JPH0710981A - Production of polybutylene terephthalate - Google Patents
Production of polybutylene terephthalateInfo
- Publication number
- JPH0710981A JPH0710981A JP15365393A JP15365393A JPH0710981A JP H0710981 A JPH0710981 A JP H0710981A JP 15365393 A JP15365393 A JP 15365393A JP 15365393 A JP15365393 A JP 15365393A JP H0710981 A JPH0710981 A JP H0710981A
- Authority
- JP
- Japan
- Prior art keywords
- butanediol
- reaction
- oligomer
- polybutylene terephthalate
- metal hydroxide
- 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
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリブチレンテレフタレ
ートの製造方法に関するものであり、特に、特定の製法
によって得られた１，４−ブタンジオールを原料として
用いるポリブチレンテレフタレートの製造方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polybutylene terephthalate, and more particularly to a method for producing polybutylene terephthalate using 1,4-butanediol obtained by a specific production method as a raw material. .
【０００２】[0002]
【従来の技術】従来、ポリブチレンテレフタレートは射
出成形材料として電気・電子部品や機械部品に使用され
てきている。ポリブチレンテレフタレートの製造方法と
しては、１，４−ブタンジオールとテレフタル酸とをエ
ステル化反応させ、得られたオリゴマーを重縮合触媒の
存在下、重縮合する製造方法が代表的である。2. Description of the Related Art Conventionally, polybutylene terephthalate has been used as an injection molding material for electric / electronic parts and mechanical parts. A typical production method of polybutylene terephthalate is a production method in which 1,4-butanediol and terephthalic acid are subjected to an esterification reaction, and the resulting oligomer is polycondensed in the presence of a polycondensation catalyst.
【０００３】この方法の場合、１，４−ブタンジオール
を通常、テレフタル酸に対して１．２〜２．０モル倍使
用するが、エステル化反応時に、供給した１，４−ブタ
ンジオールの一部が副反応によりテトラヒドロフランに
変換する傾向ある。１，４−ブタンジオールの一部がテ
トラヒドロフランに変換されると、１，４−ブタンジオ
ールの原単位低下の他、エステル化反応率が向上せず、
又、高分子量のポリマーが得られ難いという問題があっ
た。更に、このテトラヒドロフランが副生する傾向は、
特に、１，４−ブタンジオールの有機酸エステル（例え
ば、１，４−ジアセトキシブタン）を陽イオン交換樹脂
よりなる触媒を用いて加水分解することにより製造され
た１，４−ブタンジオールを原料とするエステル化反応
の場合に著しく、ポリブチレンテレフタレートを製造す
る上で大きな問題であった。In the case of this method, 1,4-butanediol is usually used in an amount of 1.2 to 2.0 mole times that of terephthalic acid, but one of 1,4-butanediol supplied during the esterification reaction is used. Part tends to be converted to tetrahydrofuran by a side reaction. When a part of 1,4-butanediol is converted to tetrahydrofuran, the basic unit of 1,4-butanediol is reduced and the esterification reaction rate is not improved.
There is also a problem that it is difficult to obtain a high molecular weight polymer. Furthermore, the tendency of this tetrahydrofuran to be a byproduct is
In particular, 1,4-butanediol produced by hydrolyzing an organic acid ester of 1,4-butanediol (for example, 1,4-diacetoxybutane) using a catalyst composed of a cation exchange resin is used as a raw material. In the case of the esterification reaction described above, it was a serious problem in producing polybutylene terephthalate.
【０００４】こうしたエステル化反応時のテトラヒドロ
フランの副生を抑制する方法としては、例えば、特公昭
５５−３００１０号公報に有機スズと有機チタンを組合
せた触媒を用いる方法が記載されているが、この方法の
場合、有機スズ触媒の使用の程度により生成するポリマ
ーの色調が黄色くなる傾向にある上、上述の１，４−ブ
タンジオールを原料とする方法においては、効果が必ら
ずしも十分ではなかった。As a method for suppressing the by-product of tetrahydrofuran at the time of the esterification reaction, for example, Japanese Patent Publication No. 55-30010 discloses a method using a catalyst in which organic tin and organic titanium are combined. In the case of the method, the color tone of the polymer produced tends to become yellow depending on the degree of use of the organotin catalyst, and the above-mentioned method using 1,4-butanediol as a raw material is not necessarily effective. There wasn't.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、エス
テル化反応におけるテトラヒドロフランの副生を抑制し
高分子量のポリマーを得ることができる、特定の製法で
得られた１，４−ブタンジオールを原料として用いるポ
リブチレンテレフタレートの製造方法を提供することに
ある。DISCLOSURE OF THE INVENTION The object of the present invention is to provide 1,4-butanediol obtained by a specific production method, which can suppress the by-product of tetrahydrofuran in the esterification reaction and obtain a high molecular weight polymer. It is to provide a method for producing polybutylene terephthalate used as a raw material.
【０００６】[0006]
【課題を解決するための手段】本発明は上述の問題を解
決するためになされたものであり、その要旨は、１，４
−ブタンジオールの有機酸エステルを陽イオン交換樹脂
よりなる触媒の存在下、加水分解することにより得た
１，４−ブタンジオールとテレフタル酸とをエステル化
反応してオリゴマーを得、次いで、該オリゴマーを重縮
合するポリブチレンテレフタレートの製造方法におい
て、前記エステル化反応に用いる１，４−ブタンジオー
ルに、該１，４−ブタンジオールに対して０．５〜１０
ｐｐｍのアルカリ金属の水酸化物又はアルカリ土類金属
の水酸化物を添加することを特徴とするポリブチレンテ
レフタレートの製造方法に存する。The present invention has been made to solve the above problems, and the gist thereof is 1, 4
An ester of 1,4-butanediol obtained by hydrolyzing an organic acid ester of butanediol in the presence of a catalyst composed of a cation exchange resin and terephthalic acid to obtain an oligomer, and then the oligomer; In the method for producing polybutylene terephthalate, which comprises polycondensation of 1,4-butanediol used in the esterification reaction, 0.5 to 10 is used with respect to the 1,4-butanediol.
It exists in the manufacturing method of the polybutylene terephthalate characterized by adding ppm alkali metal hydroxide or alkaline earth metal hydroxide.
【０００７】以下、本発明を詳細に説明する。本発明に
おける１，４−ブタンジオールとしては、１，４−ブタ
ンジオールの有機酸エステルを陽イオン交換樹脂よりな
る触媒の存在下、加水分解することによって得られるも
のを用いる。１，４−ブタンジオールの有機酸エステル
としては酢酸ジエステル（１，４−ジアセトキシブタ
ン）、プロピオン酸ジエステルなどのＣ2 〜Ｃ4 の有機
酸のジエステルを用いることができ、好ましくは１，４
−ジアセトキシブタンである。The present invention will be described in detail below. The 1,4-butanediol used in the present invention is one obtained by hydrolyzing an organic acid ester of 1,4-butanediol in the presence of a catalyst composed of a cation exchange resin. As the organic acid ester of 1,4-butanediol, a diester of C 2 to C 4 organic acid such as acetic acid diester (1,4-diacetoxybutane) and propionic acid diester can be used, and preferably 1,4
-Diacetoxybutane.
【０００８】加水分解反応は、１，４−ブタンジオール
の有機酸エステルと水とを陽イオン交換樹脂触媒の存在
下、反応温度３０〜８０℃程度において行なう。水の使
用量は１，４−ブタンジオールの有機酸エステルに対し
て０．５〜２重量倍である。陽イオン交換樹脂触媒とし
てはスルホン酸型などの強酸性陽イオン交換樹脂（Ｈ
型）を用いる。加水分解反応は充填層方式、懸濁槽方式
などで行なえるが充填層方式が好ましい。加水分解反応
後、反応液を常圧又は減圧条件下蒸留することにより、
１，４−ブタンジオールを分離回収できる。The hydrolysis reaction is carried out by reacting an organic acid ester of 1,4-butanediol with water in the presence of a cation exchange resin catalyst at a reaction temperature of about 30 to 80 ° C. The amount of water used is 0.5 to 2 times the weight of the organic acid ester of 1,4-butanediol. As a cation exchange resin catalyst, strong acid cation exchange resin (H
Type) is used. The hydrolysis reaction can be carried out by a packed bed system, a suspension tank system or the like, but the packed bed system is preferred. After the hydrolysis reaction, by distilling the reaction solution under normal pressure or reduced pressure,
1,4-butanediol can be separated and recovered.
【０００９】１，４−ブタンジオールの有機酸エステル
を加水分解することによって得られた１，４−ブタンジ
オールはテレフタール酸とエステル反応させ、オリゴマ
ーを得、次いで該オリゴマーを重縮合することによりポ
リブチレンテレフタレートを製造する。本発明において
は、このエステル化反応に用いる１，４−ブタンジオー
ルにアルカリ金属の水酸化物又はアルカリ土類金属の水
酸化物を添加する。アルカリ金属の水酸化物又はアルカ
リ土類金属の水酸化物の添加量は１，４−ブタンジオー
ルに対して合計量で０．５〜１０ｐｐｍであり、より好
ましくは１〜５ｐｐｍである。０．５ｐｐｍより少ない
とＴＨＦ副生率の低下の程度が小さくなり、又、１０ｐ
ｐｍより多いと重縮合の反応速度の低下が大きくなる。The 1,4-butanediol obtained by hydrolyzing an organic acid ester of 1,4-butanediol is subjected to ester reaction with terephthalic acid to obtain an oligomer, and then polycondensation of the oligomer is carried out to obtain a poly Produces butylene terephthalate. In the present invention, an alkali metal hydroxide or an alkaline earth metal hydroxide is added to 1,4-butanediol used in this esterification reaction. The total amount of the alkali metal hydroxide or the alkaline earth metal hydroxide added is 0.5 to 10 ppm, and more preferably 1 to 5 ppm, based on 1,4-butanediol. If it is less than 0.5 ppm, the degree of decrease in the THF byproduct rate will be small,
When it is more than pm, the reaction rate of polycondensation is greatly reduced.
【００１０】アルカリ金属の水酸化物としてはＮａＯ
Ｈ、ＫＯＨ等が挙げられ、アルカリ土類金属の水酸化物
としてはＢａ（ＯＨ）2 、Ｃａ（ＯＨ）2 、Ｍｇ（Ｏ
Ｈ）2 等が挙げられる。これらの水酸化物は二種類以上
併用することもできる。アルカリ金属の水酸化物又はア
ルカリ土類金属の水酸化物を１，４−ブタンジオールに
添加する方法としてはアルカリ金属の水酸化物又はアル
カリ土類金属の水酸化物を１，４−ブタンジオールに溶
解あるいはスラリー状で、原料である１，４−ブタンジ
オールに添加するのが好ましく、又１，４−ブタンジオ
ールとテレフタール酸との混合物中であってもエステル
化反応初期であれば添加することができる。As the alkali metal hydroxide, NaO is used.
H, KOH, and the like, and examples of hydroxides of alkaline earth metals include Ba (OH) 2 , Ca (OH) 2 , and Mg (O
H) 2 and the like. Two or more kinds of these hydroxides can be used in combination. As a method for adding an alkali metal hydroxide or an alkaline earth metal hydroxide to 1,4-butanediol, an alkali metal hydroxide or an alkaline earth metal hydroxide is added to 1,4-butanediol. It is preferable to add it in the form of a solution or a slurry to 1,4-butanediol as a raw material, and even in a mixture of 1,4-butanediol and terephthalic acid at the initial stage of the esterification reaction. be able to.
【００１１】エステル化反応及び重縮合反応は公知の方
法に準じて行なうことができる。１，４−ブタンジオー
ルのテレフタール酸に対するモル比は１．２〜１．８倍
モル程度である。エステル化反応は２００〜２５０℃程
度の反応温度において、常圧あるいは７６０〜２００ｍ
ｍ程度の減圧下に行なう。エステル化反応時に添加する
触媒は例えばチタン化合物やスズ化合物等ポリブチレン
テレフタレートの重合触媒として一般に用いられている
ものを使用することができる。The esterification reaction and polycondensation reaction can be carried out according to known methods. The molar ratio of 1,4-butanediol to terephthalic acid is about 1.2 to 1.8 times the molar ratio. The esterification reaction is carried out at a reaction temperature of about 200 to 250 ° C. under normal pressure or 760 to 200 m.
It is performed under reduced pressure of about m. As the catalyst to be added during the esterification reaction, for example, a titanium compound, a tin compound or the like which is generally used as a polymerization catalyst for polybutylene terephthalate can be used.
【００１２】重縮合反応においては、２３０〜２６０℃
程度の反応温度で圧力を常圧から１ｍｍＨｇ以下に減圧
し生成した水を系外にパージしつつ反応を行ないポリブ
チレンテレフタレートを得る。重縮合反応における触媒
としては、例えば有機チタン系触媒、有機スズ系触媒等
公知のものを用いることができる。In the polycondensation reaction, 230 to 260 ° C.
The pressure is reduced from atmospheric pressure to 1 mmHg or less at a reaction temperature of about 1%, and the reaction is performed while purging the generated water out of the system to obtain polybutylene terephthalate. As the catalyst in the polycondensation reaction, known catalysts such as organic titanium-based catalysts and organic tin-based catalysts can be used.
【００１３】[0013]
【発明の効果】１，４−ブタンジオールの有機酸エステ
ルを陽イオン交換樹脂よりなる触媒の存在下、加水分解
することによって得られた１，４−ブタンジオールとテ
レフタール酸とのエステル化反応において、副生するテ
トラヒドロフランの生成を抑制し高分子量のポリマーを
得ることができるポリブチレンテレフタレートの製造方
法を提供できる。INDUSTRIAL APPLICABILITY In the esterification reaction of terephthalic acid with 1,4-butanediol obtained by hydrolyzing an organic acid ester of 1,4-butanediol in the presence of a catalyst composed of a cation exchange resin. It is possible to provide a method for producing polybutylene terephthalate capable of suppressing the formation of by-produced tetrahydrofuran and obtaining a high molecular weight polymer.
【００１４】[0014]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明はその要旨を越えない限り、以下の実施
例に限定されるものではない。なお、オリゴマーのエス
テル化率は下記に示す式で求めた。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The esterification rate of the oligomer was determined by the formula shown below.
【００１５】[0015]
【数１】 [Equation 1]
【００１６】オリゴマーのケン化価はオリゴマーをケン
化するのに必要な水酸化ナトリウムの量から求め、オリ
ゴマーの酸価はオリゴマーをジメチルホルムアミドに溶
解後水酸化ナトリウムで滴定することにより求めた。Ｔ
ＨＦ副生率は下記に示す式で求めた。The saponification value of the oligomer was determined from the amount of sodium hydroxide required to saponify the oligomer, and the acid value of the oligomer was determined by dissolving the oligomer in dimethylformamide and titrating with sodium hydroxide. T
The HF by-product rate was calculated by the formula shown below.
【００１７】[0017]
【数２】 [Equation 2]
【００１８】ポリブチレンテレフタレートの極限粘度は
ポリマー０．５ｇをフェノール／１，１，２，２−テト
ラクロロエタン＝１／１（ｗｔ比）５０ｍｌに溶解し３
０℃でウベローデ型粘度計にて測定した。The intrinsic viscosity of polybutylene terephthalate was 3 g by dissolving 0.5 g of polymer in 50 ml of phenol / 1,1,2,2-tetrachloroethane = 1/1 (wt ratio).
It was measured with an Ubbelohde viscometer at 0 ° C.
【００１９】［実施例１］ （１４−ブタンジオールの製造方法）４００ｃｃの陽イ
オン交換樹脂（三菱化成（株）製 ＳＫ１ＢＨ型）を直
径５ｃｍ、高さ４０ｃｍのガラス製反応器に充填し（充
填層高２０ｃｍ）、反応器を５０℃に保ちながら１４−
ジアセトキシブタンと水をそれぞれ１００ｇ／ｈｒで反
応器に供給した。反応器出口より得られた反応液をガス
クロマトグラフィーで分析したところ、下記の組成であ
った。Example 1 (Production Method of 14-Butanediol) 400 cc of a cation exchange resin (SK1BH type manufactured by Mitsubishi Kasei Co., Ltd.) was filled in a glass reactor having a diameter of 5 cm and a height of 40 cm (filling). (Layer height 20 cm), 14-while keeping the reactor at 50 ° C
Diacetoxybutane and water were each fed to the reactor at 100 g / hr. When the reaction liquid obtained from the outlet of the reactor was analyzed by gas chromatography, it had the following composition.
【００２０】[0020]
【表１】 酢酸 ２３．０％（重量％） １，４−ジアセトキシブタン ５．４％ １−ヒドロキシ−４−アセトキシブタン １７．１％ １，４−ブタンジオール １１．３％ 水 ４３．１％Table 1 Acetic acid 23.0% (wt%) 1,4-diacetoxybutane 5.4% 1-hydroxy-4-acetoxybutane 17.1% 1,4-butanediol 11.3% water 43.1 %
【００２１】上記の様にして得られた反応液５ｋｇを真
空ジャケット付の８０段の７５φオルダーショウ型蒸留
装置で常圧蒸留して水と酢酸を留去した後、塔頂圧力２
０ｍｍＨｇで減圧蒸留して２５３ｇの１，４−ブタンジ
オールを得た。この１，４−ブタンジオールをガスクロ
マトグラフィーで分析したところ、純度は９９．７重量
％であった。5 kg of the reaction solution obtained as described above was subjected to atmospheric distillation using an 80-stage 75φ Oldershaw type distillation apparatus equipped with a vacuum jacket to distill off water and acetic acid, and then the top pressure 2
Vacuum distillation was performed at 0 mmHg to obtain 253 g of 1,4-butanediol. When the 1,4-butanediol was analyzed by gas chromatography, the purity was 99.7% by weight.
【００２２】（エステル化反応及び重縮合反応）分留管
付１リットルフラスコに、ＮａＯＨを１ｐｐｍ添加した
１，４−ブタンジオール１００ｇとテレフタル酸８１．
４ｇを入れ攪拌しながら昇温し内温が２１０℃になった
時点でテトラ−ｎ−ブチルチタネート０．０４３ｇを添
加し１時間で２２５℃まで昇温した。内温が２２５℃に
なった時点で、そのまま３時間エステル化反応を続け
た。反応中生成する水とテトラヒドロフランは分留管上
部より留去させた。反応は触媒添加後４時間で終了と
し、反応終了後のオリゴマーの、酸価とケン化価を測定
してエステル化率を求めた。また、留出液中のテトラヒ
ドロフランをガスクロマトグラフィーで分析して、ＴＨ
Ｆ副生率を求めた。(Esterification reaction and polycondensation reaction) In a 1-liter flask equipped with a fractionating tube, 100 g of 1,4-butanediol containing 1 ppm of NaOH and 81.terephthalic acid were added.
4 g was added and the temperature was raised with stirring. When the internal temperature reached 210 ° C, 0.043 g of tetra-n-butyl titanate was added and the temperature was raised to 225 ° C in 1 hour. When the internal temperature reached 225 ° C, the esterification reaction was continued for 3 hours. Water and tetrahydrofuran produced during the reaction were distilled off from the upper part of the fractionating tube. The reaction was terminated 4 hours after the addition of the catalyst, and the acid value and saponification value of the oligomer after the reaction were measured to determine the esterification rate. In addition, the tetrahydrofuran in the distillate was analyzed by gas chromatography to detect TH
The F byproduct rate was calculated.
【００２３】上記の様にして得られたオリゴマー１５０
ｇをガラス製の重合管に入れ、窒素雰囲気下で２２５℃
に加熱して溶解した。溶解したオリゴマーにテトラ−ｎ
−ブチルチタネート０．０４３ｇを添加し常圧から０．
５ｍｍＨｇまで４５分で徐々に減圧した。同時に２２５
℃から２４５℃まで３０分で昇温し重縮合反応させた。
触媒添加後２時間３０分で反応を終了し、抜き出したポ
リブチレンテレフタレートの極限粘度を測定した。The oligomer 150 obtained as described above
g in a polymerization tube made of glass and put in a nitrogen atmosphere at 225 ° C.
It was heated to dissolve. Tetra-n in the dissolved oligomer
-Butyl titanate 0.043 g was added and the pressure was changed from normal pressure to 0.
The pressure was gradually reduced to 5 mmHg in 45 minutes. 225 at the same time
The temperature was raised from 30 ° C. to 245 ° C. in 30 minutes to carry out a polycondensation reaction.
The reaction was completed 2 hours and 30 minutes after the catalyst was added, and the intrinsic viscosity of the extracted polybutylene terephthalate was measured.
【００２４】［実施例２］実施例１において、ＮａＯＨ
を１ｐｐｍ添加する代りに２．５ｐｐｍ添加する以外は
実施例１と全く同様に行ない、エステル化率及びＴＨＦ
副生率を求め又極限粘度を測定した。Example 2 In Example 1, NaOH
Was carried out in the same manner as in Example 1 except that 2.5 ppm was added instead of 1 ppm.
The by-product rate was obtained and the intrinsic viscosity was measured.
【００２５】［実施例３］実施例１において、ＮａＯＨ
を１ｐｐｍ添加する代りに５．０ｐｐｍ添加する以外は
実施例１と全く同様に行ない、エステル化率及びＴＨＦ
副生率を求め又極限粘度を測定した。[Example 3] In Example 1, NaOH was used.
Was carried out in the same manner as in Example 1 except that 5.0 ppm was added instead of 1 ppm.
The by-product rate was obtained and the intrinsic viscosity was measured.
【００２６】［実施例４］実施例１において、ＮａＯＨ
を１ｐｐｍ添加する代りにＫＯＨを５．０ｐｐｍ添加す
る以外は実施例１と全く同様に行ない、エステル化率及
びＴＨＦ副生率を求め又極限粘度を測定した。[Example 4] In Example 1, NaOH was used.
Was carried out in the same manner as in Example 1 except that KOH was added at 5.0 ppm instead of 1 ppm, and the esterification rate and the THF byproduct rate were determined and the intrinsic viscosity was measured.
【００２７】［実施例５］実施例１において、ＮａＯＨ
を１ｐｐｍ添加する代りにＣａ（ＯＨ）2 を５．０ｐｐ
ｍ添加する以外は実施例１と全く同様に行ない、エステ
ル化率及びＴＨＦ副生率を求め又極限粘度を測定した。[Example 5] In Example 1, NaOH
Ca (OH) 2 5.0pp instead of adding 1ppm
The same procedure as in Example 1 was carried out except that m was added, and the esterification rate and the THF byproduct rate were determined and the intrinsic viscosity was measured.
【００２８】［実施例６］実施例１において、ＮａＯＨ
を１ｐｐｍ添加する代りにＢａ（ＯＨ）2 を５．０ｐｐ
ｍ添加する以外は実施例１と全く同様に行ない、エステ
ル化率及びＴＨＦ副生率を求め又極限粘度を測定した。Example 6 In Example 1, NaOH
In place of adding 1 ppm of Ba (OH) 2 5.0 pp
The same procedure as in Example 1 was carried out except that m was added, and the esterification rate and the THF byproduct rate were determined and the intrinsic viscosity was measured.
【００２９】［比較例１］実施例１において、ＮａＯＨ
を添加しない１，４−ブタンジオールを用いる以外は実
施例１と全く同様に行ない、エステル化率及びＴＨＦ副
生率を求め又極限粘度を測定した。Comparative Example 1 In Example 1, NaOH
The same procedure as in Example 1 was carried out except that 1,4-butanediol was used in which was not added, and the esterification rate and the THF byproduct rate were determined and the intrinsic viscosity was measured.
【００３０】［比較例２］実施例１において、ＮａＯＨ
を１ｐｐｍ添加する代りに２０ｐｐｍ添加する以外は実
施例１と全く同様に行ない、エステル化率及びＴＨＦ副
生率を求め又極限粘度を測定した。[Comparative Example 2] In Example 1, NaOH was used.
Was carried out in the same manner as in Example 1 except that 20 ppm was added instead of 1 ppm, the esterification rate and the THF by-product rate were determined, and the intrinsic viscosity was measured.
【００３１】[0031]
【表２】 [Table 2]
【００３２】表１より実施例１ないし実施例６は、比較
例１に比べＴＨＦ副生率が低く、エステル化率が高く、
かつ極限粘度も高い、又比較例２に比べ、極限粘度の高
いポリブチレンテレフタレートが得られていることがわ
かる。From Table 1, Examples 1 to 6 have a lower THF by-product rate and a higher esterification rate than Comparative Example 1,
It can be seen that polybutylene terephthalate having a high intrinsic viscosity and a higher intrinsic viscosity than that of Comparative Example 2 was obtained.
Claims (1)
ルを陽イオン交換樹脂よりなる触媒の存在下、加水分解
することにより得た１，４−ブタンジオールとテレフタ
ル酸とをエステル化反応してオリゴマーを得、次いで、
該オリゴマーを重縮合するポリブチレンテレフタレート
の製造方法において、前記エステル化反応に用いる１，
４−ブタンジオールに、該１，４−ブタンジオールに対
して０．５〜１０ｐｐｍのアルカリ金属の水酸化物又は
アルカリ土類金属の水酸化物を添加することを特徴とす
るポリブチレンテレフタレートの製造方法。1. An esterification reaction of 1,4-butanediol and terephthalic acid obtained by hydrolyzing an organic acid ester of 1,4-butanediol in the presence of a catalyst composed of a cation exchange resin. Obtain the oligomer, then
In the method for producing polybutylene terephthalate in which the oligomer is polycondensed, 1, which is used in the esterification reaction,
Production of polybutylene terephthalate, characterized in that 0.5 to 10 ppm of an alkali metal hydroxide or an alkaline earth metal hydroxide is added to 4-butanediol with respect to the 1,4-butanediol. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15365393A JP3284665B2 (en) | 1993-06-24 | 1993-06-24 | Method for producing polybutylene terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15365393A JP3284665B2 (en) | 1993-06-24 | 1993-06-24 | Method for producing polybutylene terephthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710981A true JPH0710981A (en) | 1995-01-13 |
| JP3284665B2 JP3284665B2 (en) | 2002-05-20 |
Family
ID=15567246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15365393A Expired - Lifetime JP3284665B2 (en) | 1993-06-24 | 1993-06-24 | Method for producing polybutylene terephthalate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3284665B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001114884A (en) * | 1999-10-15 | 2001-04-24 | Toray Ind Inc | Method for producing polybutylene terephthalate |
| WO2013008686A1 (en) * | 2011-07-08 | 2013-01-17 | 三菱化学株式会社 | Composition containing 1,4-butanediol |
| US9598388B2 (en) | 2011-07-04 | 2017-03-21 | Mitsubishi Chemical Corporation | Method for producing tetrahydrofuran |
-
1993
- 1993-06-24 JP JP15365393A patent/JP3284665B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001114884A (en) * | 1999-10-15 | 2001-04-24 | Toray Ind Inc | Method for producing polybutylene terephthalate |
| JP4552243B2 (en) * | 1999-10-15 | 2010-09-29 | 東レ株式会社 | Process for producing polybutylene terephthalate |
| US9598388B2 (en) | 2011-07-04 | 2017-03-21 | Mitsubishi Chemical Corporation | Method for producing tetrahydrofuran |
| WO2013008686A1 (en) * | 2011-07-08 | 2013-01-17 | 三菱化学株式会社 | Composition containing 1,4-butanediol |
| US9434706B2 (en) | 2011-07-08 | 2016-09-06 | Mitsubishi Chemical Corporation | 1,4-butanediol-containing composition |
| US10472311B2 (en) | 2011-07-08 | 2019-11-12 | Mitsubishi Chemical Corporation | 1,4-butanediol-containing composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3284665B2 (en) | 2002-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6472500B2 (en) | Crystalline polyester resins and processes for their preparation | |
| TW575597B (en) | Process for producing polytrimethylene terephthalate | |
| KR100517853B1 (en) | Improved Process for Preparing High Molecular Weight Polyesters | |
| US5840957A (en) | Transesterification process using lanthanum compound catalyst | |
| US6245879B1 (en) | Purification of 1,3-propanediol in carbonyl-containing stream | |
| WO1995027749A1 (en) | Process for producing hydroxyl-terminated polycarbonate | |
| US7122698B2 (en) | Method for producing α-hydroxycarboxylate | |
| KR101020423B1 (en) | Process for the preparation of trimethylene terephthalate oligomers | |
| KR100734121B1 (en) | Zero-heel polyester process | |
| MXPA01012853A (en) | Method for the continuous production of polybutyleneterephthalate from terephthalic acid and butanediol. | |
| JP3720040B2 (en) | Naphthalenedicarboxylic acid esterification reaction product mixture or mixture, production method thereof, and production method of polyethylene naphthalate | |
| JPH0710981A (en) | Production of polybutylene terephthalate | |
| JP2005133093A6 (en) | Naphthalenedicarboxylic acid esterification reaction product mixture or mixture, production method thereof, and production method of polyethylene naphthalate | |
| JP3904532B2 (en) | Method for producing butylene terephthalate oligomer and method for producing polybutylene terephthalate | |
| JP4306038B2 (en) | Process for producing polybutylene terephthalate | |
| JP2004035742A (en) | Crystalline polyester resin and method for producing the same | |
| CA2261293C (en) | Improved process for preparing high molecular weight polyesters | |
| EP1378533A1 (en) | Crystalline polyester resins and processes for their preparation | |
| JPH06211979A (en) | Method for purifying polyoxytetramethylene glycol | |
| JPH07103073B2 (en) | Method for esterification of terephthalic acid | |
| KR20040006633A (en) | Crystalline polyester resins and processes for their preparation | |
| JPS5850975B2 (en) | Method for producing bis-(ω-hydroxybutyl) terephthalate and its low polymer | |
| MXPA01007635A (en) | Purification of recycled 1,3-propanediol during polyester preparation | |
| KR20140077342A (en) | Reparation method for ester oligomer with low acidity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090308 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090308 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100308 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110308 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120308 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130308 Year of fee payment: 11 |