JPH05214089A - Method for separating sticky foreign matter from by-product produced in polymerization step for producing polymer - Google Patents
Method for separating sticky foreign matter from by-product produced in polymerization step for producing polymerInfo
- Publication number
- JPH05214089A JPH05214089A JP5433592A JP5433592A JPH05214089A JP H05214089 A JPH05214089 A JP H05214089A JP 5433592 A JP5433592 A JP 5433592A JP 5433592 A JP5433592 A JP 5433592A JP H05214089 A JPH05214089 A JP H05214089A
- Authority
- JP
- Japan
- Prior art keywords
- products
- product
- foreign substances
- produced
- foreign matter
- 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.)
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- Polyesters Or Polycarbonates (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、例えばポリエステルエ
ーテル共重合体を重縮合反応させて生成するに際して、
この過程で副生するエチレングリコールや蒸気等の副生
物に同伴した未反応のモノマーやオリゴマー等の付着性
異物が真空吸引系統に悪影響を及ぼすことがないだけで
なく、副生物と付着性異物が容易に分離できる重合体の
重合反応過程で副生する副生物とこれに同伴した付着性
異物の分離方法に関する。BACKGROUND OF THE INVENTION The present invention relates to, for example, polycondensation reaction of a polyester ether copolymer
Not only does adhering foreign matter such as unreacted monomers and oligomers that accompany by-products such as ethylene glycol and steam produced as by-products in this process not adversely affect the vacuum suction system, but also by-products and adhesive foreign matter The present invention relates to a method for separating by-products by-produced in the course of a polymerization reaction of a polymer that can be easily separated and adherent foreign substances accompanying the by-products.
【0002】[0002]
【従来の技術】従来、ポリエステルエーテル共重合体を
生成する場合、重縮合反応機とこれの内部をほぼ完全真
空状態下にする真空ポンプ、エジェクタ等の真空手段を
真空配管で連結して構成した重縮合反応装置を利用し
て、重合原料を入れた重縮合反応機内部を、例えば0.
5〜1mmHg・abs 程度のほぼ完全真空状態下にして、内
容物温度で、例えば260〜290℃程度に加熱させ、
重縮合反応させている。ところで、この重縮合反応過程
では、未反応のモノマーやオリゴマー等の付着性異物を
同伴したグリコール類や蒸気等の副生物が副生すること
が知られている。このため、重縮合反応機とこの内部を
ほぼ完全真空状態下にする真空ポンプ、エジェクタ等の
真空手段を連結する真空配管やこの真空手段の内部にこ
れら副生物に同伴した付着性異物が付着、成長して、早
期に真空手段の真空吸引能力が低下する。2. Description of the Related Art Conventionally, when a polyester ether copolymer is produced, a polycondensation reactor and a vacuum means such as a vacuum pump and an ejector for keeping the inside of the polycondensation reactor in a nearly completely vacuum state are connected by vacuum piping. Using the polycondensation reactor, the inside of the polycondensation reactor containing the polymerization raw material is, for example, 0.
In a substantially complete vacuum state of about 5 to 1 mmHg · abs, heat the contents at a temperature of, for example, about 260 to 290 ° C.
It is polycondensed. By the way, in this polycondensation reaction process, it is known that by-products such as glycols and steam accompanied by adherent foreign substances such as unreacted monomers and oligomers are by-produced. Therefore, the polycondensation reactor and a vacuum pump for bringing the inside into a substantially complete vacuum state, a vacuum pipe connecting the vacuum means such as an ejector and the adhering foreign substances entrained in these by-products adhere inside the vacuum means, It grows and the vacuum suction capability of the vacuum means is reduced at an early stage.
【0003】こうしたことから、従来、図2に概略を示
す重縮合反応装置のように、重縮合反応機aと真空手段
bを連結する真空配管cの途中に図中dとして示す凝縮
機を設置している。この凝縮機dは、図3に示すように
密閉された筒状の本体e内部の長さ方向の一端と他端に
のぞませて真空配管cの重縮合反応機a側に連結する入
口配管fとこれの真空手段b側に連結する出口配管gを
設けるとともに、本体e内部の入口配管fと出口配管g
の開口端より中央部側に横断的に一対の隔壁h、hを設
け、この一対の隔壁h、h間に副生物に同伴した付着性
異物を選択的に固形物にしたり、凝縮副生物の一部の中
に混入又は溶融させて、凝固又は凝縮捕集させる複数の
処理配管iを両端を入口配管fと出口配管gに連通させ
て平行に間隔をあけて配設して副生物の流動経路jを形
成し、更にはこの一対の隔壁h、h間にのぞませて副生
物を凝縮させる水等の処理流体の流入配管kと流出配管
lを設けたものである。尚、図中mは本体eの出口配管
g側に設けた副生物を凝縮させた凝縮副生物の排出配管
で、これは下方に設けた受槽nに連通させている。又、
oは真空手段bから外部にのぞませて設けた気体状の副
生物の排気配管である。この他、こうした重縮合反応機
aには、内部を加熱させる加熱ソケットが外装されてい
るが、図示を省略している。For this reason, conventionally, as in the polycondensation reactor schematically shown in FIG. 2, the condenser shown as d in the figure is installed in the middle of the vacuum pipe c connecting the polycondensation reactor a and the vacuum means b. is doing. As shown in FIG. 3, the condenser d is an inlet pipe connected to the polycondensation reactor a side of the vacuum pipe c, with one end and the other end in the length direction inside the closed cylindrical main body e. f and an outlet pipe g connected to the vacuum means b side thereof are provided, and an inlet pipe f and an outlet pipe g inside the main body e are provided.
A pair of partition walls h, h are provided transversely to the central portion side from the opening end of the, and the adherent foreign substances entrained by by-products are selectively solidified between the pair of partition walls h, h, or condensed by-products Flow of by-products by arranging a plurality of processing pipes i, which are mixed or melted in a part and solidified or condensed and collected, with both ends in communication with the inlet pipe f and the outlet pipe g and spaced in parallel. A passage j is formed, and further, an inflow pipe k and an outflow pipe l for a treatment fluid such as water for condensing by-products are provided between the pair of partition walls h, h. In the figure, m is a discharge pipe for the condensed by-product, which is provided on the outlet pipe g side of the main body e and in which the by-product is condensed, and is connected to a receiving tank n provided below. or,
Reference numeral o is an exhaust pipe for gaseous by-products provided outside the vacuum means b. In addition, a heating socket for heating the inside of the polycondensation reactor a is externally mounted, but not shown.
【0004】[0004]
【発明が解決しようとする課題】ところが、このような
凝縮機を重縮合反応機と真空手段を連結する真空配管の
途中に設けた場合でも、未反応のモノマーやポリマー等
の付着性異物を同伴した高温の気体状の副生物がこの本
体内部に入口配管を通じて流入したときに、水等の処理
流体で冷却されている副生物が流動する流動経路を形成
する処理配管の入口配管側の開口端に接触して、この部
分に特に付着性異物が付着、成長することは避けられな
い。そして、こうした態様の凝縮機では、筒状の本体内
部の長さ方向に複数の処理配管を平行に配設する関係
上、ここを付着性異物が横断的に閉塞するのを防止する
自由度が少なく、早期に真空手段の真空吸引能力が低下
する問題が依然残る。又、副生物に同伴した付着性異物
が選択的に固形物として凝固して処理配管に付着する
他、凝縮副生物の一部の中に混入又は溶融して、凝縮機
の下方に設けた受槽に溜まるのであるが、この付着性異
物を含有した凝縮副生物はTOD(全酸素要求量)が高
いという理由から環境上問題がある。However, even when such a condenser is provided in the middle of the vacuum pipe connecting the polycondensation reactor and the vacuum means, unreacted monomers and polymers such as adherent foreign substances are entrained. The open end of the processing pipe that forms the flow path through which the by-product, which is cooled by the processing fluid such as water, flows when the high-temperature gaseous by-product flows into the main body through the inlet pipe. It is unavoidable that, in particular, adherent foreign matter adheres to and grows on this part by contacting with. In the condenser of such an aspect, since a plurality of processing pipes are arranged in parallel in the lengthwise direction inside the cylindrical main body, there is a degree of freedom to prevent the adhering foreign matter from being blocked transversely. However, there is still a problem that the vacuum suction capability of the vacuum means is lowered at an early stage. In addition, the adhering foreign substances entrained in the by-products selectively solidify as solids and adhere to the processing pipes, and are mixed or melted in a part of the condensed by-products and are installed in the receiving tank below the condenser. However, the condensed by-product containing the adherent foreign matter is environmentally problematic because of its high TOD (total oxygen demand).
【0005】このような従来の問題点に鑑みて発明され
たのが本発明に係る重合体の重合反応過程で副生する副
生物とこれに同伴した付着性異物の分離方法で、例えば
ポリエステルエーテル共重合体を重縮合反応させて生成
するに際して、この過程で副生するエチレングリコール
や蒸気等の副生物に同伴した未反応のモノマーやオリゴ
マー等の付着性異物が真空吸引系統に悪影響を及ぼすこ
とがなく、しかも副生物と付着性異物が容易に分離でき
ることを目的とする。In view of such conventional problems, a method of separating the by-product by-produced in the polymerization reaction process of the polymer according to the present invention and the adhering foreign substance accompanied with the by-product, for example, polyester ether Adhesive foreign substances such as unreacted monomers and oligomers that accompany by-products such as ethylene glycol and steam that are by-produced in this process during the polycondensation reaction of the copolymer adversely affect the vacuum suction system. It is intended that the by-products and adherent foreign substances can be easily separated from each other.
【0006】[0006]
【課題を解決するための手段】こうした目的を達成する
ため、本発明の請求項1では、重合体を重合反応させて
生成するに際して、この過程で副生する未反応のモノマ
ーやオリゴマー等の付着性異物を同伴した副生物を付着
性異物の融点以上にして誘導排出させ、この誘導排出中
又は後に未反応のモノマーやオリゴマー等の付着性異物
を同伴した副生物を付着性異物の融点以下にした処理液
体と接触させて副生物と付着性異物を分離させることを
特徴とした重合体の重合反応過程で副生する副生物とこ
れに同伴した付着性異物の分離方法を要旨とする。又、
請求項2では、処理液体が凝縮副生物と同種のものであ
ることを例示している。更に、請求項3では、未反応の
モノマーやオリゴマー等の付着性異物を同伴した副生物
を付着性異物の融点以上に加熱して誘導排出させること
を例示している。In order to achieve these objects, according to claim 1 of the present invention, when a polymer is produced by a polymerization reaction, unreacted monomers and oligomers by-produced in this process are attached. By-products with entrained foreign substances are heated to a temperature above the melting point of the adherent foreign substances and induced to be discharged. The gist is a method for separating a by-product by-produced in a polymerization reaction process of a polymer and an adhering foreign substance entrained in the by-product, which is characterized in that the by-product is brought into contact with the treated liquid to separate the adhering foreign substance. or,
Claim 2 exemplifies that the treated liquid is of the same type as the condensed by-product. Further, the third aspect exemplifies that the by-product accompanied by the adhering foreign matter such as unreacted monomer or oligomer is heated to a temperature equal to or higher than the melting point of the adhering foreign matter and induced to be discharged.
【0007】[0007]
【作用】而して、このような分離方法では、未反応のモ
ノマーやオリゴマー等の付着性異物を同伴した副生物が
付着性異物の融点以下にした処理液体と接触したとき
に、付着性異物が固形物として析出し、副生物と付着性
異物の分離ができるのである。According to such a separation method, when the by-product accompanied by the unreacted adhesive foreign matter such as monomer or oligomer is brought into contact with the processing liquid whose melting point is lower than that of the adhesive foreign matter, the adhesive foreign matter is removed. Is deposited as a solid matter, and the by-product and adherent foreign matter can be separated.
【0008】[0008]
【実施例】本発明に係る重合体の重合反応過程で副生す
る副生物とこれに同伴した付着性異物の分離方法の詳細
を更に添付の図面に基づき説明する。EXAMPLES The details of the method for separating by-products by-produced in the course of the polymerization reaction of the polymer according to the present invention and the adhering foreign substances entrained therein will be described with reference to the accompanying drawings.
【0009】図示した実施例では、本出願人が今度、ポ
リエステルエーテル共重合体を連続的に、且つ反応時間
を短くして生成させることを目的に提案した連続式重縮
合反応装置を基に説明している。The illustrated embodiment is described based on the continuous polycondensation reaction apparatus proposed by the present applicant for the purpose of producing a polyester ether copolymer continuously and with a short reaction time. is doing.
【0010】そして、この連続式重縮合反応装置では、
ポリエステルとポリエーテル類を溶融混合した後、又は
溶融混合しながら、連続的に供給して、重縮合反応を行
わせるものである。And in this continuous polycondensation reactor,
After the polyester and the polyethers are melt-mixed, or while being melt-mixed, they are continuously supplied to carry out the polycondensation reaction.
【0011】図1には、このような連続式重縮合反応装
置の概略を示している。図中1として示すのが連続式横
型重縮合反応機、又図中2として示すのがこれの内部
を、例えば0.5〜1.0mmHg・abs 程度のほぼ完全真
空状態下にする真空ポンプの一種の封液を用いるナッシ
ュポンプを利用した真空手段、更に図中3として示すの
は重縮合反応機1と真空手段2を連結する真空配管であ
る。FIG. 1 shows an outline of such a continuous polycondensation reaction apparatus. A continuous horizontal polycondensation reactor is shown as 1 in the figure, and a vacuum pump for making the inside of this a substantially complete vacuum state of about 0.5 to 1.0 mmHg · abs is shown as 2 in the figure. A vacuum means using a Nash pump that uses a kind of sealing liquid, and further shown as 3 in the figure is a vacuum pipe connecting the polycondensation reactor 1 and the vacuum means 2.
【0012】そして、この真空配管3の途中にはメカニ
カルブースター4、5が二つ、直列に設けられている。
ところで、封液を用いるナッシュポンプを利用した真空
手段2では達成減圧度が15mmHg・abs 程度が限度で、
必要とされる0.5〜1.0mmHg・abs 程度のほぼ完全
真空状態下に到達させることができない。このため、こ
こでは真空配管3の途中にメカニカルブースター4、5
を設けて、所望の減圧度が達成できるようにしている。
又、この真空配管3の重縮合反応機1とこれの側のメカ
ニカルブースター4の間にある部分には、この内部を流
動する未反応のモノマーやオリゴマー等の付着性異物を
同伴した副生物を付着性異物の融点である100℃程度
以上のこれ自身の温度で、100〜250℃、好ましく
は100〜120℃程度の範囲内に加熱する加熱ソケッ
ト6が設けられている。この付着性異物を同伴した副生
物を、こうした100℃以上に加熱させることで、付着
性異物は溶融粘度が小さくなって、重縮合反応機1の内
部圧力を前記した範囲内にしたときに、通常3〜500
m3 /分程度とされる排気速度では、真空配管3の管壁
への付着の問題がなくなる。又、これの加熱温度を25
0℃以下にするのは、加熱媒体に一般にシリコンオイル
を用いることの制約と経済効果によるものである。Two mechanical boosters 4 and 5 are provided in series in the vacuum pipe 3.
By the way, with the vacuum means 2 using a Nash pump that uses a sealing liquid, the achieved decompression degree is limited to about 15 mmHg · abs,
It is not possible to reach the required almost complete vacuum state of about 0.5 to 1.0 mmHg · abs. Therefore, here, mechanical boosters 4, 5 are provided in the middle of the vacuum pipe 3.
Is provided so that a desired degree of reduced pressure can be achieved.
In addition, in the portion of the vacuum pipe 3 between the polycondensation reactor 1 and the mechanical booster 4 on the side thereof, by-products accompanied by adhering foreign substances such as unreacted monomers and oligomers flowing inside the reactor are provided. A heating socket 6 is provided for heating within a range of 100 to 250 ° C., preferably 100 to 120 ° C., at its own temperature of 100 ° C. or higher which is the melting point of the adherent foreign substance. By heating the by-product accompanied by the adherent foreign matter to such 100 ° C. or higher, the meltable viscosity of the adherent foreign matter becomes small, and when the internal pressure of the polycondensation reactor 1 is set within the above range, Usually 3 to 500
At an exhaust rate of about m 3 / min, the problem of adhesion of the vacuum pipe 3 to the pipe wall is eliminated. Also, the heating temperature of this is 25
The reason why the temperature is 0 ° C. or lower is due to the restriction and economic effect of using silicone oil as a heating medium.
【0013】又、7はナッシュポンプを利用した真空手
段2の封液配管である。これの途中には、封液貯液槽8
とこの封液を冷却する冷却機9が設けられている。尚、
図中10は配管の封液貯液槽8の液中にのぞませた端部に
設けたフィルターである。又、11は封液貯液槽8に設け
たオバーフロー用配管、12は同じく排気配管である。更
に、図中13は冷却機9に冷却水を流入させる流入配管、
14は冷却機9から冷却水を流出させる流出配管である。
この冷却機9は、こうした重縮合反応機に従来凝縮機と
して用いられている図3に示すのと同態様のものであ
る。尚、ここでは封液として、エチレングリコール液を
用いる。そして、これは付着性異物の融点である100
℃程度以下のこれ自身の温度で5〜50℃、好ましくは
10〜30℃程度の範囲内に調整されている。Reference numeral 7 is a liquid sealing pipe of the vacuum means 2 using a Nash pump. In the middle of this, a sealing liquid storage tank 8
A cooling machine 9 for cooling the sealing liquid is provided. still,
Reference numeral 10 in the figure denotes a filter provided at the end of the pipe, which is filled with the liquid in the liquid-sealing liquid storage tank 8 and looked into the liquid. Further, 11 is an overflow pipe provided in the liquid storage tank 8 and 12 is an exhaust pipe. Further, reference numeral 13 in the figure is an inflow pipe for flowing cooling water into the cooler 9,
Reference numeral 14 is an outflow pipe for outflowing the cooling water from the cooler 9.
This cooler 9 has the same configuration as that shown in FIG. 3 which is conventionally used as a condenser in such a polycondensation reactor. Here, an ethylene glycol liquid is used as the sealing liquid. This is 100 which is the melting point of the adherent foreign matter.
The temperature is adjusted to be within the range of 5 to 50 ° C., preferably 10 to 30 ° C. at its own temperature of about 0 ° C. or less.
【0014】次に、15、16は重縮合反応機1の入口配管
と出口配管を示している。又、図中17はこれら入口配管
15と出口配管16に設けたバルブである。更に、18はのぞ
き窓、19は内容物を混合攪拌させる攪拌翼である。そし
て、このような重縮合反応機1には、この他、内部を内
容物温度で、例えば260〜290℃に加熱する加熱ソ
ケットが外装されているが、ここでは図示を省略してい
る。Next, 15 and 16 show the inlet pipe and the outlet pipe of the polycondensation reactor 1. Also, in the figure, 17 are these inlet pipes.
15 and a valve provided in the outlet pipe 16. Further, 18 is a sight glass, and 19 is a stirring blade for mixing and stirring the contents. In addition to this, the polycondensation reactor 1 is also provided with a heating socket for heating the inside to, for example, 260 to 290 ° C. at the content temperature, but it is not shown here.
【0015】而して、こうした連続式重縮合反応装置で
は、次に示すようにしてポリエステルエーテル共重合体
を生成させるものである。Thus, in such a continuous polycondensation reactor, a polyester ether copolymer is produced as follows.
【0016】先ず、連続式横型重縮合反応機1の入口配
管15を通じてポリエステルとポリエーテル類を溶融混合
した後、又は溶融混合しながら、連続的に供給する。具
体的には、ここではポリエステルの100量体を70重
量%とポリエーテル類を30重量%溶融混合させて用い
る。このとき、重縮合反応機1の内部は、圧力が0.1
〜2.0mmHg・abs 、好ましくは0.5〜1.0mmHg・
abs 程度の範囲内のほぼ完全真空状態下に維持され、又
温度は内容物温度で260〜290℃程度に加熱されて
いる。又、これら内容物は約30〜120分程度、この
内部で重縮合反応させるように調整されている。このよ
うにして、ポリエステルエーテル共重合体の100量体
が生成され、これは出口配管16を通じて流出する。First, polyester and polyether are melt-mixed through the inlet pipe 15 of the continuous horizontal polycondensation reactor 1 or are continuously supplied while being melt-mixed. Specifically, here, 70% by weight of a 100-mer polyester and 30% by weight of polyethers are melt mixed and used. At this time, the pressure inside the polycondensation reactor 1 is 0.1
~ 2.0mmHg ・ abs, preferably 0.5 ~ 1.0mmHg ・
It is maintained under a near-complete vacuum state within the range of abs, and the temperature is heated to about 260 to 290 ° C. at the content temperature. Further, these contents are adjusted so as to undergo a polycondensation reaction within the inside for about 30 to 120 minutes. In this way, a 100-mer polyester ether copolymer is produced, which flows out through the outlet pipe 16.
【0017】一方、この重縮合反応機1での重縮合反応
過程で副生するエチレングリコールや蒸気等の副生物は
未反応のモノマーやオリゴマー等の付着性異物を同伴し
て、真空手段2に吸引されて重縮合反応機1から真空配
管3を通じて外部に誘導排出される。このとき、真空配
管3を流動する付着性異物を同伴した副生物は、加熱ソ
ケット6によってこれ自身の温度で100〜250℃、
好ましくは100〜120℃程度の範囲内に加熱されて
いるから、付着性異物の溶融粘度は小さくなって、重縮
合反応機1の内部応力を前記した範囲内にしたときに、
通常3〜500m3 /分程度とされる排気速度では、真
空配管3の管壁への付着の問題はないのである。そし
て、二つのメカニカルブースター4、5を通過した付着
性異物を同伴した副生物は、真空手段2の後方に設けた
封液貯液槽8内のこれ自身の温度が5〜50℃、好まし
くは10〜30℃程度の範囲内に調整されたエチレング
リコール液と誘導排出中に接触して、付着性異物が固形
物として析出するとともに、副生物であるエチレングリ
コールや蒸気等はエチレングリコール液中に凝縮した
り、気化状態のまま、排気配管12から外部に排気される
のである。On the other hand, by-products such as ethylene glycol and steam that are by-produced in the polycondensation reaction process in the polycondensation reactor 1 are accompanied by unreacted adhering foreign matters such as monomers and oligomers, and are then transferred to the vacuum means 2. It is sucked and guided and discharged from the polycondensation reactor 1 to the outside through the vacuum pipe 3. At this time, the by-product accompanied by the adherent foreign matter flowing in the vacuum pipe 3 is heated by the heating socket 6 at its own temperature of 100 to 250 ° C.,
Since it is preferably heated within the range of about 100 to 120 ° C., the melt viscosity of the adherent foreign matter becomes small, and when the internal stress of the polycondensation reactor 1 is set within the above range,
At an evacuation speed of usually about 3 to 500 m 3 / min, there is no problem of adhesion of the vacuum pipe 3 to the pipe wall. The by-product accompanied by the adherent foreign matter that has passed through the two mechanical boosters 4 and 5 has its own temperature in the liquid storage tank 8 provided behind the vacuum means 2 of 5 to 50 ° C., preferably Contact with the ethylene glycol solution adjusted to within the range of 10 to 30 ° C during induction discharge causes adherent foreign substances to be deposited as solid matter, and by-products such as ethylene glycol and steam are contained in the ethylene glycol solution. The condensed or vaporized state is exhausted to the outside through the exhaust pipe 12.
【0018】本発明で用いられるポリエステルとして
は、芳香族ジカルボン酸又はそのアルキルエステル、例
えばテレフタル酸、イソフタル酸、2、6−ナフタレン
ジカルボン酸、4、4′−ジカルボキシルジフェニル、
4、4′−ジカルボキシルベンゾフェノン、ビス(4−
カルボキシルフェニル)エタン等、又はこれらのメチ
ル、エチル、プロピル等のアルキルエステルを単独又は
二種以上と、一方グリコールとしてはエチレングリコー
ル、プロピレングリコール、1、4−ブタンジオール、
ネオペンチルグリコール、シクロヘキサンジメタノール
等を単独又は二種以上から合成されるホモポリマー又は
共重合ポリマー又はそれらの混合物が挙げられる。これ
らの内、耐熱性を有するポリエチレンテレフタレートが
好適である。The polyester used in the present invention includes aromatic dicarboxylic acids or alkyl esters thereof, such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxylicdiphenyl,
4,4'-dicarboxylbenzophenone, bis (4-
(Carboxylphenyl) ethane and the like, or these alkyl esters such as methyl, ethyl and propyl, alone or in combination of two or more, while as the glycol, ethylene glycol, propylene glycol, 1,4-butanediol,
Examples include homopolymers or copolymers of neopentyl glycol, cyclohexanedimethanol and the like, or homopolymers or copolymers synthesized from two or more thereof, or a mixture thereof. Of these, polyethylene terephthalate having heat resistance is preferable.
【0019】又、ポリエーテル類としては、一般式
(I) (I)Further, as the polyethers, general formulas (I) and (I) are used.
【化1】 R:C2 〜C9 のアルキレン基 (式中、l個のRは同じものである必要はない。) 一般式(II) (II)[Chemical 1] R: (. Wherein, l number of R need not be the same as) C 2 -C 9 alkylene group of general formula (II) (II)
【化2】 R1 ,R2 :C2 〜C9 のアルキレン基 (式中、(m+n)個のR1 ,R2 は同じものである必
要はない。)[Chemical 2] R 1 , R 2 : C 2 -C 9 alkylene group (wherein (m + n) R 1 , R 2 need not be the same)
【化3】 で示される少なくとも一種又は二種以上が好適に用いら
れる。これらの一般式(I)、(II)において、末端の
ヒドロキシ基は、例えばエステル化された誘導体でもよ
いことは当然である。又、一般式(II)において、芳香
族がハロゲン等の置換基を有するものであってもよい。
更に、一般式(I)、(II)において、R,R1 ,R2 は
好ましくはC2 〜C5 のアルキレン基である。これらの
内で、ビスフェノールA、ビスフェノールS等のポリア
ルキレンオキシド付加物等のように、分子鎖中に芳香環
を有するものが、比較的高温で溶融混合できるので特に
好適である。ポリエーテル類の分子量は、200以上、
好ましくは200〜10000である。ここで、200
未満では生成したポリマーの融点が低下して好ましくな
い。又、10000を越えると、相溶性が悪く、均一な
品質の製品が得にくくなる。ポリエーテル量は1〜60
重量部、好ましくは5〜35重量部である。そして、ポ
リエーテル量が1重量部未満では目的とするポリマーの
物性が得られず、好ましくない。又、60重量部を越え
ると、劣化が激しく、品質が低下するため、好ましくな
い。[Chemical 3] At least one kind or two kinds or more shown by is preferably used. In the general formulas (I) and (II), the terminal hydroxy group may be, for example, an esterified derivative. Further, in the general formula (II), the aromatic may have a substituent such as halogen.
Further, in the general formulas (I) and (II), R, R 1 and R 2 are preferably C 2 to C 5 alkylene groups. Among these, those having an aromatic ring in the molecular chain, such as polyalkylene oxide adducts of bisphenol A, bisphenol S, etc., are particularly preferable because they can be melt-mixed at a relatively high temperature. The molecular weight of polyethers is 200 or more,
It is preferably 200 to 10,000. Where 200
If it is less than the above range, the melting point of the produced polymer is lowered, which is not preferable. On the other hand, if it exceeds 10,000, the compatibility is poor and it becomes difficult to obtain a product of uniform quality. The amount of polyether is 1-60
Parts by weight, preferably 5 to 35 parts by weight. If the amount of polyether is less than 1 part by weight, the desired physical properties of the polymer cannot be obtained, which is not preferable. On the other hand, if the amount exceeds 60 parts by weight, deterioration is severe and the quality is deteriorated, which is not preferable.
【0020】ポリエステルの粘度は、0.3〔dl/
g〕以上、好ましくは0.5〔dl/g〕以上に調整さ
れるのが、成形時のフローが良好になり、成形した成形
品の機械的強度が向上する等して、好適である。The viscosity of polyester is 0.3 [dl /
g] or more, preferably 0.5 [dl / g] or more is preferable because the flow at the time of molding becomes good and the mechanical strength of the molded product is improved.
【0021】ところで、封液としてはエチレングリコー
ル液の他、水、高沸点アルコール等が利用可能である。
そして、この封液は副生物が溶融しないものも利用でき
る。Incidentally, as the sealing liquid, water, high-boiling alcohol, etc. can be used in addition to the ethylene glycol liquid.
Further, as this sealing liquid, one in which the by-product does not melt can be used.
【0022】又、真空配管3の内外が断熱されていた
り、それの長さが相対的に短くて、付着性異物を同伴し
た副生物がこれ自身の温度で付着性異物の融点以下に低
下するおそれがないならば、重縮合反応機1からの誘導
排出中に必ずしも加熱させる必要性はない。Further, the inside and outside of the vacuum pipe 3 are thermally insulated, or the length thereof is relatively short, and the by-product entrained with the adhering foreign matter lowers below the melting point of the adhering foreign matter at its own temperature. If there is no fear, it is not always necessary to heat during the induction discharge from the polycondensation reactor 1.
【0023】更に、付着性異物を同伴した副生物を重縮
合反応機1から誘導排出させて、例えばタンク等に一旦
貯えた後、処理液体と接触させることで、副生物と付着
性異物を分離させることも可能である。Further, the by-product accompanied by the adherent foreign matter is induced and discharged from the polycondensation reactor 1 and once stored in, for example, a tank or the like, and then brought into contact with the treatment liquid, thereby separating the by-product and the adherent foreign matter. It is also possible to let.
【0024】又、本発明は、図示した実施例のように、
ポリエステルエーテル共重合体を連続式で生成する場合
の他、回分式で生成する場合にも適用できる。The present invention, like the illustrated embodiment,
The present invention can be applied not only when the polyester ether copolymer is produced by the continuous system but also when it is produced by the batch system.
【0025】更に、ポリエステルエーテル共重合体の
他、ポリアミド、ポリカーボネート、ポリエステルカー
ボネイト等の重合系樹脂を生成する場合に適用すること
もできる。Further, in addition to the polyester ether copolymer, it can be applied to the case of producing a polymer resin such as polyamide, polycarbonate, polyester carbonate.
【0026】[0026]
【発明の効果】以上のような本発明に係る重合体の重合
反応過程で副生する副生物とこれに同伴した付着性異物
の分離方法では、例えばポリエステルエーテル共重合体
を重縮合反応させて生成するに際して、この過程で副生
するエチレングリコールや蒸気等の副生物に同伴した未
反応のモノマーやオリゴマー等の付着性異物が真空吸引
系統に悪影響を及ぼすことがなく、しかも副生物と付着
性異物が容易に分離できるのである。INDUSTRIAL APPLICABILITY As described above, in the method for separating the by-product by-produced in the course of the polymerization reaction of the polymer according to the present invention and the adhering foreign matter entrained therein, for example, the polyester ether copolymer is subjected to a polycondensation reaction. When it is generated, adhering foreign substances such as unreacted monomers and oligomers that accompany by-products such as ethylene glycol and steam that are by-produced in this process do not adversely affect the vacuum suction system. Foreign matter can be easily separated.
【図1】本発明に係る重合体の重合反応過程で副生する
副生物とこれに同伴した付着性異物の分離方法で用いる
連続式重縮合反応装置の概略を示す説明図FIG. 1 is an explanatory view showing an outline of a continuous polycondensation reaction apparatus used in a method for separating a by-product by-produced in a polymerization reaction process of a polymer according to the present invention and an adhering foreign substance accompanying the by-product.
【図2】従来の重縮合反応装置の概略を示す説明図FIG. 2 is an explanatory view showing the outline of a conventional polycondensation reaction device.
【図3】これに設置する凝縮機を示す断面図FIG. 3 is a sectional view showing a condenser installed therein.
1 連続式横型重縮合反応機 2 真空手段 3 真空配管 4 メカニカルブースター 5 メカニカルブースター 6 加熱ソケット 7 封液配管 8 封液貯液槽 9 冷却機 10 フィルター 11 オーバーフロー用配管 12 排気配管 13 流入配管 14 流出配管 15 入口配管 16 出口配管 17 バルブ 18 のぞき窓 19 攪拌翼 1 Continuous horizontal polycondensation reactor 2 Vacuum means 3 Vacuum piping 4 Mechanical booster 5 Mechanical booster 6 Heating socket 7 Sealing liquid piping 8 Sealing liquid storage tank 9 Cooling machine 10 Filter 11 Overflow piping 12 Exhaust piping 13 Inflow piping 14 Outflow Piping 15 Inlet piping 16 Outlet piping 17 Valve 18 Peephole 19 Stirrer
Claims (3)
て、この過程で副生する未反応のモノマーやオリゴマー
等の付着性異物を同伴した副生物を付着性異物の融点以
上にして誘導排出させ、この誘導排出中又は後に未反応
のモノマーやオリゴマー等の付着性異物を同伴した副生
物を付着性異物の融点以下にした処理液体と接触させて
副生物と付着性異物を分離させることを特徴とした重合
体の重合反応過程で副生する副生物とこれに同伴した付
着性異物の分離方法。1. When a polymer is produced by a polymerization reaction, by-products accompanied by adhering foreign substances such as unreacted monomers and oligomers produced as a by-product in this process are heated to a temperature above the melting point of the adhering foreign substances and then induced and discharged. During or after the induced discharge, by-products accompanied by adherent foreign substances such as unreacted monomers and oligomers are contacted with a treatment liquid whose melting point is lower than the melting point of the adherent foreign substances to separate the by-products from the adherent foreign substances. A method for separating by-products by-produced during the polymerization reaction process of the above-mentioned polymer and adherent foreign substances accompanying them.
る請求項1記載の重合体の重合反応過程で副生する副生
物とこれに同伴した付着性異物の分離方法。2. The method for separating a by-product produced as a by-product in a polymerization reaction process of a polymer and an adhering foreign substance accompanied with the by-product according to claim 1, wherein the treated liquid is the same kind as the condensed by-product.
性異物を同伴した副生物を付着性異物の融点以上に加熱
して誘導排出させる請求項1又は2記載の重合体の重合
反応過程で副生する副生物とこれに同伴した付着性異物
の分離方法。3. A by-product in the polymerization reaction process of the polymer according to claim 1 or 2, wherein by-products accompanied by unreacted adhering foreign substances such as monomers and oligomers are heated to a temperature not lower than the melting point of the adhering foreign substances and induced to be discharged. A method for separating the by-product that forms and the adhering foreign substances that accompany it.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5433592A JPH05214089A (en) | 1992-02-04 | 1992-02-04 | Method for separating sticky foreign matter from by-product produced in polymerization step for producing polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5433592A JPH05214089A (en) | 1992-02-04 | 1992-02-04 | Method for separating sticky foreign matter from by-product produced in polymerization step for producing polymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05214089A true JPH05214089A (en) | 1993-08-24 |
Family
ID=12967737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5433592A Pending JPH05214089A (en) | 1992-02-04 | 1992-02-04 | Method for separating sticky foreign matter from by-product produced in polymerization step for producing polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH05214089A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004026938A1 (en) * | 2002-09-20 | 2004-04-01 | Mitsubishi Chemical Corporation | Process for producing polyester |
-
1992
- 1992-02-04 JP JP5433592A patent/JPH05214089A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004026938A1 (en) * | 2002-09-20 | 2004-04-01 | Mitsubishi Chemical Corporation | Process for producing polyester |
CN1297585C (en) * | 2002-09-20 | 2007-01-31 | 三菱化学株式会社 | Process of producing polyesters |
US7732556B2 (en) | 2002-09-20 | 2010-06-08 | Mitsubishi Chemical Corporation | Process of producing polyesters |
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