蒸留塔の塔底よシ取出されたEGと、新しく補
給されるEGとの組成が異なるだめ、EG調合槽の容量
が小さ過ぎる場合には、水、オリゴマーなどEG以外の
組成変動が大きくなることが考えられる。This is because the composition of the EG taken out from the bottom of the distillation column is different from the newly replenished EG, and if the capacity of the EG mixing tank is too small, the composition of water, oligomers, etc. other than EG may change. It is possible that it will become larger.
また逆に大きくなり過ぎるとオリゴマー等を含むEGが
高い温度で長時間滞留することになり好ましくないから
である。On the other hand, if it becomes too large, EG containing oligomers etc. will remain at high temperature for a long time, which is not preferable.
次に図面を用いて本発明方法を説明する。Next, the method of the present invention will be explained using the drawings.
第1図は本発明の方法を示す一具体例である。FIG. 1 is a specific example illustrating the method of the present invention.
2はスラリー混合槽であってテレフタル酸は供給管25
より、EGはポンプ8によって供給され混合される。2 is a slurry mixing tank, and terephthalic acid is supplied through a supply pipe 25.
Therefore, EG is supplied and mixed by the pump 8.
このスラリーはポンプ12によって配管19により第1
番目のエステル化反応器3に送られる。This slurry is pumped through the pipe 19 by the pump 12 to the first
It is sent to the second esterification reactor 3.
エステル化反応温度は240〜270℃、反応圧力は0
〜2kg/cr!Gであって、ここでテレフタル酸の6
0〜70係がエステル化される。Esterification reaction temperature is 240-270℃, reaction pressure is 0
~2kg/cr! G, where 6 of terephthalic acid
Groups 0 to 70 are esterified.
反応により発生する蒸気は配管21によって蒸留塔5に
送られる。The vapor generated by the reaction is sent to the distillation column 5 via a pipe 21.
11は圧力検出端、10は圧力調整用コントロール弁で
あって蒸留塔5は反応缶と異なる圧力で操作される。11 is a pressure detection end, 10 is a pressure regulating control valve, and the distillation column 5 is operated at a pressure different from that of the reaction vessel.
反応物は配管20によって第2番目のエステル化反応器
4に送られ、ここでテレフタル酸の90〜98%がエル
テル化され、配管24によって減圧下に操作される重合
反応器に送られる。The reactants are conveyed by line 20 to a second esterification reactor 4, where 90-98% of the terephthalic acid is eruterized and conveyed by line 24 to a polymerization reactor operated under reduced pressure.
この反応においてはEGを添加し反応を促進させるのも
効果的である。In this reaction, it is also effective to add EG to accelerate the reaction.
EGはポンプ9によって配管18よりより供給される。EG is supplied from a pipe 18 by a pump 9.
反応温度は第1番目の反応器と同じく240〜270℃
、反応圧力は常圧で反応し得る。The reaction temperature is 240-270℃, same as the first reactor.
, the reaction pressure may be normal pressure.
発生する蒸気は配管22によって蒸留塔5に送られる。The generated steam is sent to the distillation column 5 via a pipe 22.
蒸留塔5では水および少量のアルデヒド類等、EGより
沸点の低い成分は、塔頂より配管23によって反応系外
に抜き出される。In the distillation column 5, components having a boiling point lower than that of EG, such as water and a small amount of aldehydes, are extracted from the top of the column through a pipe 23 to the outside of the reaction system.
塔底には若干の水およびオリゴマーを含むEGが滞留す
る。EG containing some water and oligomers remains at the bottom of the column.
これを配管16によりEG調合槽1に導びく。This is led to the EG mixing tank 1 through a pipe 16.
また調合槽1へは配管15によってEGが補給される。Further, EG is supplied to the mixing tank 1 through a pipe 15.
補給量はEG調合槽の貯留量が一定になる様に制御され
る。The amount of replenishment is controlled so that the amount stored in the EG mixing tank is constant.
Tは滑液量検出端であり、6はコントロール弁である。T is a synovial fluid amount detection end, and 6 is a control valve.
EG調合槽1で混合されたEGは配管17よりポンプ8
によって計量されスラリ−混合槽に供給される。The EG mixed in the EG mixing tank 1 is transferred from the pipe 17 to the pump 8.
The slurry is metered and supplied to the slurry mixing tank.
13は攪拌翼、14は加熱ジャケットである。13 is a stirring blade, and 14 is a heating jacket.
以上かかる構成よりなる本発明方法によると循iEG量
の変動を補償し、反応系内のEG量を一定にし、簡単に
過不足なく必要最少量のEGを反応系に補給することが
出来るので、EG使用量を最少にすることが出来、その
結果ポリエステルの製造コストを従来よりも下げること
が出来る。According to the method of the present invention having the above configuration, it is possible to compensate for fluctuations in the amount of circulating iEG, keep the amount of EG in the reaction system constant, and easily replenish the minimum necessary amount of EG to the reaction system without excess or deficiency. The amount of EG used can be minimized, and as a result, the manufacturing cost of polyester can be lowered than before.
また操作を安定化させることが可能となるので、均一な
品質のエステル化物が得られる。Furthermore, since it becomes possible to stabilize the operation, an esterified product of uniform quality can be obtained.
次に本発明方法の実施例、比較例を示すが、本発明はこ
れらに限定されるものではない。Next, Examples and Comparative Examples of the method of the present invention will be shown, but the present invention is not limited thereto.
実施例 1
第1図に示す装置において、スラリー混合槽2にテレフ
タル酸を24.2kg/時、ポンプ8によってEGを2
2.6ky/時また2酸化チタンをポリマー濃度に換算
して0.5重量係になる量を、および重合触媒とし、て
蓚酸チタニルカリウムをテレフタル酸1モルに対して2
0μmol添加して混合攪拌1スラリー状にした。Example 1 In the apparatus shown in FIG.
2.6ky/hour Also, titanium dioxide was added in an amount equivalent to 0.5 weight ratio in terms of polymer concentration, and titanyl potassium oxalate was added as a polymerization catalyst to 2.6ky/hour per mole of terephthalic acid.
0 μmol was added and mixed and stirred to form a slurry.
このスラリー46.8k[を反応温度260℃、反応圧
力0.5 kg/crrt Gで操作されるエステル化
反応器3に供給し連続的に反応させた結果、テレフタル
酸のエステル化率が87%のオリゴマーが得られた。This slurry (46.8k) was supplied to the esterification reactor 3 operated at a reaction temperature of 260°C and a reaction pressure of 0.5 kg/crrtG and reacted continuously. As a result, the esterification rate of terephthalic acid was 87%. oligomers were obtained.
これをさらに反応温度260℃、常圧のエステル化反応
器4に供給し2、01v/時のEGと共にエステル化反
応を続けたところエステル化率が96%のオリゴマーが
得られた。This was further fed to the esterification reactor 4 at a reaction temperature of 260° C. and normal pressure, and the esterification reaction was continued with 2.01 v/hour of EG, resulting in an oligomer with an esterification rate of 96%.
次に反応温度260℃、反応圧力50Torr。の反応
器にて連続的に反応させると、平均重合度14.5のプ
レポリマーが得られた。Next, the reaction temperature was 260°C and the reaction pressure was 50 Torr. When the reaction was carried out continuously in a reactor, a prepolymer having an average degree of polymerization of 14.5 was obtained.
このプレポリマーを横型1軸反応器にて反応温度275
℃、反応圧力5Torr、で連続的に反応させ、極限粘
度0.35のプレポリマーにした後、横型2軸反応器に
て、反応温度275℃、反応圧力0.7Torr、 K
て連続的に反応させ極限粘度0.63.DEG値(ポリ
エチレンテレフタレート単位数当りのエーテル結合単位
数、%)1.31、の品質良好なポリエステルを得た。This prepolymer was reacted at a reaction temperature of 275 in a horizontal uniaxial reactor.
℃ and a reaction pressure of 5 Torr to obtain a prepolymer with an intrinsic viscosity of 0.35.Then, in a horizontal twin-shaft reactor, the reaction temperature was 275℃ and the reaction pressure was 0.7 Torr.
The intrinsic viscosity was 0.63. A good quality polyester with a DEG value (number of ether bond units per polyethylene terephthalate unit, %) of 1.31 was obtained.
一刀エステル化反応器3および4で発生する蒸気は常圧
で操作される蒸留塔5に供給され、塔頂より水を排出す
ると同時に、塔底より若干のオリゴマー、および7重量
係の水分を含むEGをEG調合槽1に導いた。The steam generated in the Itto esterification reactors 3 and 4 is supplied to a distillation column 5 operated at normal pressure, and at the same time water is discharged from the top of the column, and at the same time some oligomers and 7 parts by weight of water are contained from the bottom of the column. EG was introduced into EG mixing tank 1.
また配管15より水分0.5重量係のEGをEG調合槽
1の貯留量が一定となる様にコントロール弁で制御しな
がら供給した。Further, EG having a water content of 0.5 weight was supplied from the pipe 15 while being controlled by a control valve so that the amount stored in the EG mixing tank 1 was kept constant.
この運転を4日間連続的に行なった結果、テレフタル酸
に対して補給されたEGのモル比は平均して1.08で
あった。As a result of continuously performing this operation for four days, the molar ratio of EG supplied to terephthalic acid was 1.08 on average.
比較例 1
従来の反応装置を用いてテレフタル酸とその1.08モ
ル倍のEGを混合し、反応温度260℃、反応圧力4k
g/cAGにて発生する蒸気からEGを還流しつつ連続
的にエステル化反応を行ない、テレフタル酸のエステル
化率が85係になったオリゴマーを反応温度260℃、
反応圧力常圧の反応器に導ひき、エステル化反応を続け
た。Comparative Example 1 Using a conventional reaction apparatus, terephthalic acid and 1.08 moles of EG were mixed at a reaction temperature of 260°C and a reaction pressure of 4k.
The esterification reaction was carried out continuously while refluxing EG from the steam generated in g/cAG, and the oligomer whose esterification rate of terephthalic acid became 85 was heated at a reaction temperature of 260°C.
The reaction pressure was introduced into a reactor at normal pressure to continue the esterification reaction.
ここでエステル化率を92%址で反応させたオリゴマー
を実施例1と反じ方法で重縮合反応を行ない、極限粘度
0.61のポリエステルを得られたが、DEG値は2.
18もあった。Here, the oligomers reacted at an esterification rate of 92% were subjected to a polycondensation reaction in the same manner as in Example 1, and a polyester with an intrinsic viscosity of 0.61 was obtained, but the DEG value was 2.
There were also 18.
比較例 2
比較例1において最初のエステル化反応器の圧力を4k
g/crAGから常圧に下げて実験を行なったところエ
ステル化率が急激に下がり次の反応器への移送が出来す
くすり、実験を中止した。Comparative Example 2 In Comparative Example 1, the pressure of the first esterification reactor was set to 4k.
When the experiment was carried out by lowering the pressure from g/crAG to normal pressure, the esterification rate dropped rapidly, and the experiment was discontinued as the pressure could not be transferred to the next reactor.
比較例 3
実施例1においてEG調合槽を用いず蒸留塔底から排出
するEGを直接スラリー混合槽2に供給し、また別にE
Gをテレフタル酸に対して1.25モル倍(10,8k
g/時)スラリー混合槽2に供給した。Comparative Example 3 In Example 1, the EG discharged from the bottom of the distillation column was directly supplied to the slurry mixing tank 2 without using the EG mixing tank, and the EG was separately supplied to the slurry mixing tank 2.
G is 1.25 times the mole of terephthalic acid (10,8k
g/hour) was supplied to the slurry mixing tank 2.
又スラリーのエステル化反応器への移送はスラリー混合
槽の貯留量が一定になる様制御した。Further, the transfer of the slurry to the esterification reactor was controlled so that the amount stored in the slurry mixing tank was kept constant.
こうして実施例1と同様に反応を続けたところスラリー
のテレフタル酸に対するEGのモル比が初め2.5であ
ったが除々に増加し続け3.5以上となりまたエステル
化反応器3における熱供給量が不足して来て設定温度が
下がり始めだので反応を中止した。When the reaction was continued in the same manner as in Example 1, the molar ratio of EG to terephthalic acid in the slurry was initially 2.5, but gradually continued to increase and reached 3.5 or more, and the amount of heat supplied to the esterification reactor 3 The reaction was stopped because the set temperature started to drop due to insufficient amount of water.
第1図は本発明の具体例を示す模式図である。
1・・・・・・EG調合槽、2・・・・・・スラリー混
合槽、3.4・・・・・・エステル化反応器、5・・・
・・・蒸留塔、6.10・・・・・・コントロール弁、
7・・・・・・滑液量検出端、8,9,12・・・・・
・ポンプ、11・・・・・・圧力検出端、13・・・・
・・攪拌翼、14・・・・・・加熱ジャケット、15.
16,17,18,19,20,21゜22.23.2
4・・・・・・配管。FIG. 1 is a schematic diagram showing a specific example of the present invention. 1...EG mixing tank, 2...Slurry mixing tank, 3.4...Esterification reactor, 5...
... Distillation column, 6.10 ... Control valve,
7... Synovial fluid amount detection end, 8, 9, 12...
・Pump, 11...Pressure detection end, 13...
... Stirring blade, 14 ... Heating jacket, 15.
16, 17, 18, 19, 20, 21゜22.23.2
4...Piping.
Claims (1)
槽にて混合しスラリーとなし、該スラリーを連続的に0
〜2に9/crAGの圧力に保たれたエステル化反応器
に供給してエステル化反応を行なわせるに際し、前記エ
ステル化反応器で発生する蒸気よりエチレングリコール
を回収してエチレングリコール調合槽に導ひき、該調合
槽の貯留量が一定となるように、反応系外から反応によ
って消費された量のエチレングリコールを補給し、混合
した後計量して前記スラリー混合槽または/およびエス
テル化反応器へ循環することを特徴とするテレフタル酸
の連続エステル化方法。1. Mix terephthalic acid and ethylene glycol in a slurry mixing tank to form a slurry, and continuously make the slurry 0.
When supplying to the esterification reactor maintained at a pressure of 9/crAG to perform the esterification reaction, ethylene glycol is recovered from the steam generated in the esterification reactor and introduced into the ethylene glycol preparation tank. Then, the amount of ethylene glycol consumed by the reaction is replenished from outside the reaction system so that the amount stored in the slurry mixing tank is constant, and after mixing, it is weighed and transferred to the slurry mixing tank or/and esterification reactor. A method for continuous esterification of terephthalic acid characterized by circulation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9898677A JPS5817453B2 (en) | 1977-08-17 | 1977-08-17 | Continuous esterification method of terephthalic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9898677A JPS5817453B2 (en) | 1977-08-17 | 1977-08-17 | Continuous esterification method of terephthalic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5432433A JPS5432433A (en) | 1979-03-09 |
JPS5817453B2 true JPS5817453B2 (en) | 1983-04-07 |
Family
ID=14234311
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9898677A Expired JPS5817453B2 (en) | 1977-08-17 | 1977-08-17 | Continuous esterification method of terephthalic acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5817453B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0761713A3 (en) * | 1995-08-28 | 1999-04-14 | Toray Industries, Inc. | Method for producing polyesters |
-
1977
- 1977-08-17 JP JP9898677A patent/JPS5817453B2/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0761713A3 (en) * | 1995-08-28 | 1999-04-14 | Toray Industries, Inc. | Method for producing polyesters |
CN1082969C (en) * | 1995-08-28 | 2002-04-17 | 东丽株式会社 | Poly-ester mfg. method |
Also Published As
Publication number | Publication date |
---|---|
JPS5432433A (en) | 1979-03-09 |
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