JP4134325B2 - Process for producing aromatic polyester - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、芳香族ポリエステルの製造法に関する。詳しくは色調の改良された、芳香族ポリエステルを製造する方法に関する。
【０００２】
【従来の技術】
芳香族ヒドロキシカルボン酸類、芳香族ジカルボン酸類および芳香族ジオール類から選ばれる原料モノマー類を無水酢酸でアセチル化して得られる反応生成物、または予めアセチル化された原料モノマー類を縮重合して芳香族ポリエステルを製造する方法は良く知られており、その際、縮重合槽に分縮器を設けて留出物を分縮して凝縮物を回収しながら縮重合する方法も知られている（特許文献１参照。）。
一方、縮重合槽として工業的には、通常、ＳＵＳ３１６製のものが使用され（例えば、特許文献２参照）、分縮器もＳＵＳ３１６製のものが用いられる。
【０００３】
【特許文献１】
特開２０００−２１２２６４号公報（段落［０００５］）
【特許文献２】
特開２０００−１９１７６２号公報（段落［００２４］）
【０００４】
【発明が解決しようとする課題】
しかしながら、上記従来の方法で製造した芳香族ポリエステルの色調は必ずしも十分でなく、また近年、色調のより良い芳香族ポリエステルが望まれるようになってきている。
本発明の目的は色調の改良された芳香族ポリエステルの製造方法を提供することにある。
【０００５】
【発明が解決するための手段】
本発明者らは、かかる課題を解決するために鋭意検討した結果、縮重合槽に設けた分縮器の接液面の材質として、ＳＵＳ３１６は耐食性の点からは使用可能であるが、得られる芳香族ポリエステルの色調の点からは不十分であり、分縮器の接液面の材質として、ニッケル−モリブデン合金とすることによって、色調が改良された芳香族ポリエステルが得られることを見出し、本発明に至った。
【０００６】
すなわち本発明は、芳香族ポリエステルの原料モノマー類を無水酢酸でアセチル化して得られる反応生成物、または予め原料モノマー類の一部がアセチル化された原料モノマー類を、分縮器を設けた縮重合槽を用いて加熱して縮重合し、留出物を分縮して凝縮物を縮重合槽に回収しながら芳香族ポリエステルを製造する方法において、分縮器の接液面の材質をニッケル−モリブデン合金とすることを特徴とする芳香族ポリエステルの製造法である。
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
図１は本発明で使用する製造装置の概略図である。アセチル化反応槽（１）において原料モノマー類を無水酢酸で還流下にアセチル化する。反応生成物は移送管（５）によって縮重合槽（２）に移送される。反応生成物は加熱され、縮重合が行われる。留出物は留出管（７）によって分縮器（３）に送られ、冷媒（１２、１３）で冷却され、一部が凝縮し、凝縮物は回収管（８）によって縮重合槽に回収される。反応終了後、得られた縮重合体（６）は縮重合槽の底部から抜出される。分縮器で凝縮しなかった留出分は導管（９）によって凝縮器（４）に送られ、冷媒（１４、１５）で冷却され、凝縮液（１０）および未凝縮ガス（１１）に分離される。
【０００８】
本発明に用いられる芳香族ポリエステルの原料モノマー類としては、芳香族ヒドロキシカルボン酸類、芳香族ジカルボン酸類および芳香族ジオール類から選ばれ、通常、芳香族ヒドロキシルカルボン酸類、芳香族ジカルボン酸類および芳香族ジオール類が用いられる。
【０００９】
芳香族ヒドロキシカルボン酸類としては、例えば、下記一般式（１）、
ＨＯ−Ｘ−ＣＯＯＲ1 （１）
（式中、Ｒ1は水素、炭素数１〜６のアルキル基または炭素数６〜１６のアリール基を表し、Ｘは２価の芳香族基を表す。）で表されるものが挙げられる。
【００１０】
芳香族キドロキシルカルボン酸類として具体的には、ｐ−ヒドロキシ安息香酸、ｐ−ヒドロキシ安息香酸メチル、ｐ−ヒドロキシ安息香酸プロピル、ｐ−ヒドロキシ安息香酸フェニル、ｐ−ヒドロキシ安息香酸ベンジル、ｐ−（４−ヒドロキシフェニル）安息香酸、ｐ−（４−ヒドロキシフェニル）安息香酸メチル、２−ヒドロキシ−６−ナフトエ酸、２−ヒドロキシ−６−ナフトエ酸メチルおよび２−ヒドロキシ−６−ナフトエ酸フェニル等が例示される。中でもｐ−ヒドロキシ安息香酸、２−ヒドロキシ−６−ナフトエ酸等が好適である。
【００１１】
芳香族ジカルボン酸類としては、例えば、下記一般式（２）、
Ｒ2−Ｏ−ＣＯ−Ｙ−ＣＯ−Ｏ−Ｒ2 （２）
（式中、Ｒ2は水素、炭素数１〜６のアルキル基または炭素数６〜１６のアリール基または炭素数６〜１６のアリール基を表し、Ｙは２価の芳香族基を表す。）で表されるものが挙げられる。
【００１２】
この芳香族ジカルボン酸類として具体的には、テレフタル酸、イソフタル酸、４，４’−ジカルボキシジフェニル、１，２−ビス（４−カルボキシフェノキシ）エタン、２，５−ジカルボキシナフタレン、２，６−カルボキシナフタレン、１，４−ジカルボキシナフタレン、１，５−ジカルボキシナフタレン、テレフタル酸ジメチル、イソフタル酸ジメチル、テレフタル酸ジフェニル、イソフタル酸ジフェニル、４，４’−ジメトキシカルボニルジフェニル、２，６−ジメトキシカルボニルナフタレン、１，４−ジクロロカルボニルナフタレンおよび１，５−ジフェノキシカルボニルナフタレン等が例示される。中でも、テレフタル酸、イソフタル酸および２，６−ジカルボキシナフタレン等が好適である。
【００１３】
芳香族ジオール類としては、例えば、下記一般式（３）、
ＨＯ−Ｚ−ＯＨ （３）
（式中、Ｚは２価の芳香族基を表す。）で表されるのものが挙げられる。
【００１４】
この芳香族ジオール類として具体的には、ヒドロキノン、レゾルシン、カテコール、４，４’−ジヒドロキシジフェニル、４，４’−ヒドロキシベンゾフェノン、４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルエタン、４，４’−ジヒドロキシジフェニルエーテル、２，２−ビス（４−ヒドロキシフェニル）プロパン、４，４’−ヒドロキシジフェニルスルフォン、４，４’−ジヒドロキシジフェニルスルフィド、２，６−ジヒドロキシナフタレンおよび１，５−ヒドロキシナフタレン等が例示される。中でも、ヒドロキノン、レゾルシン、４，４’−ジヒドロキシジフェニル、２，２−ビス（４−ヒドロキシフェニル）プロパンおよび４，４’−ジヒドロキシジフェニルスルフォン等が好適である。
【００１５】
芳香族ヒドロキシカルボン酸類、芳香族ジカルボン酸類および芳香族ジオール類の使用比率は特に限定されないが、芳香族ヒドロキシカルボン酸類、芳香族ジカルボン酸類及び芳香族ジオール類の合計１００モルに対して、通常、芳香族ヒドロキシカルボン酸類が約３０〜８０モル、芳香族ジカルボン酸類が約１０〜３５モル、芳香族ジオール類が約１０〜３５モルから選ばれる範囲である。
【００１６】
アセチル化反応は還流下に行われ、その温度および圧力は特に限定されないが、通常、常圧下、約１４０〜１５０℃で実施される。アセチル化反応は、還流が開始してから、約１〜５時間実施される。アセチル化した反応生成物とは上記アセチル化反応終了後の溶液を表し、通常、未反応原料モノマー類、アセチル化された原料モノマー類、酢酸および未反応の無水酢酸等が含まれる溶液である。
【００１７】
アセチル化反応槽の材質は、上記アセチル化反応物に耐腐食性があることが好ましく、通常、ＧＬ製等が用いられる。
【００１８】
アセチル化した反応生成物は、通常、縮重合槽に移送され、縮重合が実施される。なお、縮重合とアセチル化反応槽は同じ槽を使用しても良い。
また、本発明においては、予め一部の原料モノマー類がアセチル化された原料モノマー類を使用して縮重合しても良い。アセチル化された原料モノマー類として、例えば、ｐ−アセトキシ安息香酸や４，４’−ジアセトキシジフェニル等が挙げられる。
【００１９】
縮重合槽の材質はアセチル化反応生成物等に対して耐腐食性であることが好ましく、具体的にはＳＵＳ３１６、ＳＵＳ３１６Ｌ、２相ステンレス、ニッケル−モリブデン系合金、不浸透黒鉛、チタン、ジルコニウム、ＧＬおよびタンタル等が例示される。ニッケル−モリブデン系合金の市販品の例としては、ハステロイ（Ｒ）Ｂ、ハステロイ（Ｒ）Ｃ等が挙げられる。
縮重合槽およびその翼の形状は公知のものを使用すれば良く、具体的には、縦型の撹拌槽などの場合、多段のパドル翼、タービン翼、ダブルヘリカム翼、錨形翼、櫛形翼等が用いられる。
【００２０】
縮重合は、通常、低沸物を留出させながら、常圧下、徐々に内温を約２７０〜３５０℃まで昇温させ、引き続き同温度を維持したまま、０〜５時間程度保温する。
縮重合の最終温度が２７０℃未満で維持されると重縮合が遅くなる傾向にあり、３５０℃を越えて維持されると、得られた芳香族ポリエステルの分解などの副反応が生じる傾向にある。
【００２１】
縮重合槽からの留出物には、低分子化合物、酢酸および未反応の無水酢酸等が挙げられる。低分子化合物とは、具体的には芳香族カルボン酸類等の原料モノマー類およびアセチル化されたモノマー類等の芳香族ポリエステルの構成成分である。また、他にも重合反応によって生じる水、アルコール類、フェノール類が含まれることもある。
上記低分子化合物が縮重合槽から大量に留去されると、目的の芳香族ポリエステルの得量が低下したり、原料モノマー類の仕込み組成比の製品が得られないため、製品の品質が安定化しない等の問題があり、好ましくない。
【００２２】
分縮器では、上記の低分子化合物のほとんどを凝縮させ、凝縮物を縮重合槽に回収する。分縮器における凝集温度、すなわち分縮器から凝縮器への未凝縮ガスの温度を、約８０〜１５０℃、好ましくは約１００〜１５０℃にすることによって行われる。この温度が約８０℃未満では、低分子化合物等が分縮器に付着する量が多くなる傾向にあり好ましくなく、また約１５０℃を超えると、低分子化合物が分縮器で回収されることなく、凝縮器に同伴留出したり、あるいは低分子化合物等が分縮器および凝縮器等に付着するため、好ましくない。
留出温度を上記温度範囲に制御するためには、通常、分縮器の冷媒を約７０℃〜１４０℃、好ましくは約１００℃〜１３０℃の温度範囲に制御する。
【００２３】
本発明において、分縮器の接液面の材質をニッケル−モリブデン合金とする。ＪＩＳ Ｈ４５５１に記載の合金記号で示すと、ＮｉＭｏ３０Ｆｅ５、ＮｉＭｏ２８およびＮｉＭｏ１６Ｃｒ１５Ｆｅ６Ｗ４であり、具体的な市販品として、ハステロイ（Ｒ）Ｂ、ハステロイ（Ｒ）Ｃ等が挙げられる。
【００２４】
【実施例】
以下、本発明を実施例でさらに詳細に説明するが、本発明はこれらによって限定されるものではない。
【００２５】
参考例１
（縮重合反応による芳香族ポリエステルの製造）
ｐ-アセトキシ安息香酸１，３０４ｋｇ（７，２３８モル）、４,４’−ジアセトキシジフェニル６３１ｋｇ（２，３３６モル）、テレフタル酸３００ｋｇ（１，８０６モル）、イソフタル酸１００ｋｇ（６０２モル）を仕込み、櫂型攪拌機を有する３ｍ３のＳＵＳ３１６Ｌ製の重合槽に仕込んだ。窒素ガス雰囲気下で１．５℃／分の速度で攪拌、副生する酢酸を除去しながら１８０℃から３００℃まで昇温し、さらに３００℃で６０分保持した。その後、重合槽を密閉し窒素で０．１ＭＰａに加圧した状態で、ベルトクーラーで冷却しながら芳香族ポリエステルの抜取りを行った。留出物は伝熱面積が１５ｍ２の縦型多管式熱交換器（ＳＵＳ３１６製）の下部に導入して凝縮させ、下部から凝縮液、上部から未凝集ガスを取り出し、凝集液は酢酸タンクに回収した（図１の分縮器を凝縮器として使用し、凝縮液は縮重合槽に戻さず、酢酸タンクに回収。）。この時の凝縮液の温度は約９０℃、未凝縮ガスの温度は約３０℃であった。
縦型多管式熱交換器の下部の空間部にステンレス製棒で台を作製し、ＳＵＳ３１６、三菱マテリアル（株）が販売しているハステロイ（Ｒ）Ｂ−２、ハステロイ（Ｒ）Ｃ−２２、ハステロイ（Ｒ）Ｃ−２７６製のテストピース(Ｕバンド)を装着し、６３９時間重縮合を繰り返した後、テストピースを取り出して評価を行った。腐食度、浸漬前後の重量変化率、外観観察、ミクロ組織検査および断面観察により各材質の腐食状況を評価した。
結果を表１に示す。
【００２６】
【表１】
参考例２
不浸透黒鉛製(角棒)のテストピースを装着した以外は参考例１と同様に行った。浸漬前後の重量変化率は＋０．９６％であったが、若干、流体の浸透している範囲であった。外観観察では異常は確認されなかったが、断面観察では外表面から１ｍｍ程度が若干こげ茶色に変色し、ミクロ組織検査では外表面部分に含浸樹脂の基材からの剥離や脱落が認められた。
【００２８】
実施例１、比較例１および２
(アセチル化反応)
水冷されたリービッヒ冷却器、温度計、窒素導入管、および、錨型攪拌翼を備え付けた３Ｌの筒型フラスコに、ｐ-ヒドロキシ安息香酸９９４ｇ（７．２モル）、４,４’−ジヒドロキシジフェニル４４６ｇ（４．４モル）、テレフタル酸２９９ｇ（１．８モル）、イソフタル酸１００ｋｇ（０．６モル）、および無水酢酸（１３．２モル）を仕込み、窒素雰囲気下、内溶液を攪拌しつつマントルヒーターにて液温を１４５℃まで昇温し、同温度で還流下に３時間攪拌してアセチル化反応生成物を得た。
【００２９】
(縮重合反応)
続いて、上記冷却器を、リボンヒーターで約１２５℃に温度調節された冷媒が流れている分縮器（検討材質製のチューブからなる多管式冷却器）に付け替え、さらに該分縮器に水冷された凝縮器（リービッヒ冷却器）を接続した。次に、１℃／分の割合で加熱して内温を３００〜３０５℃まで昇温し、同温度で６０分間攪拌を続け、縮重合を終了した。分縮器を出る未凝縮ガスの温度は約１３０℃であった。その後、系を密閉し、重合槽底部のバルブを開け、反応物をステンレス製トレーに約１ｃｍの厚みに抜き出した。これをホソカワミクロン（株）製のハンマーミルで粉砕し、スクリーン径が２ｍｍφの篩にかけた。
得られた芳香族ポリエステルを６０メッシュ以下に分級し、日本電色工業（株）製色調差計Ｚ−１００１ＤＰを用いて、Ｌ値（明度）、ａ値（赤み）を測定した。また、得られた芳香族ポリエステルの含有金属量は、灰化−硝酸溶解−ＩＣＰ発光分析法にて測定した。
チューブがＳＵＳ３１６、ハステロイ（Ｒ）Ｂ−２、不浸透黒鉛の分縮器について、それぞれ５バッチ、反応を行った。得られたポリエステルの色調、含有金属量についての測定結果を表２、表３に示す。
【００３０】
【表２】
【表３】
ＳＵＳ３１６は、耐食性の点からは使用が可能な材質であるが、得られる芳香族ポリエステルの色調改良の点から好ましくない。不浸透黒鉛は、耐食性および色調の点からは使用可能であるが、含浸樹脂の一部が剥離し、得られる芳香族ポリエステルに混入するので好ましくない。ハステロイ（Ｒ）Ｂは色調改良の点から好ましく、ハステロイ（Ｒ）Ｃはハステロイ（Ｒ）Ｂより腐食が少なく色調改良に好適である。
【００３３】
【発明の効果】
本発明によれば、色調が改良された芳香族ポリエステルを容易に得ることができる。
【図面の簡単な説明】
【図１】本発明で使用する製造装置の概略図である。
【符号の説明】
１：アセチル化反応槽
２：縮重合槽
３：分縮器
４：凝縮器
５：移送管
６：縮重合体
７：留出管
８：回収管
９：導管
１０：凝縮液
１１：未凝縮ガス
１２、１３、１４、１５：冷媒[0001]
BACKGROUND OF THE inventions]
The present invention relates to a method for producing an aromatic polyester. More particularly, the present invention relates to a method for producing an aromatic polyester having an improved color tone.
[0002]
[Prior art]
Reaction products obtained by acetylating raw material monomers selected from aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols with acetic anhydride, or aromatic products obtained by condensation polymerization of pre-acetylated raw material monomers A method for producing polyester is well known, and in that case, a method is also known in which a condensing unit is provided in a condensation polymerization tank, and the condensation is recovered while collecting the condensate (patent). Reference 1).
On the other hand, industrially, a SUS316-made one is used as the condensation polymerization tank (see, for example, Patent Document 2), and a partial condenser made of SUS316 is also used.
[0003]
[Patent Document 1]
JP 2000-212264 (paragraph [0005])
[Patent Document 2]
JP 2000-191762 (paragraph [0024])
[0004]
[Problems to be solved by the invention]
However, the color tone of the aromatic polyester produced by the conventional method is not always sufficient, and in recent years, an aromatic polyester having a better color tone has been desired.
An object of the present invention is to provide a method for producing an aromatic polyester having an improved color tone.
[0005]
[Means for Solving the Invention]
As a result of intensive studies to solve such problems, the present inventors obtained SUS316 as a material for the wetted surface of the partial condenser provided in the condensation polymerization tank, although it can be used from the viewpoint of corrosion resistance. is insufficient in terms of the color tone of the aromatic polyester, the material of the wetted surface of the partial condenser, nickel - by molybdenum alloys, found that an aromatic polyester tone is improved is obtained, The present invention has been reached.
[0006]
That is, the present invention relates to a reaction product obtained by acetylating aromatic polyester raw monomers with acetic anhydride, or raw monomer in which a part of the raw monomers is acetylated in advance. In the method for producing aromatic polyester while heating and condensation polymerization using a polymerization tank, fractionating the distillate and recovering the condensate in the condensation polymerization tank, the material of the wetted surface of the partial condenser is nickel. - a process for producing aromatic polyester, which comprises a molybdenum alloy.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
FIG. 1 is a schematic view of a manufacturing apparatus used in the present invention. In the acetylation reaction tank (1), raw material monomers are acetylated with acetic anhydride under reflux. The reaction product is transferred to the condensation polymerization tank (2) by the transfer pipe (5). The reaction product is heated and condensation polymerization is performed. The distillate is sent to the condenser (3) by the distillation pipe (7), cooled by the refrigerant (12, 13), partially condensed, and the condensate is sent to the condensation polymerization tank by the recovery pipe (8). Collected. After completion of the reaction, the obtained condensation polymer (6) is withdrawn from the bottom of the condensation polymerization tank. The distillate not condensed in the partial condenser is sent to the condenser (4) by the conduit (9), cooled by the refrigerant (14, 15), and separated into the condensate (10) and the uncondensed gas (11). Is done.
[0008]
The raw material monomers for the aromatic polyester used in the present invention are selected from aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols, and are usually aromatic hydroxyl carboxylic acids, aromatic dicarboxylic acids and aromatic diols. Kind is used.
[0009]
As aromatic hydroxycarboxylic acids, for example, the following general formula (1),
HO-X-COOR 1 (1)
(Wherein R 1 represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 16 carbon atoms, and X represents a divalent aromatic group).
[0010]
Specific examples of the aromatic hydroxyloxycarboxylic acids include p-hydroxybenzoic acid, p-hydroxybenzoic acid methyl, p-hydroxybenzoic acid propyl, p-hydroxybenzoic acid phenyl, p-hydroxybenzoic acid benzyl, p- (4 -Hydroxyphenyl) benzoic acid, methyl p- (4-hydroxyphenyl) benzoate, 2-hydroxy-6-naphthoic acid, methyl 2-hydroxy-6-naphthoate and phenyl 2-hydroxy-6-naphthoate Is done. Of these, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid and the like are preferable.
[0011]
As aromatic dicarboxylic acids, for example, the following general formula (2),
R 2 —O—CO—Y—CO—O—R 2 (2)
(Wherein R 2 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and Y represents a divalent aromatic group.) The thing represented by is mentioned.
[0012]
Specific examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4′-dicarboxydiphenyl, 1,2-bis (4-carboxyphenoxy) ethane, 2,5-dicarboxynaphthalene, 2,6 -Carboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, dimethyl terephthalate, dimethyl isophthalate, diphenyl terephthalate, diphenyl isophthalate, 4,4'-dimethoxycarbonyldiphenyl, 2,6-dimethoxy Examples thereof include carbonylnaphthalene, 1,4-dichlorocarbonylnaphthalene and 1,5-diphenoxycarbonylnaphthalene. Of these, terephthalic acid, isophthalic acid, 2,6-dicarboxynaphthalene, and the like are preferable.
[0013]
As aromatic diols, for example, the following general formula (3),
HO-Z-OH (3)
(Wherein Z represents a divalent aromatic group).
[0014]
Specific examples of the aromatic diols include hydroquinone, resorcin, catechol, 4,4′-dihydroxydiphenyl, 4,4′-hydroxybenzophenone, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane, 4,4'-dihydroxydiphenyl ether, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-hydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 2,6-dihydroxynaphthalene and 1,5- Examples thereof include hydroxynaphthalene and the like. Of these, hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, and the like are preferable.
[0015]
The use ratio of the aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols is not particularly limited, but the aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols are usually added to a total of 100 moles. The range is selected from about 30 to 80 mol of the aromatic hydroxycarboxylic acid, about 10 to 35 mol of the aromatic dicarboxylic acid, and about 10 to 35 mol of the aromatic diol.
[0016]
The acetylation reaction is carried out under reflux, and its temperature and pressure are not particularly limited, but it is usually carried out at about 140 to 150 ° C. under normal pressure. The acetylation reaction is carried out for about 1 to 5 hours after the start of reflux. The acetylated reaction product represents a solution after completion of the acetylation reaction, and is usually a solution containing unreacted raw material monomers, acetylated raw material monomers, acetic acid, unreacted acetic anhydride and the like.
[0017]
As the material of the acetylation reaction tank, the acetylation reaction product preferably has corrosion resistance, and GL or the like is usually used.
[0018]
The acetylated reaction product is usually transferred to a condensation polymerization tank and subjected to condensation polymerization. The same tank may be used for the condensation polymerization and the acetylation reaction tank.
In the present invention, condensation polymerization may be performed using raw material monomers in which some raw material monomers are acetylated in advance. Examples of the acetylated raw material monomers include p-acetoxybenzoic acid and 4,4′-diacetoxydiphenyl.
[0019]
The material of the condensation polymerization tank is preferably resistant to corrosion with respect to acetylation reaction products and the like. Specifically, SUS316, SUS316L, two-phase stainless steel, nickel-molybdenum alloy, impervious graphite, titanium, zirconium, Examples include GL and tantalum. Examples of commercially available nickel-molybdenum alloys include Hastelloy (R) B and Hastelloy (R) C.
The condensation polymerization tank and its blade shape may be of a known type. Specifically, in the case of a vertical stirring tank, etc., multistage paddle blades, turbine blades, double helicam blades, saddle blades, comb blades, etc. Is used.
[0020]
In the condensation polymerization, the internal temperature is gradually raised to about 270 to 350 ° C. under normal pressure while distilling low boiling substances, and the temperature is maintained for about 0 to 5 hours while maintaining the same temperature.
If the final temperature of the polycondensation is maintained below 270 ° C., the polycondensation tends to be slow, and if maintained above 350 ° C., side reactions such as decomposition of the resulting aromatic polyester tend to occur. .
[0021]
Examples of the distillate from the condensation polymerization tank include low molecular weight compounds, acetic acid and unreacted acetic anhydride. The low molecular compound is specifically a constituent component of an aromatic polyester such as raw material monomers such as aromatic carboxylic acids and acetylated monomers. In addition, water, alcohols and phenols generated by the polymerization reaction may be included.
If a large amount of the low molecular weight compound is distilled off from the condensation polymerization tank, the yield of the desired aromatic polyester will be reduced, or a product with a composition ratio of raw material monomers will not be obtained, resulting in stable product quality. It is not preferable because there is a problem that it is not converted.
[0022]
In the partial condenser, most of the low molecular compounds are condensed, and the condensate is collected in a condensation polymerization tank. The condensation temperature in the partial condenser, that is, the temperature of the uncondensed gas from the partial condenser to the condenser is set to about 80 to 150 ° C., preferably about 100 to 150 ° C. If this temperature is less than about 80 ° C., the amount of low-molecular compounds and the like attached to the pressure reducer tends to increase, which is not preferable. If the temperature exceeds about 150 ° C., the low-molecular weight compounds are recovered by the pressure reducer. In addition, it is not preferable because it is entrained in the condenser or low molecular weight compounds adhere to the condenser and condenser.
In order to control the distillation temperature within the above temperature range, the refrigerant of the partial condenser is usually controlled within a temperature range of about 70 ° C to 140 ° C, preferably about 100 ° C to 130 ° C.
[0023]
In the present invention, the material of the wetted surface of the partial condenser nickel - and molybdenum alloys. When represented by an alloy symbol described in JIS H4551, they are NiMo30Fe5, NiMo28, and NiMo16Cr15Fe6W4. Specific examples of commercially available products include Hastelloy (R) B and Hastelloy (R) C.
[0024]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.
[0025]
Reference example 1
(Production of aromatic polyester by condensation polymerization reaction)
p-Acetoxybenzoic acid 1,304 kg (7,238 mol), 4,4′-diacetoxydiphenyl 631 kg (2,336 mol), terephthalic acid 300 kg (1,806 mol), isophthalic acid 100 kg (602 mol) And a 3 m 3 SUS316L polymerization tank equipped with a vertical stirrer. The mixture was stirred at a rate of 1.5 ° C./min in a nitrogen gas atmosphere, the temperature was raised from 180 ° C. to 300 ° C. while removing by-product acetic acid, and the temperature was further maintained at 300 ° C. for 60 minutes. Thereafter, the aromatic polyester was extracted while cooling with a belt cooler in a state where the polymerization tank was sealed and pressurized to 0.1 MPa with nitrogen. The distillate is introduced into the lower part of a vertical multitubular heat exchanger (made of SUS316) with a heat transfer area of 15 m 2 and condensed, and condensate is taken out from the lower part and unaggregated gas is taken out from the upper part. (The condenser of FIG. 1 was used as a condenser, and the condensate was not returned to the condensation polymerization tank but recovered in an acetic acid tank.) At this time, the temperature of the condensate was about 90 ° C., and the temperature of the uncondensed gas was about 30 ° C.
A stand is made of stainless steel rods in the lower space of the vertical multi-tubular heat exchanger, and SUS316, Hastelloy (R) B-2 and Hastelloy (R) C-22 sold by Mitsubishi Materials Corporation. A test piece (U band) made of Hastelloy (R) C-276 was attached, and after polycondensation was repeated for 639 hours, the test piece was taken out and evaluated. The corrosion status of each material was evaluated by the degree of corrosion, weight change rate before and after immersion, appearance observation, microstructure inspection and cross-sectional observation.
The results are shown in Table 1.
[0026]
[Table 1]
Reference example 2
The same procedure as in Reference Example 1 was performed except that a test piece made of impervious graphite (square bar) was attached. Although the weight change rate before and after immersion was + 0.96%, it was in a range where the fluid permeated slightly. Although no abnormalities were observed in the appearance observation, about 1 mm from the outer surface turned slightly dark brown in the cross-sectional observation, and in the microstructural examination, peeling and dropping of the impregnated resin from the base material were observed on the outer surface portion.
[0028]
Example 1, Comparative Examples 1 and 2
(Acetylation reaction)
Into a 3 L cylindrical flask equipped with a water-cooled Liebig condenser, a thermometer, a nitrogen inlet tube, and a vertical stirring blade, 994 g (7.2 mol) of p-hydroxybenzoic acid and 4,4′-dihydroxydiphenyl were added. 446 g (4.4 mol), 299 g (1.8 mol) terephthalic acid, 100 kg (0.6 mol) isophthalic acid, and acetic anhydride (13.2 mol) were charged, and the inner solution was stirred under a nitrogen atmosphere. The liquid temperature was raised to 145 ° C. with a mantle heater, and the mixture was stirred at reflux at the same temperature for 3 hours to obtain an acetylation reaction product.
[0029]
(Condensation polymerization reaction)
Subsequently, the above cooler is replaced with a pressure reducer (multi-tube cooler made of a tube made of the material to be studied) in which a refrigerant whose temperature is adjusted to about 125 ° C. by a ribbon heater flows. A water-cooled condenser (Liebig condenser) was connected. Next, heating was performed at a rate of 1 ° C./min to raise the internal temperature to 300 to 305 ° C., and stirring was continued at the same temperature for 60 minutes to complete the condensation polymerization. The temperature of the uncondensed gas leaving the partial condenser was about 130 ° C. Thereafter, the system was sealed, the valve at the bottom of the polymerization tank was opened, and the reaction product was extracted to a thickness of about 1 cm in a stainless steel tray. This was pulverized with a hammer mill manufactured by Hosokawa Micron Corporation, and passed through a sieve having a screen diameter of 2 mmφ.
The obtained aromatic polyester was classified to 60 mesh or less, and L value (lightness) and a value (redness) were measured using a color difference meter Z-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. The amount of metal contained in the obtained aromatic polyester was measured by ashing-nitric acid dissolution-ICP emission analysis.
The tubes were reacted in batches of 5 batches for SUS316, Hastelloy (R) B-2, and impregnated graphite. Tables 2 and 3 show the measurement results of the color tone and the amount of contained metal of the obtained polyester.
[0030]
[Table 2]
[Table 3]
SUS316 is a material that can be used from the viewpoint of corrosion resistance, but is not preferable from the viewpoint of improving the color tone of the resulting aromatic polyester. Although impervious graphite can be used from the viewpoint of corrosion resistance and color tone, it is not preferable because part of the impregnated resin is peeled off and mixed into the resulting aromatic polyester. Hastelloy (R) B is preferable from the viewpoint of color tone improvement, and Hastelloy (R) C is less corrosive than Hastelloy (R) B and is suitable for color tone improvement.
[0033]
【The invention's effect】
According to the present invention, an aromatic polyester having improved color tone can be easily obtained.
[Brief description of the drawings]
FIG. 1 is a schematic view of a production apparatus used in the present invention.
[Explanation of symbols]
1: acetylation reaction tank 2: condensation polymerization tank 3: condensation condenser 4: condenser 5: transfer pipe 6: condensation polymer 7: distillation pipe 8: recovery pipe 9: conduit 10: condensate 11:
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003130024A JP4134325B2 (en) | 2003-05-08 | 2003-05-08 | Process for producing aromatic polyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003130024A JP4134325B2 (en) | 2003-05-08 | 2003-05-08 | Process for producing aromatic polyester |
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| JP2004331829A JP2004331829A (en) | 2004-11-25 |
| JP2004331829A5 JP2004331829A5 (en) | 2006-03-09 |
| JP4134325B2 true JP4134325B2 (en) | 2008-08-20 |
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| JP2006299027A (en) * | 2005-04-19 | 2006-11-02 | Sumitomo Chemical Co Ltd | Method for producing aromatic polyester |
| JP2006307007A (en) * | 2005-04-28 | 2006-11-09 | Sumitomo Chemical Co Ltd | Method for producing aromatic polyester |
| JP2006307006A (en) * | 2005-04-28 | 2006-11-09 | Sumitomo Chemical Co Ltd | Method for manufacturing aromatic polyester |
| US20090297752A1 (en) * | 2005-08-09 | 2009-12-03 | Toyo Boseki Kabushiki Kaisha | Polyester resin, polyester resin composition therefrom and use thereof |
| JP2007332076A (en) * | 2006-06-15 | 2007-12-27 | Sumitomo Chemical Co Ltd | Method for producing allyl chloride |
| JP5742706B2 (en) * | 2010-12-27 | 2015-07-01 | 東レ株式会社 | Method for producing liquid crystalline polyester resin |
| WO2012090746A1 (en) * | 2010-12-27 | 2012-07-05 | 東レ株式会社 | Apparatus for production of aromatic polyester, and process for production of aromatic polyester |
| CN103201310B (en) | 2010-12-27 | 2015-01-14 | 东丽株式会社 | Process for production of liquid crystalline polyester resin, and apparatus for production of liquid crystalline polyester resin |
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