JPS60238318A - Polymerization of polyester and polymerization apparatus using therefor - Google Patents

Polymerization of polyester and polymerization apparatus using therefor

Info

Publication number
JPS60238318A
JPS60238318A JP24579083A JP24579083A JPS60238318A JP S60238318 A JPS60238318 A JP S60238318A JP 24579083 A JP24579083 A JP 24579083A JP 24579083 A JP24579083 A JP 24579083A JP S60238318 A JPS60238318 A JP S60238318A
Authority
JP
Japan
Prior art keywords
polymerization
polyester
ethylene glycol
reaction
medium
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
Application number
JP24579083A
Other languages
Japanese (ja)
Inventor
Hiroshi Terada
寺田　拡
Takayuki Tajiri
象運 田尻
Masao Hamada
浜田　雅郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Priority to JP24579083A priority Critical patent/JPS60238318A/en
Publication of JPS60238318A publication Critical patent/JPS60238318A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

PURPOSE:To improve the rate of polymerization of a polyester, by atomizing bishydroxyalkyl terephthalate (or its precondensate) in molten state, supplying the particles to a reactor containing a liquid thermal medium, and carrying out the thermal polymerization at a specific temperature. CONSTITUTION:Bis-omega-hydroxyalkyl terephthalate (or its precondensate) is atomized in molten state with the atomizer 2 to particles having the representative particle diameter of <=500mu. The particles are supplied to the polymerization reactor 7 filled with a molten thermal medium to form an emulsion, and heated at a temperature above the melting point of the molten monomer and below 320 deg.C to obtain a polyester. The polyester is separated from the thermal medium by the solid-liquid separator 8, and ethylene glycol and the thermal medium are separated from each other with the distillation column 10.

Description

【発明の詳細な説明】 〔技術分野〕 本発明はポリエステルの重合法並びにポリエステルを重
合するための重合装置に関するものであり、と（にビス
ーＷ−ヒドロキシアルキルテレフタレート（以下ＢＨＴ
と略記する）又はその初期給金物を非水工マルジョ／状
に有機媒体中に微粒子状に分散せした状態で加熱重合せ
しめポリエステルを製造する方法に関するものである。Detailed Description of the Invention [Technical Field] The present invention relates to a method for polymerizing polyester and a polymerization apparatus for polymerizing polyester.
The present invention relates to a method for producing polyester by heating and polymerizing the initial feed (hereinafter referred to as "polyester") or its initial feed, which is dispersed in the form of fine particles in an organic medium in the form of a non-aqueous slurry.

〔従来技術〕[Prior art]

従来、開発されてきたポリエステルの重合法としては繊
維便覧（丸善株式会社、昭和４３年１１月３０日刊）に
示される如く、バッチ重合法、連続重合法が知られてい
るが、これらの方法は未だその重合効率を高める必要が
あること、或いは装置が複雑である点を改良する必要が
あることなどが指摘されている。As shown in the Fiber Handbook (Maruzen Co., Ltd., November 30, 1961), known polyester polymerization methods that have been developed so far include batch polymerization methods and continuous polymerization methods. It has been pointed out that there is still a need to increase the polymerization efficiency or to improve the complexity of the equipment.

ポリエステルの重合速度の向上を図る方法としては特公
昭３９−６８４８号公報、又は特公昭４Ｂ−５１１９号
公報に示される如（、ＢＥＴ又はその初期縮合物を０．
１〜４罪厚の薄膜とし工、或いは無端状金属ベルト上に
０．０２６〜０６３朋の薄膜な形成して加熱帯域に送り
脱エチレングリコール反応によりポリエステルを作る方
法が示されているが、これらの方法にてもＢ）ＩＴ又は
その初期縮合物からエチレングリコールを離脱するには
十分な表面積とはなっておらず、ポリエステルの重合速
度の向上という観点からは更に一歩進んだ改良法の出現
が望まれている。As a method for improving the polymerization rate of polyester, as shown in Japanese Patent Publication No. 39-6848 or Japanese Patent Publication No. 4B-5119, BET or its initial condensate is added to 0.
Methods for producing polyester by forming a thin film of 1 to 4 mm thick or forming a thin film of 0.026 to 0.63 mm on an endless metal belt and sending it to a heating zone by removing ethylene glycol reaction have been shown. Even with method B), the surface area is not sufficient to remove ethylene glycol from IT or its initial condensate, and from the viewpoint of improving the polymerization rate of polyester, it is necessary to develop an improved method that goes one step further. desired.

また他の方法としては特公昭３５”４９９３号公報に示
される如（、ＢＨＴ又はその初期縮合物を溶融し気体と
共に真空中に噴射し１５０〜３００℃の温度で重合する
方法が示されているか、この方法もＢＨＴ又はその初期
縮合物粉体の媒体が真空中又は不活性ガス雰囲気である
ため粉体の粒径コントロールが難しく、しかも粉体の重
力により粉体が容器底部に沈堆することはさけられず重
合効率の向上という観点からは一層の改良が必要といわ
れている。Another method is as shown in Japanese Patent Publication No. 35''4993 (1984), in which BHT or its initial condensate is melted and injected into a vacuum together with gas, and polymerized at a temperature of 150 to 300°C. In this method, the medium of BHT or its initial condensate powder is in a vacuum or an inert gas atmosphere, so it is difficult to control the particle size of the powder, and furthermore, the powder tends to settle at the bottom of the container due to the gravity of the powder. Further improvements are said to be necessary from the viewpoint of improving polymerization efficiency.

そこで本発明者等はＢＨＴ又はその初期縮合物よりのエ
チレングリコールの拡散及び離脱速度の向上を図りかつ
反応の均一化を図ることを目的として検討したところ、
Ｂ）ＩＴ又はその初期縮合物を微粉体として扱うのがそ
の表面積の増大に最も効果的であり、脱エチレングリコ
ール反応による重合反応の促進効果が高いこと、又、反
応媒体として液状媒体を使用する方法がＢＨＴ又はその
初期縮合物の均一分散に有効であり脱エチレングリコー
ル反応の促進効果か得られ易いことを見出し本発明を完
成した。Therefore, the present inventors conducted studies with the aim of improving the rate of diffusion and separation of ethylene glycol from BHT or its initial condensate and homogenizing the reaction.
B) It is most effective to increase the surface area of IT or its initial condensate as a fine powder, and the effect of promoting the polymerization reaction through the ethylene glycol removal reaction is high, and a liquid medium is used as the reaction medium. We have completed the present invention by discovering that this method is effective for uniformly dispersing BHT or its initial condensate, and that it is easy to obtain the effect of promoting the deethylene glycol reaction.

〔発明の構成〕[Structure of the invention]

本発明の要旨とするところはビスーＷ−ヒドロキシアル
キルテレフタレート又はその初期１ｆａ金物を溶融状態
で、その代表粒径が５００μ以下となるように微粒化し
て、溶液状熱媒体の満たされた重合反応器中に供給して
エマルジョ／を形成し、ビスーＷ−ヒドロキシアルキル
テレフタレート又はその初期縮合物の融点以上、好しく
は２７０℃以上３２０℃以下の温度に加熱して縮合反応
せしめ、生成するエチレングリコール及び低沸点成分を
熱媒体中に吸収せしめることを特徴とする承りエステル
の重合法にある。The gist of the present invention is to micronize bis-W-hydroxyalkyl terephthalate or its initial 1fa metal material in a molten state so that its typical particle size is 500 μm or less, and then to form a polymerization reactor filled with a solution heating medium. The ethylene glycol and This invention relates to a method for polymerizing esters, which is characterized by absorbing a low-boiling point component into a heat medium.

本発明を実施するに際して用いるビスーＷ−ヒドロキシ
アルキルテレフタレート又はその初期縮合物はテレフタ
ル酸、オルトフタル酸、イソフタル酸、２，６−ナツタ
レンジカルボ／酸などの芳香族ジカルボン酸又はこれら
のジアルキルエステル類とエチレングリコール、ｌ、３
−プロパンジオール、１，４−ブタ／ジオール、１，６
−ヘキサンジオールなとのα、ω−ジオール類とを縮合
ないしエステル交換することによって作られるものであ
る。The bis-W-hydroxyalkyl terephthalate or its initial condensate used in carrying out the present invention is an aromatic dicarboxylic acid such as terephthalic acid, orthophthalic acid, isophthalic acid, 2,6-natutale dicarbo/acid, or a dialkyl ester thereof. ethylene glycol, l, 3
-propanediol, 1,4-buta/diol, 1,6
It is produced by condensation or transesterification of α,ω-diols such as -hexanediol.

本発明を集卵するに際してはＢＨＴ又はその初期縮合物
を５００μ以下、とくに３００μ以下の微粒子体にして
取扱い、その表面積の増大効果を利用して脱エチレング
リコール反応を促進する点に特徴を有するものである。The present invention is characterized in that when collecting eggs, BHT or its initial condensate is handled in the form of fine particles of 500μ or less, particularly 300μ or less, and the ethylene glycol removal reaction is promoted by utilizing the effect of increasing the surface area. It is.

この微粒化はＢＨＴ又はその初期縮合物を溶融状態で、
アトマイザ−等を利用することにより所望の粒径のもの
とすることができる。これら微粒子化物の代表直径が５
００μを越えて大きくなると微粒子化物よりの脱エチレ
ングリコール化速度が低下するので好しくない。This atomization involves BHT or its initial condensate in a molten state,
A desired particle size can be obtained by using an atomizer or the like. The representative diameter of these fine particles is 5
If the particle diameter exceeds 00 μm, the rate of deethylene glycolization from the fine particles decreases, which is not preferable.

本発明を実施するに際して用いる溶液状熱媒体としては
ＢＨＴ又はその初期縮合物と非反応性であり、好しくは
エチレングリコールとの親和性の高い有機溶媒であるこ
とがよく、例えばべ／ゼン、トルエン、キシン／、テト
ラリン、デカリン、ヘキサメチルベンゼン、ア／トラセ
ン、メチルエチルケトン、ナフタリン、パラフィｙ系炭
化水素、ビフェニル、ジフェニルメタン、トリフェニル
メタン、ビベ／ジル、フエナントレリン、シリコ／オイ
ルなどをその具体例として挙げることができる。The solution heat medium used in carrying out the present invention is preferably an organic solvent that is non-reactive with BHT or its initial condensate and preferably has a high affinity with ethylene glycol, such as be/zene, Specific examples include toluene, xine/, tetralin, decalin, hexamethylbenzene, a/thracene, methyl ethyl ketone, naphthalene, paraphylic hydrocarbons, biphenyl, diphenylmethane, triphenylmethane, bibe/zil, phenanthreline, silico/oil, etc. It can be mentioned as follows.

本発明はＢＨＴ又はその初期縮合物を微粒子化して、液
状熱媒体中に分散せしめるため、反応系全体が均一なエ
マルション状態を形成しているため、微粒子化物が沈殿
したり、凝集したりすることな（当該微粒子体よりのエ
チレングリコール及び低揮発性成分の液状媒体中への吸
収を極めてスムースに行なうことができる。In the present invention, BHT or its initial condensate is made into fine particles and dispersed in a liquid heat medium, so that the entire reaction system forms a uniform emulsion state, so that the fine particles do not precipitate or aggregate. (Ethylene glycol and low-volatility components can be absorbed into the liquid medium extremely smoothly from the fine particles.

反応温度としてはＢＨＴ又はその初期縮合物の融点以上
、と（に２７０℃〜３２０℃の間の温度を用いるのが望
しく、余り低温では縮合反応が遅（なり、一方余り高温
であるとＢｌ（Ｔ又はその初期縮合物の分解反応など不
都合な反応が起るので好しくない。As for the reaction temperature, it is desirable to use a temperature above the melting point of BHT or its initial condensate, and a temperature between 270°C and 320°C. If the temperature is too low, the condensation reaction will be slow, while if it is too high, the Bl (This is not preferred because undesirable reactions such as decomposition reactions of T or its initial condensate occur.

本発明を実施するに際してはＢＨＴ又はその初期縮合物
の微粒体を不活性な液状熱媒体に分散せしめることによ
ってなしつるが微粒体の熱媒体への均一分散化は機械的
に攪拌する方法、或いは有機、無機の分散安定剤を用い
ることによってなすことができる。When carrying out the present invention, the fine particles of BHT or its initial condensate are dispersed in an inert liquid heat medium, and the fine particles are uniformly dispersed in the heat medium by mechanical stirring, or by mechanical stirring. This can be achieved by using an organic or inorganic dispersion stabilizer.

本発明によるとＢＨＴ又はその初期縮合物を微粒化物と
して取扱うため、その表面積を従来法に較べ著るしく増
大することができるため、脱エチレングリコール反応を
効率よく行なうことができる。また、ＢＨＴ又はその初
期縮合物の分散媒体が液状熱媒であるため、反応系の温
度コントロールを均一に行なりことかでき、かつこれら
媒体がエチレングリコールとの親和性を有するものであ
るのでＢＨＴ又はその初期縮合物からの脱エチレングリ
コール反応ラスムースに行なうことかできる。更にＢＨ
Ｔ又はその初期縮合物微粒体の沈堆などの不都合を起す
ことな（熱媒体中に均一に分散せしめ得たため、これら
の反応は更にスムースに行なうことができる。According to the present invention, since BHT or its initial condensate is treated as a finely divided product, its surface area can be significantly increased compared to conventional methods, and therefore the ethylene glycol removal reaction can be carried out efficiently. In addition, since the dispersion medium of BHT or its initial condensate is a liquid heating medium, the temperature of the reaction system can be uniformly controlled, and since these mediums have an affinity for ethylene glycol, BHT Alternatively, the initial condensate may be subjected to an ethylene glycol removal reaction in a laminated form. Furthermore, BH
These reactions can be carried out even more smoothly because fine particles of T or its initial condensate can be uniformly dispersed in the heating medium without causing any inconvenience such as precipitation.

本発明を実施するに際しては熱媒体にＢＨＴ又はその初
期縮合物から離脱するエチレングリコール及び低沸点成
分を吸収せしめる方法をとっており、この液状熱媒体は
反応系外に取出し、これらの成分を除去した后反応系に
もどして再利用する。When carrying out the present invention, a method is used in which the heat transfer medium absorbs ethylene glycol and low boiling point components released from BHT or its initial condensate, and this liquid heat transfer medium is taken out of the reaction system and these components are removed. After that, it is returned to the reaction system and reused.

反応を終了したポリエステルは反応容器より取出し、熱
媒体が低沸点溶媒である場合には単に乾燥することによ
って、また熱媒体が高沸点溶媒である場合には他の低沸
点溶媒にて洗浄乾燥すればよい。After the reaction, the polyester is taken out from the reaction vessel, and if the heating medium is a low boiling point solvent, it is simply dried, or if the heating medium is a high boiling point solvent, it is washed and dried with another low boiling point solvent. Bye.

本発明を実施するに際しては！８ｇ１図に示す如き反応
容器を用いるのがよい。When implementing the present invention! It is preferable to use a reaction vessel as shown in Figure 8g1.

本発明を図面によって説明をする。第１図は本′発明の
概略図であ□り芳香族ジカルボ／酸およびエチレングリ
コールからなるエステル化物を微粒化し、一時貯蔵し重
合工程で縮重合反応を行わせるシステムを示す。１は前
工程よ、り送られてくるエステル化物を貯蔵するりｙり
である。The present invention will be explained with reference to the drawings. FIG. 1 is a schematic diagram of the present invention, showing a system in which an esterified product consisting of an aromatic dicarbo/acid and ethylene glycol is atomized, temporarily stored, and subjected to a polycondensation reaction in the polymerization process. 1 is a tank for storing the esterified product sent from the previous process.

エステル化物は貯蔵タンク１より微粒化装置２へ送られ
所定の粒径分布を示すように微粒化が行なわれる。微粒
化装置としてはφ８４翳回転円板式アトマイザーを使用
した。微粒子の粉体暴発を防止するために微粒化は窒素
中で行い、窒素は循環して使用する。４は循環用の送風
機で２．２　ｋｗ、２０イ毎分の能力のターボプロアで
ある。５は微粒子と気体の分離を行うサイクロンである
。６は微粒化の際、気体中に拡散す入Ｔキ「ノｙ　７ｆ
　１１ゴー７１７か兜ＩＮす六畳訊ハツカ→バーで、３
は窒素の再加熱を行うシースヒーターで、３０　ｋｗの
能力を有している。サイクロン５により分離されたエス
テル化物の微粒子は１１の貯蔵タンクへ一時貯蔵される
。微粒子は反応容器７へ序々に送られ有機物媒体中へ分
散させられその中へエチレングリコールを拡散させなが
ら縮重合反応を進行させる。反応容器７には３０７のジ
ャケット付の釜を使用し、有機物媒体としては例えばシ
リコンオイルを使用した。The esterified product is sent from the storage tank 1 to the atomization device 2, where it is atomized to exhibit a predetermined particle size distribution. As the atomization device, a φ84 rotary disk type atomizer was used. In order to prevent powder explosion of fine particles, atomization is carried out in nitrogen, and the nitrogen is recycled for use. 4 is a circulation blower, which is a turbo blower with a capacity of 2.2 kW and 20 i/min. 5 is a cyclone that separates fine particles and gas. 6 diffuses into the gas during atomization.
11 Go 717 or Kabuto IN Su Rokujokan Hatsuka → At the bar, 3
is a sheath heater that reheats nitrogen and has a capacity of 30 kW. The fine particles of the esterified product separated by the cyclone 5 are temporarily stored in a storage tank 11. The fine particles are gradually sent to the reaction vessel 7, where they are dispersed in an organic medium, and the polycondensation reaction proceeds while ethylene glycol is diffused therein. A 307 jacketed pot was used as the reaction vessel 7, and silicone oil, for example, was used as the organic medium.

重合が終了した段階で有機物媒体の温度を、ポリマーの
溶融点以下に下げ、ポリマーといっしょに容器外へ排出
し固液分離装置８１Ｃよりポリマーを回収する。有機物
媒体はオイルキャッチャ−９により集められ、蒸留塔１
０へ送られエチレングリコールを回収した後再度使用す
る。When the polymerization is completed, the temperature of the organic medium is lowered to below the melting point of the polymer, and the organic medium is discharged from the container together with the polymer, and the polymer is recovered from the solid-liquid separator 81C. The organic medium is collected by oil catcher 9 and sent to distillation column 1.
0, where the ethylene glycol is recovered and used again.

固液分離装置としては粒径に応じたメツショのステンレ
ス製金網のコンベアを使用した。As the solid-liquid separator, a mesh conveyor made of stainless steel wire mesh according to the particle size was used.

第２図は微粒化装置２を反応容器７に直接取りつげたシ
ステムを示す。微粒化装置２には第１図のシステムと同
じものを使用した。反応容器７は一部ジャケット付の釜
を使用し、上部に高さ１００（１＋ｇの微粒化室を設け
た。窒素の循環系は第１図と同一で、サイクロンにより
補集された微粒子も反応容器７へ再投入される。微粒子
は直接有機物媒体中へ落下し重合反応を行う。重合反応
終了後固液分離装置８で分離され、ポリマーは後工程へ
有機物媒体はエチレングリコール回収の為に蒸留塔へ送
られた後、再使用される。FIG. 2 shows a system in which the atomization device 2 is directly attached to the reaction vessel 7. The atomization device 2 used was the same as the system shown in FIG. The reaction vessel 7 used a partially jacketed pot, and had an atomization chamber with a height of 100 (1+g) at the top.The nitrogen circulation system was the same as in Figure 1, and the particles collected by the cyclone were also reacted. The particles are re-injected into the container 7.The fine particles fall directly into the organic medium and undergo a polymerization reaction.After the polymerization reaction is completed, they are separated in a solid-liquid separator 8, and the polymer is sent to a subsequent process.The organic medium is distilled to recover ethylene glycol. After being sent to the tower, it will be reused.

第３図は本発明において使用される縮重合反応器の別の
例である。攪拌機を設けた耐圧槽式反応器を３基直列に
連結したもので、第１槽１２の反応物供給口１３より、
ビスーＷ−ヒドロキシアルキルテレフタレート及びその
低重合体を供給し、別に設けた溶媒供給口１４より溶媒
を供給する。留出口１５よりエチレングリコールを含む
溶媒が留出する。FIG. 3 is another example of a polycondensation reactor used in the present invention. Three pressure tank reactors equipped with a stirrer are connected in series, and from the reactant supply port 13 of the first tank 12,
Bis-W-hydroxyalkyl terephthalate and its low polymer are supplied, and a solvent is supplied from a separately provided solvent supply port 14. A solvent containing ethylene glycol is distilled out from the distillation port 15.

抜取ポンプ１６１／Ｃより反応槽１２から、一定量の反
応溶液を抜取り、反応槽１７に供給する。A certain amount of the reaction solution is extracted from the reaction tank 12 by the extraction pump 161/C and supplied to the reaction tank 17.

第２番目の反応槽１７かう、留出口１８を経てエチレン
グリコールを含む溶媒が留出する。A solvent containing ethylene glycol is distilled out through the second reaction tank 17 and the distillation port 18.

抜取ポンプ１９により反応槽１７から一定量の反応溶液
を抜取って、第３番目の反応槽２０に供給する。反応槽
２０には溶媒供給口２１より、溶媒を供給する。第３番
目の反応槽２０かも、留出口２２を経てエチレングリコ
ールを含む溶媒が留出する。A certain amount of the reaction solution is extracted from the reaction tank 17 by the extraction pump 19 and supplied to the third reaction tank 20 . A solvent is supplied to the reaction tank 20 from a solvent supply port 21 . A solvent containing ethylene glycol is also distilled out from the third reaction tank 20 via the distillation port 22.

抜取ポンプ２３により、反応槽から一定量の反応溶液を
抜取った後、溶剤を分離してポリエチレンテレフタレー
トを取り出ス。After a certain amount of the reaction solution is withdrawn from the reaction tank by the withdrawal pump 23, the solvent is separated and the polyethylene terephthalate is taken out.

第４図は本発明の別の実施態様である。多段反応器２４
は堰２７，２８，２９．３０を有する仕切板によって区
分され工おり、ビス−ｗ　−ヒドロキシアルキルテレフ
タレート及びその低重合体は塔頂による供給口２５かも
反応器内に供給され、各段の堰２７，２８，２９，３０
を経て反応を伴ないながら順次塔頂より塔底に移行する
。反応により生成したエチレングリコールは仕切板に設
けられた小孔より蒸気状で各段を順次上方に移行して塔
頂より留出口２６を経て、溶媒蒸気とともに留出する。FIG. 4 is another embodiment of the invention. Multistage reactor 24
The reactor is separated by partition plates having weirs 27, 28, 29, and 30, and bis-w-hydroxyalkyl terephthalate and its low polymer are also fed into the reactor through the feed port 25 from the top of the column, and 27, 28, 29, 30
It sequentially moves from the top of the column to the bottom of the column, accompanied by a reaction. The ethylene glycol produced by the reaction moves upward through each stage in a vapor form through small holes provided in the partition plate, passes through the distillation port 26 from the top of the column, and is distilled out together with the solvent vapor.

エチレングリコールと、溶媒は蒸留塔３２で分離され、
エチレングリコールは塔頂より３３を経て系外へ、溶媒
は塔底より３４を経て再び反応系内に移行される。Ethylene glycol and the solvent are separated in a distillation column 32,
Ethylene glycol is transferred from the top of the column to the outside of the system via 33, and the solvent is transferred from the bottom of the column via 34 to the reaction system again.

反応溶液は塔底より３５を経て抜取られ脱気押出機３７
ｖ？−より溶媒を３８に分離した後、紡糸頭３９を経て
ポリエチレンテレフタレート繊維として４０に巻取られ
る。The reaction solution is extracted from the bottom of the tower via 35 and transferred to a degassing extruder 37
v? - After separating the solvent into 38, it passes through a spinning head 39 and is wound up into 40 as a polyethylene terephthalate fiber.

別のライ／４１より脱気押出機４２に供給された反応溶
液は溶媒を４３に分離した後、フィルムダイ４４を経て
、ポリエチレンテレフタレートフィルムとして４５に巻
取られる。The reaction solution supplied to the degassing extruder 42 from another lie/41 separates the solvent into 43, passes through a film die 44, and is wound up into a polyethylene terephthalate film 45.

別のライン４６よりコンデンサー４７に供給された反応
液は、ポリエチレンテレフタレートの融点以下に冷却さ
れて、ポリエチレンテレフタレートの微粒子が析出し、
分離機４８１／！：より別に４９より供給した溶剤によ
り洗浄されて５１よりポリエチレンテレフタレートの微
粒子が取出される。別の取出口５０から洗浄用溶剤及び
反応系に使用される溶媒が取出される。The reaction liquid supplied to the condenser 47 from another line 46 is cooled to below the melting point of polyethylene terephthalate, and fine particles of polyethylene terephthalate are precipitated.
Separator 481/! : Separately, the fine particles of polyethylene terephthalate are taken out from 51 after being washed with a solvent supplied from 49. A cleaning solvent and a solvent used in the reaction system are taken out from another outlet 50.

実施例１ 極限粘度０１１２の芳香族カルボン酸とエチレングリコ
ールのエステル化物を２８０℃まで加熱し溶融状態とし
、φ８４謁の回転円板式ロータリーアトマイザ−を３０
００　Ｏｒｐｍ　で回転させることにより平均粒径３０
μｍの微粒子とし有機物媒体東しシリコンオイル８ＲＸ
−３１０中に分散後２８０℃まで加熱、２０分経過後、
２００℃まで冷却し回収したポリマーの極限粘度は０．
３８であった。Example 1 An esterified product of aromatic carboxylic acid and ethylene glycol having an intrinsic viscosity of 0112 was heated to 280°C to melt it, and a rotating disc type rotary atomizer with a diameter of 84 mm was heated to 30 °C.
By rotating at 00 Orpm, the average particle size is 30
Silicone oil 8RX with μm fine particles and organic medium
After dispersing in -310 and heating to 280℃, after 20 minutes,
The intrinsic viscosity of the polymer recovered after cooling to 200°C is 0.
It was 38.

−実施例２ テレフタル酸１００部、二チン／グリコール４５部およ
びエチレングリコールに溶解させた三酸化アンチモン０
．０５部を攪拌混合し、スラリー化して１２ｋｇ／ｈ　
の割合で内容積３０Ｊのエステル化反応器に供給し、連
続的にエステル化反応させた後にエステル化率９３％、
平均重合度８．３のエステル化物を得た。このエステル
化物を１０ｋ１９／ｈ　の割合で微粒化装置（コロ・ア
トマイザ−社製２回転式アトマイザーＰ−６．３型）に
供給し、溶融液状のまま平均粒径１３８μｍの微粒子状
にして連続的にアルキル・ジフェニル（新日鉄化学製、
サームエス７００）を２０ｋｇ／ｈ　で循環している第
３図に示した、夫々の内容積が６１の３連式重合反応器
に供給した。- Example 2 100 parts of terephthalic acid, 45 parts of ditin/glycol and 0 antimony trioxide dissolved in ethylene glycol
．． Stir and mix 0.05 parts to form a slurry and produce 12 kg/h.
was fed to an esterification reactor with an internal volume of 30 J at a ratio of
An esterified product with an average degree of polymerization of 8.3 was obtained. This esterified product was fed into an atomization device (two-rotation atomizer P-6.3 type manufactured by Coro Atomizer Co., Ltd.) at a rate of 10k19/h, and continuously converted into fine particles with an average particle size of 138 μm while remaining in a molten liquid state. Alkyl diphenyl (Nippon Steel Chemical Co., Ltd.,
Therm-S 700) was supplied to a triple polymerization reactor, each having an internal volume of 61, as shown in FIG. 3, which was circulating at 20 kg/h.

第１槽目を２７０℃、真空度５００　Ｔｏｒｒ、第２槽
目を２８０℃、真空度３００　Ｔｏｒｒ、第３槽目を２
８５℃、真空度２００　Ｔｏｒｒ　で縮合反応させたと
ころ、第１槽からエチレングリコール１０．７％を含む
アルキル・ジフェニル溶液が、第２槽目かもエチレング
リコール２．６％を含むアルキル・ジフェニル溶液が、
第３槽目からエチレングリコール０＋４％を含むアルキ
ル・ジフェニル溶液が留出し、第３槽目かもフェノール
・テトロクロルエタン（重量比１対１）溶液で、３０℃
で測定したＩｖ値０．５８のポリエチレンテレフタレー
トが９．７ｋｇ／ｈ　の割合で得られた。The first tank was set at 270°C and the vacuum level was 500 Torr, the second tank was set at 280°C and the vacuum level was 300 Torr, and the third tank was set at 280°C and the vacuum level was 300 Torr.
When the condensation reaction was carried out at 85°C and a vacuum of 200 Torr, an alkyl diphenyl solution containing 10.7% ethylene glycol was produced in the first tank, and an alkyl diphenyl solution containing 2.6% ethylene glycol was produced in the second tank. ,
An alkyl diphenyl solution containing 0+4% ethylene glycol is distilled out from the third tank, and a phenol/tetrochloroethane (1:1 weight ratio) solution is distilled out at 30°C.
Polyethylene terephthalate with an Iv value of 0.58 was obtained at a rate of 9.7 kg/h.

実施例３ ジメチルテレフタレート１００部に対して、エチレング
リコール７２部、酢酸マ／ガン０．０４部、トリフェニ
ルホフファイト０．１部、三酸化ア／テモン０．０３部
の割合で連続的にエステル交換反応器に供給して得られ
たビスーＷ−ヒドロキシアルキルテレフタレート及びそ
の低重合物を１５ｋｐ／ｈ　の割合で、微粒化装置（コ
ロ・アトマイザ−社製９回転式アトマイザーＰ−６．３
型）に供給し、溶融液状のまま平均粒径６３μｍの微粒
子状にして連続的に第４図に示したような直径１００朋
、各段の高さ１５０ｍｍの４段式重合反応器に供給した
。この重合反応器の底部から３０ｋｇ／ｈ　の割合でト
ルエ／を供給し、２７０℃、加圧下で縮合反応を行なわ
せた結果、塔頂からエチレングリコール１２％を含むト
ルエン蒸気が留出した。塔底より取出したトルエン溶液
を冷却したところ、微粒子状のポリエチレンテレフタレ
ート析出分離した。得られたポリエチレンテレフタレー
トのＩＶ値を実施例２と同様な方法で測定した結果０．
５８であった。Example 3 Ester was continuously added to 100 parts of dimethyl terephthalate in a ratio of 72 parts of ethylene glycol, 0.04 part of acetate/magnetic acid, 0.1 part of triphenylhofite, and 0.03 part of atom/temon trioxide. The bis-W-hydroxyalkyl terephthalate and its low polymer obtained by supplying it to the exchange reactor were fed into an atomizer (9-rotary atomizer P-6.3 manufactured by Coro Atomizer Co., Ltd.) at a rate of 15 kp/h.
The molten liquid was turned into fine particles with an average particle size of 63 μm and continuously fed into a four-stage polymerization reactor with a diameter of 100 mm and a height of each stage of 150 mm as shown in Figure 4. . Toluene was supplied from the bottom of the polymerization reactor at a rate of 30 kg/h to carry out a condensation reaction at 270° C. under pressure, and as a result, toluene vapor containing 12% ethylene glycol was distilled from the top of the column. When the toluene solution taken out from the bottom of the tower was cooled, fine particles of polyethylene terephthalate were precipitated and separated. The IV value of the obtained polyethylene terephthalate was measured in the same manner as in Example 2, and the result was 0.
It was 58.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明のポリエステルの重合装置の一例を示す
ものであり、第２図は微粒化装置と反応容器とを直結し
た本発明のポリエステルの重合装置の他の態様を示す図
である。 第３図及び第４図は本発明のポリエステル重合装置の他
の態様を示す図である。 ！包の浄ＩＩ（内容に変疋ない −”＝１−　）　ｅ シャ　２　回 手続補正書（方式） ％式％ １、事件の表示 特願昭５８−２４５７９０号 ２、発明の名称 ポリエステルの重合法およびそれに用いる重合装置３、
補正をする者 事件との関係　特許出願人 東京都中央区京橋二丁目３番１９号 （６０３）三菱レイヨン株式会社 取締役社長　河　崎　晃　夫 ４、代理人 東京都中央区京橋二丁目３番１９号 ７、補正の内容 明細書および図面の浄書（内容に変更なし）手続補正書 昭和６０年　３月（８日 特許庁長官　志　賀　学　殿 ２、発明の名称 ポリエステルの重合法およびそれに用いる重合装置３、
補正をする者 事件との関係　特許出願人 東京都中央区京橋二丁目３番１９号 （６０３）三菱レイヨン株式会社 取締役社長　河　崎　晃　夫 ４、代　理　人 東京都中央区京橋二丁目３番１９号 自発 ６、補正の対象 （１）　訂正明細書第２頁、第９行の「分散せした」を
「分散せしめた」に訂正する。 （２）同第６頁、第７行〜第８行の「溶液状熱媒体」を
「液状熱媒体」に訂正する。 （３）　同第１０頁、第１７行の「メツショ」を「メツ
シュ」に訂正する。 （４）　同第１６頁、第４行の「トリフェニルホスファ
イト」を「トリフェニルホスファイト」に訂正する。 （５）　同第１６頁、第１８行〜第１９行の「ポリエチ
レンテレフタレート析出分離」を「ポリエチレンテレフ
タレートが析出分離」に訂正する。 以上FIG. 1 shows an example of the polyester polymerization apparatus of the present invention, and FIG. 2 shows another embodiment of the polyester polymerization apparatus of the present invention in which the atomization device and the reaction vessel are directly connected. FIGS. 3 and 4 are diagrams showing other embodiments of the polyester polymerization apparatus of the present invention. ! Bao no Jyo II (no change in content-”=1-) e Sha 2nd procedural amendment (method) % formula % 1, Indication of the case Patent Application No. 1982-245790 2, Name of the invention Polyester polymerization method and a polymerization device 3 used therein,
Relationship with the person making the amendment Patent applicant: 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Akio Kawasaki, President and CEO of Mitsubishi Rayon Co., Ltd. 4; Agent: 2-3-19 Kyobashi, Chuo-ku, Tokyo 7. Amendments to the description and drawings (no changes to the contents) Procedural amendments March 8, 1985 Manabu Shiga, Commissioner of the Patent Office 2 Title of the invention Polyester polymerization method and polymerization apparatus used therein 3 ,
Relationship with the case of the person making the amendment Patent applicant: 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Akio Kawasaki, President and CEO of Mitsubishi Rayon Co., Ltd. 4, Agent: 2-3-19 Kyobashi, Chuo-ku, Tokyo No. 6, Subject of amendment (1) "Distributed" on page 2, line 9 of the amended specification is corrected to "distributed". (2) On page 6, lines 7 to 8, "solution heat medium" is corrected to "liquid heat medium." (3) On page 10, line 17, "Metsusho" is corrected to "Metsushu". (4) On page 16, line 4, "triphenyl phosphite" is corrected to "triphenyl phosphite." (5) "Polyethylene terephthalate precipitation separation" on page 16, lines 18 to 19 is corrected to "polyethylene terephthalate precipitation separation."that's all

Claims (2)

【特許請求の範囲】[Claims] （１）　ビスーＷ−ヒドロキシアルキルテレフタレート
又はその初期給金物を溶融状態で、その代表粒径が５０
０μ以下なる粒状体に微粒化し、溶液状熱媒体を満たし
た重合反応器中に供給してエマルジョンを形成し、前記
溶融物の融点以上３２０℃以下の温度に加熱して重合せ
しめることを特徴とするポリエステルの重合法。(1) Bis-W-hydroxyalkyl terephthalate or its initial charge in a molten state with a typical particle size of 50
It is characterized in that it is atomized into granules of 0μ or less, fed into a polymerization reactor filled with a solution heating medium to form an emulsion, and heated to a temperature above the melting point of the melt and below 320°C to polymerize it. Polyester polymerization method. （２）　ビスーＷ−ヒドロキシアルキルテレフタレート
又はその初期給金物を、代表粒径が５００μ以下に微粒
子化する微粒化装置と、熱媒加熱部を備えた反応容器、
ポＩＪ　エステルと熱媒とを分離するための固液分離装
置、エチレングリコールと熱媒とを分離するための蒸留
塔を備えたポリエステルの重合装置。(2) a reaction vessel equipped with an atomization device that atomizes bis-W-hydroxyalkyl terephthalate or its initial feed to a typical particle size of 500μ or less, and a heat medium heating section;
Polyester polymerization equipment equipped with a solid-liquid separator for separating ester and heat medium, and a distillation column for separating ethylene glycol and heat medium.
JP24579083A 1983-12-28 1983-12-28 Polymerization of polyester and polymerization apparatus using therefor Pending JPS60238318A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP24579083A JPS60238318A (en) 1983-12-28 1983-12-28 Polymerization of polyester and polymerization apparatus using therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24579083A JPS60238318A (en) 1983-12-28 1983-12-28 Polymerization of polyester and polymerization apparatus using therefor

Publications (1)

Publication Number Publication Date
JPS60238318A true JPS60238318A (en) 1985-11-27

Family

ID=17138865

Family Applications (1)

Application Number Title Priority Date Filing Date
JP24579083A Pending JPS60238318A (en) 1983-12-28 1983-12-28 Polymerization of polyester and polymerization apparatus using therefor

Country Status (1)

Country Link
JP (1) JPS60238318A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61157524A (en) * 1984-12-28 1986-07-17 Toyobo Co Ltd Production of polyester

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61157524A (en) * 1984-12-28 1986-07-17 Toyobo Co Ltd Production of polyester

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