JPS627923B2 - - Google Patents
Info
- Publication number
- JPS627923B2 JPS627923B2 JP4213979A JP4213979A JPS627923B2 JP S627923 B2 JPS627923 B2 JP S627923B2 JP 4213979 A JP4213979 A JP 4213979A JP 4213979 A JP4213979 A JP 4213979A JP S627923 B2 JPS627923 B2 JP S627923B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- condenser
- vinyl chloride
- polymerization tank
- water
- 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.)
- Expired
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 80
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 35
- 239000003595 mist Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Description
【発明の詳細な説明】 本発明は塩化ビニルの重合法に関する。[Detailed description of the invention] The present invention relates to a method for polymerizing vinyl chloride.
さらに詳細には、還流凝縮器を使用して水性媒
体中で塩化ビニルを重合する方法の改良に関す
る。 More particularly, it relates to improvements in the process of polymerizing vinyl chloride in an aqueous medium using a reflux condenser.
塩化ビニルモノマーの重合は、工業的には熱水
あるいは冷水を通過させて重合槽の内容物を加熱
あるいは冷却させるためのジヤケツトを備えた20
m3またはこれ以上の容量を有する大きな重合槽を
用い回分式操作で行われている。 Polymerization of vinyl chloride monomer is carried out industrially using a 20-liter polymerization tank equipped with a jacket for heating or cooling the contents of the polymerization tank by passing hot or cold water through it.
It is carried out in batch operation using large polymerization vessels with a capacity of m 3 or more.
従来、重合中に生ずる熱は重合槽のジヤケツト
に冷水を通すことにより除去されている。 Traditionally, the heat generated during polymerization is removed by passing cold water through the jacket of the polymerization vessel.
重合に要する時間は、触媒活性による違いを別
にすれば、主としてジヤケツト冷却能力に依存し
ている。それ故に生産性を改善するために還流凝
縮器をジヤケツト冷却と併用することが以前から
提案されているが、凝縮器内壁に付着するポリマ
ースケールを除去するために手間がかかり、重合
時間を短縮するのがむづかしく工業的には殆んど
採用されていない。 The time required for polymerization, apart from differences due to catalyst activity, depends primarily on the jacket cooling capacity. Therefore, it has been previously proposed to use a reflux condenser in combination with jacket cooling to improve productivity, but it is time-consuming to remove the polymer scale that adheres to the inner walls of the condenser and shortens the polymerization time. This is difficult and is rarely used industrially.
かかる不都合を改善する方法として凝縮器の内
部表面を水と接触させて該内部表面にポリマース
ケールが付着するのを実質的に減少させる方法が
提案された（特公昭50−30105号公報）。 As a method for improving this disadvantage, a method has been proposed in which the internal surface of the condenser is brought into contact with water to substantially reduce the adhesion of polymer scale to the internal surface (Japanese Patent Publication No. 30105/1983).
しかし、該方法は還流凝縮器の工業的利用を可
能となし、極めて有効なものではあるが、それで
も該内部表面にポリマースケールが付着しさらに
改善の必要が認められている。 However, although this method enables the industrial use of reflux condensers and is extremely effective, it still causes polymer scale to adhere to the internal surface of the condenser, and further improvements are recognized as necessary.
また、前記方法における水の使用量を減ずる方
法として、重合に必要な全水量に対して少なくと
も約10容量％の量で導入し、ノズルを介して微細
に噴射する方法が提案されている（特開昭51−
84887号公報）。 In addition, as a method for reducing the amount of water used in the above method, a method has been proposed in which water is introduced in an amount of at least about 10% by volume based on the total amount of water required for polymerization, and the water is finely injected through a nozzle (especially 1978-
Publication No. 84887).
しかし、該方法によつても還流凝縮器内部表面
にポリマースケールが形成し、さらに改善の必要
がある。 However, even with this method, polymer scale is formed on the internal surface of the reflux condenser, and further improvement is required.
本発明の目的は還流凝縮器を有する重合槽を用
いて塩化ビニルを重合するに際し、還流凝縮器の
内部表面に生ずるポリマースケールの形成を実質
的乃至完全に回避することにある。 An object of the present invention is to substantially or completely avoid the formation of polymer scale on the internal surface of a reflux condenser when vinyl chloride is polymerized using a polymerization tank having a reflux condenser.
すなわち、本発明は重合槽中で、水媒体を使用
し、重合槽から塩化ビニル蒸気を回収し、凝縮器
内で凝縮し、そして該重合槽へ液体として還流さ
せることにより該水媒体中で塩化ビニルを重合す
る方法において、該凝縮器への塩化ビニル蒸気の
導入口近傍に塩化ビニル蒸気に同伴されてくるミ
ストのセパレーターを設けることにより該凝縮器
内に生ずるポリマースケールの形成を実質的乃至
完全に防止せしめうる還流凝縮器を使用する塩化
ビニルの重合法を提供するにある。 That is, the present invention uses an aqueous medium in a polymerization tank, recovers vinyl chloride vapor from the polymerization tank, condenses it in a condenser, and returns it as a liquid to the polymerization tank. In the method of polymerizing vinyl, by providing a separator for the mist entrained in the vinyl chloride vapor near the inlet of the vinyl chloride vapor into the condenser, the formation of polymer scale that occurs in the condenser can be substantially or completely prevented. The object of the present invention is to provide a method for polymerizing vinyl chloride using a reflux condenser which can prevent the above-mentioned problems.
本発明方法において“ミストセパレーター”と
は構造体を意味する。このようなミストセパレー
ターとしては、ガラス、炭素、アルミナ、シリカ
ーアルミナ、石綿等の無機質繊維の積層体又は充
填体あるいは前記無機質物質の粉末、成形体の充
填体；ポリオレフイン、ポリアミド、ポリエステ
ル、ポリアクリロニトリル等の有機質繊維の積層
体又は充填体あるいは前記有機物質の粉末、成形
体の充填体；公用のプレート式ミストセパレータ
ー等を挙げることができる。特にガラス繊維の積
層体又は充填体が好ましい。 In the method of the present invention, "mist separator" means a structure. Such mist separators include laminates or fillers of inorganic fibers such as glass, carbon, alumina, silica alumina, and asbestos, powders of the above-mentioned inorganic substances, and fillers of molded bodies; polyolefins, polyamides, polyesters, and polyacrylonitrile. Examples include laminates or fillers of organic fibers, powders of the organic substances, and fillers of molded bodies; public plate-type mist separators; and the like. Particularly preferred are glass fiber laminates or fillers.
本発明方法の好ましい実施形式は重合槽と凝縮
器を結ぶ導管の途中に前記ミストセパレーターを
設置することである。 A preferred embodiment of the method of the present invention is to install the mist separator in the middle of a conduit connecting the polymerization tank and the condenser.
しかして、本発明方法によれば重合槽上部の蒸
気スペースにあるガスがミストを同伴して導管を
経て凝縮器に達するのであるが、導管の途中に設
けられたミストセパレーターにより、ガスに同伴
されているミストが捕捉され、その結果凝縮器に
達するガス中にはミスト分が実質的乃至完全に除
かれ、結果として凝縮器内部表面へのポリマース
ケールの形成が実質的乃至完全に防止できる。そ
れ故凝縮器の洗浄に要する時間が短縮し、しかも
凝縮器の伝熱係数が高く、且つ維持経費が軽減さ
れる。 According to the method of the present invention, the gas in the steam space at the top of the polymerization tank is accompanied by mist and reaches the condenser through the conduit. As a result, the gas reaching the condenser is substantially or completely free of mist, and as a result, the formation of polymer scale on the internal surface of the condenser can be substantially or completely prevented. Therefore, the time required to clean the condenser is reduced, the heat transfer coefficient of the condenser is high, and maintenance costs are reduced.
これに対し、スプレーによりポリマースケール
の形成を防止する場合にはミストが完全に捕捉さ
れないためか、凝縮器内部表面へのポリマースケ
ールの形成防止能が本発明方法に比較して劣つて
いる。 On the other hand, when the formation of polymer scale is prevented by spraying, the ability to prevent the formation of polymer scale on the internal surface of the condenser is inferior to that of the method of the present invention, probably because the mist is not completely captured.
以下に図面により本発明方法をさらに詳細に説
明する。 The method of the present invention will be explained in more detail below with reference to the drawings.
本発明方法で使用される装置は通常の塩化ビニ
ル重合槽１に多管式還流凝縮器２を設けた装置に
おいて、該凝縮器への塩化ビニル蒸気の導入口近
傍にミストセパレーター３を設けたものである。 The apparatus used in the method of the present invention is an apparatus in which a conventional vinyl chloride polymerization tank 1 is equipped with a multi-tubular reflux condenser 2, and a mist separator 3 is installed near the inlet for introducing vinyl chloride vapor into the condenser. It is.
重合槽１は冷却のため重合槽の周囲にジヤケツ
トを有している。重合槽１へ装入する物質は図に
は図示されていない頂部の開口から導入され、主
成分は塩化ビニルモノマー及び水から成つてい
る。このモノマーは完全な塩化ビニルかあるいは
酢酸ビニル、アクリル酸あるいはアクリル酸エス
テルあるいは塩化ビニリデン等と共用してもよ
い。 The polymerization tank 1 has a jacket around the polymerization tank for cooling. The materials to be charged into the polymerization tank 1 are introduced through an opening at the top, not shown in the figure, and the main components are vinyl chloride monomer and water. This monomer may be pure vinyl chloride or may be used in combination with vinyl acetate, acrylic acid or acrylic ester, vinylidene chloride, etc.
重合槽１内の内容物の液体の高さより上は蒸気
スペースから成る。 Above the level of the liquid contents in the polymerization vessel 1 consists of a vapor space.
先ず、反応成分の温度を重合に適した望ましい
温度にまで上昇させる。反応が始まつたら、その
反応は発熱反応であるために、ジヤケツト及び凝
縮器に冷水を通して重合槽１の中の反応成分を実
質的に一定の重合温度に調節維持する。 First, the temperature of the reactants is raised to a desired temperature suitable for polymerization. Once the reaction has begun, cold water is passed through the jacket and condenser to control and maintain the reactants in the polymerization vessel 1 at a substantially constant polymerization temperature since the reaction is exothermic.
反応が進行するにつれて、塩化ビニル蒸気が発
生して重合槽１のトツプから凝縮器２の中へ導管
４、ミストセパレーター３を通つて上昇してい
く。また導管４にはミストセパレーター３の上方
にミストセパレーターに付着した重合内容物ミス
トを洗い流すためにノズル５に連結しているパイ
プ６を設けることが好ましい。これによりミスト
セパレーター３表面へのポリマースケールの形成
を長期に防止することができる。パイプ６からは
水単独は勿論消泡剤を含む液体をノズル５から塩
化ビニル蒸気の流れに対向して噴霧することがで
きる。このノズル５からは通常、重合に必要な全
水量の約３〜20容量％の水を散布すればよい。こ
のようなノズル５を設けない場合にはミストセパ
レーター３は適当な重合サイクル毎に取外し、ポ
リマースケールを洗浄除去し再使用する必要があ
る。 As the reaction progresses, vinyl chloride vapor is generated and rises from the top of the polymerization vessel 1 into the condenser 2 through the conduit 4 and the mist separator 3. Further, it is preferable that the conduit 4 is provided with a pipe 6 connected to a nozzle 5 above the mist separator 3 in order to wash away the polymerized content mist adhering to the mist separator. Thereby, formation of polymer scale on the surface of the mist separator 3 can be prevented for a long period of time. From the pipe 6, not only water but also a liquid containing an antifoaming agent can be sprayed from the nozzle 5 against the flow of vinyl chloride vapor. Usually, water in an amount of about 3 to 20% by volume of the total amount of water required for polymerization may be sprayed from this nozzle 5. If such a nozzle 5 is not provided, it is necessary to remove the mist separator 3 every appropriate polymerization cycle, wash off the polymer scale, and reuse it.
ミストセパレーター３において、ミスト分が除
かれた塩化ビニル蒸気は還流凝縮器２のチユーブ
７に入り込み、そこで冷却され凝縮される。凝縮
器２にはポリマースケールの生成防止のために散
水することができる。この場合、散水は凝縮器２
のトツプに挿入されており、且つノズル８に連結
しているパイプ９から導入される。チユーブの上
に一定の間隔をあけた複数の点に水を導入する手
段としては他にも種々考えられるが、スプレー法
が好ましい方法である。ノズル８からスプレーさ
れる水の量は凝縮器のサイズによつても変わる
が、通常重合に必要な全水量の約３〜20容量％で
ある。チユーブ７を通過したらこの水は塩化ビニ
ル凝縮物を伴つてチユーブから重合槽１に流下す
る。 In the mist separator 3, the vinyl chloride vapor from which the mist has been removed enters the tube 7 of the reflux condenser 2, where it is cooled and condensed. Water can be sprinkled into the condenser 2 to prevent the formation of polymer scale. In this case, watering is carried out by condenser 2
It is introduced from a pipe 9 inserted into the top of the pipe and connected to a nozzle 8. Although various other methods are possible for introducing water at regularly spaced points on the tube, spraying is the preferred method. The amount of water sprayed from nozzle 8 will vary depending on the size of the condenser, but will typically be about 3-20% by volume of the total amount of water required for polymerization. After passing through tube 7, this water flows down from the tube into polymerization tank 1, accompanied by vinyl chloride condensate.
若し、塩化ビニルモノマーが凝縮できないよう
な不活性ガス、例えば窒素を含んでいる場合は、
重合がはじまつてからバルブ１０を時々開けてそ
のガスを放出させる必要がある。 If the vinyl chloride monomer contains an inert gas that cannot be condensed, such as nitrogen,
After polymerization begins, it is necessary to open the valve 10 from time to time to release the gas.
冷却水は凝縮器２の胴部分から流れて入口１１
に入り、出口１２から出る。バツフル１４は凝縮
器２からくる冷却水の流れを制御する。 Cooling water flows from the body of the condenser 2 to the inlet 11.
Enter and exit through exit 12. The baffle 14 controls the flow of cooling water coming from the condenser 2.
導管４中に設けたミストセパレーター３の圧損
が生ずる場合には必要に応じ重合槽１と凝縮器２
の接続部１３に逆止弁、ミストセパレーターと同
様な構造体等を設けることにより、塩化ビニル、
蒸気の流れを有効に制御することが可能である。 If a pressure loss occurs in the mist separator 3 installed in the conduit 4, the polymerization tank 1 and condenser 2 may be removed as necessary.
By providing a check valve, a structure similar to a mist separator, etc. in the connecting part 13 of
It is possible to effectively control the flow of steam.
別の方法としては、導管４を使用せず、塩化ビ
ニル蒸気の上向き通過及び塩化ビニル液体凝縮物
の下向き返しの両方に単一の導管を使用する方法
がある。勿論、重合槽１のトツプと凝縮器２とを
連結する接続部１３は液体凝縮物の下向き流れに
逆流する上向き流れである塩化ビニル蒸気流を重
合槽１内の液体内に流下させるに充分な大きさが
なければならないしまた、ミストセパレーターは
圧損が極力小さい構造のものを使用するのが望ま
しい。 An alternative method is to omit conduit 4 and use a single conduit for both the upward passage of the vinyl chloride vapor and the downward return of the vinyl chloride liquid condensate. Of course, the connection 13 connecting the top of the polymerization vessel 1 and the condenser 2 is sufficient to allow the upward flow of vinyl chloride vapor to flow down into the liquid in the polymerization vessel 1, counteracting the downward flow of liquid condensate. The size of the mist separator must be large, and it is desirable to use a mist separator with a structure that has as little pressure loss as possible.
塩化ビニルの重合で普通に使用される温度及び
圧力が本発明では使用される。 Temperatures and pressures commonly used in the polymerization of vinyl chloride are used in the present invention.
重合は約０〜100℃の温度範囲で実施される
が、普通使用される温度範囲は約35〜75℃であ
る。圧力はモノマーの気化によつて生ずる自圧下
で実施される。 The polymerization is carried out at a temperature range of about 0-100°C, although the commonly used temperature range is about 35-75°C. The pressure is carried out under autogenous pressure generated by vaporization of the monomer.
以上詳述したように本発明方法によれば、公知
方法に比較して約1.5倍またはそれ以上の重合サ
イクルによつても還流凝縮器の内部表面にポリマ
ースケールの形成が実質的に認められずその結
果、凝縮器の洗浄に要する時間が短縮し維持経費
が軽減される。 As detailed above, according to the method of the present invention, substantially no polymer scale is formed on the internal surface of the reflux condenser even after polymerization cycles of about 1.5 times or more compared to known methods. As a result, the time required to clean the condenser is reduced and maintenance costs are reduced.
また、既設の重合槽でもつて、その生産性を顕
著に高め得ることができるという利点が発揮され
る。 Furthermore, even if an existing polymerization tank is used, there is an advantage that the productivity can be significantly increased.
以下に実施例により本発明方法を説明するが本
発明方法はこれにより制限されるものではない。 The method of the present invention will be explained below with reference to Examples, but the method of the present invention is not limited thereto.
実施例 １
内容積22000の重合槽に多管式還流凝縮器を
取り付けた。この凝縮器は45m2の伝熱面積を有
し、塩化ビニル蒸気の導入管である重合槽との導
管の途中にガラス繊維の積層体を内蔵したミスト
セパレーターを有する。この還流凝縮器を装着し
た重合槽を用い、塩化ビニルの懸濁重合を連続し
て多数バツチを行つた。典型的な重合処方は以下
の通りであつた。Example 1 A multi-tubular reflux condenser was attached to a polymerization tank with an internal volume of 22,000. This condenser has a heat transfer area of 45 m 2 and has a mist separator containing a glass fiber laminate in the middle of the conduit that connects to the polymerization tank, which is the introduction pipe for vinyl chloride vapor. Using this polymerization tank equipped with a reflux condenser, suspension polymerization of vinyl chloride was continuously carried out in many batches. A typical polymerization recipe was as follows.
脱イオン水 8400
塩化ビニル 7000Kg
懸濁剤（ポリ酢酸ビニルの部分ケン化物） ７Kg
触 媒（ジ２−エチルヘキシルパーオキシジカー
ボネートの50％トルエン溶液） ９Kg
先ず、脱イオン水、懸濁剤および触媒を重合槽
に導入する。次いで重合槽内を脱気した後塩化ビ
ニルモノマーを導入する。内容物を撹拌下57℃に
昇温することにより重合を開始し、その後57℃に
維持した。Deionized water 8400 Vinyl chloride 7000Kg Suspending agent (partially saponified polyvinyl acetate) 7Kg Catalyst (50% toluene solution of di-2-ethylhexyl peroxydicarbonate) 9Kg First, add deionized water, suspending agent, and catalyst. Introduce into polymerization tank. Next, after deaerating the inside of the polymerization tank, vinyl chloride monomer is introduced. Polymerization was initiated by raising the temperature of the contents to 57°C while stirring, and then maintained at 57°C.
重合を開始して約3.5時間後に重合槽内の圧力
が重合初期の圧力により１Kl／cm2低下したが、そ
の時点で重合槽より未反応塩化ビニルモノマーを
排除して重合を停止した。 Approximately 3.5 hours after starting the polymerization, the pressure inside the polymerization tank decreased by 1 Kl/cm 2 due to the initial pressure of the polymerization, but at that point, the unreacted vinyl chloride monomer was removed from the polymerization tank to stop the polymerization.
この間に脱イオン水を凝縮器上部のノズルより
500、ミストセパレーター上部のノズルより500
をそれぞれスプレーした。 During this time, pour deionized water through the nozzle at the top of the condenser.
500, 500 from the nozzle at the top of the mist separator
were sprayed on each.
重合反応により発生した反応熱の約70％が還流
凝縮器より、また残りの約30％が重合槽のジヤケ
ツトより除去された。 Approximately 70% of the reaction heat generated by the polymerization reaction was removed from the reflux condenser, and the remaining 30% was removed from the jacket of the polymerization tank.
上記の方法で20バツチの重合が行われ、これら
の重合の平均重合時間は3.5時間であつた。一方
還流凝縮器を使用しない場合の重合時間は７時間
以下には短縮されなかつた。 Twenty batches of polymerization were carried out in the above manner, and the average polymerization time of these polymerizations was 3.5 hours. On the other hand, when a reflux condenser was not used, the polymerization time could not be shortened to less than 7 hours.
各バツチ毎および20バツチの重合終了後に凝縮
器チユーブを検査したが、ポリマースケールの生
成は全く認められなかつた。これに対しミストセ
パレーターを装着せずただ凝縮器上部のノズルよ
り脱イオン水を900スプレーして同様の重合を
行つた場合、チユーブの表面にポリマースケール
が付着するため５回の重合の間に凝縮器の総括伝
熱係数が500から100Kca／時・m2・℃に減少し
た。 The condenser tube was inspected after each batch and after 20 batches of polymerization, and no polymer scale formation was observed. On the other hand, if the same polymerization was carried out by spraying 900 ml of deionized water from the nozzle at the top of the condenser without installing a mist separator, polymer scale would adhere to the tube surface and condensation would occur during the 5 polymerizations. The overall heat transfer coefficient of the vessel decreased from 500 to 100 Kca/hr・m 2・℃.
実施例 ２
実施例１と同じ装置を用い、塩化ビニルのエマ
ルジヨン重合を連続して多数行つた。典型的な重
合処方は以下の通りであつた。Example 2 Using the same equipment as in Example 1, a number of emulsion polymerizations of vinyl chloride were carried out in succession. A typical polymerization recipe was as follows.
脱イオン水 7700
塩化ビニル 7000Kg
乳化剤（ラウリル硫酸ナトリウム） ７Kg
触 媒（過硫酸カリウム） 14Kg
先ず、脱イオン水、乳化剤および触媒を重合槽
に導入する。次いで重合槽内を脱気窒素置換した
後、塩化ビニルモノマーを導入する。内容物を撹
拌下53℃に昇温することにより重合を開始し、そ
の後53℃に維持した。重合を開始して約７時間後
に重合槽内の圧力が重合初期の圧力より１Kl／cm2
低下したが、その時点で重合槽より未反応塩化ビ
ニルモノマーを排除して重合を停止した。Deionized water 7700 Vinyl chloride 7000Kg Emulsifier (sodium lauryl sulfate) 7Kg Catalyst (potassium persulfate) 14Kg First, deionized water, emulsifier and catalyst are introduced into the polymerization tank. Next, after the interior of the polymerization tank was degassed and replaced with nitrogen, vinyl chloride monomer was introduced. Polymerization was initiated by raising the temperature of the contents to 53°C while stirring, and then maintained at 53°C. Approximately 7 hours after starting polymerization, the pressure inside the polymerization tank decreased by 1 Kl/cm 2 from the pressure at the beginning of polymerization.
However, at that point, the unreacted vinyl chloride monomer was removed from the polymerization tank and the polymerization was stopped.
この間に脱イオン水を凝縮器上部のノズルより
500、ミストセパレーター上部のノズルより500
それぞれスプレーした。 During this time, pour deionized water through the nozzle at the top of the condenser.
500, 500 from the nozzle at the top of the mist separator
Sprayed each.
重合反応により発生した反応熱の約60％が還流
凝縮器より、また残りの約40％が重合槽のジヤケ
ツトより除去された。 Approximately 60% of the reaction heat generated by the polymerization reaction was removed from the reflux condenser, and the remaining 40% was removed from the jacket of the polymerization tank.
上記の方法で20バツチの重合が行われ、これら
の重合の平均重合時間は7.5時間であつた。一
方、還流凝縮器を使用しない場合の重合時間は16
時間以下には短縮されなかつた。 Twenty batches of polymerization were carried out in the above manner, and the average polymerization time of these polymerizations was 7.5 hours. On the other hand, the polymerization time without using a reflux condenser is 16
It could not be reduced to less than an hour.
各バツチ毎および20バツチの重合終了後に凝縮
器チユーブを検査したが、ポリマースケールの生
成は全く認められなかつた。これに対し、ミスト
セパレーターを装着せず、ただ凝縮器上部のノズ
ルより脱イオン水を900スプレーして同様の重
合を行つた場合、２バツチの重合後にポリマース
ケールの生成によりチユーブが閉塞し除熱能力が
消失したため凝縮器を解体してチユーブを洗浄し
なければならなかつた。 The condenser tube was inspected after each batch and after 20 batches of polymerization, and no polymer scale formation was observed. On the other hand, if the same polymerization was carried out by simply spraying 900ml of deionized water from the nozzle at the top of the condenser without installing a mist separator, the tube would become clogged due to the formation of polymer scale after two batches of polymerization, and the heat would be removed. Due to loss of capacity, the condenser had to be dismantled and the tube cleaned.
第１図は本発明方法で使用される装置の一例を
示したものであり、図中１は塩化ビニル重合槽、
２は多管式還流凝縮器、３はミストセパレータ
ー、４は導管、５，８はノズル、６，９はパイ
プ、７は凝縮器のチユーブ、１０はバルブ、１１
は冷却水入口、１２は冷却水出口、１３は重合槽
と凝縮器の接続部、１４はバツフルを示す。
Figure 1 shows an example of the equipment used in the method of the present invention, in which 1 is a vinyl chloride polymerization tank;
2 is a multi-tubular reflux condenser, 3 is a mist separator, 4 is a conduit, 5, 8 are nozzles, 6, 9 are pipes, 7 is a condenser tube, 10 is a valve, 11
12 is a cooling water inlet, 12 is a cooling water outlet, 13 is a connection between the polymerization tank and the condenser, and 14 is a baffle.
Claims (1)
ビニル蒸気を回収し、凝縮器内で凝縮し、そして
該重合槽へ液体として還流させることにより該水
媒体中で塩化ビニルを重合する方法において、該
凝縮器への塩化ビニル蒸気の導入口近傍に、塩化
ビニル蒸気に同伴されてくるミストのセパレータ
ーを設けることを特徴とする還流凝縮器を使用す
る塩化ビニルの重合法。 ２ 凝縮器の内部表面を水と接触させることを特
徴とする特許請求の範囲第１項記載の方法。 ３ ミストセパレーターを水と接触させることを
特徴とする特許請求の範囲第１または２項記載の
方法。[Claims] 1. Using an aqueous medium in a polymerization tank, recovering vinyl chloride vapor from the polymerization tank, condensing it in a condenser, and returning it as a liquid to the polymerization tank. A method for polymerizing vinyl chloride using a reflux condenser characterized in that a separator for the mist entrained in the vinyl chloride vapor is provided near the inlet of the vinyl chloride vapor into the condenser. legal. 2. The method according to claim 1, characterized in that the internal surface of the condenser is brought into contact with water. 3. The method according to claim 1 or 2, characterized in that the mist separator is brought into contact with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4213979A JPS55135114A (en) | 1979-04-06 | 1979-04-06 | Polymerization of vinyl chloride using reflux condenser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4213979A JPS55135114A (en) | 1979-04-06 | 1979-04-06 | Polymerization of vinyl chloride using reflux condenser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55135114A JPS55135114A (en) | 1980-10-21 |
| JPS627923B2 true JPS627923B2 (en) | 1987-02-19 |
Family
ID=12627596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4213979A Granted JPS55135114A (en) | 1979-04-06 | 1979-04-06 | Polymerization of vinyl chloride using reflux condenser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55135114A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101637292B1 (en) | 2015-02-16 | 2016-07-20 | 현대자동차 주식회사 | Apparatus of condensing gas with reflux separator |
-
1979
- 1979-04-06 JP JP4213979A patent/JPS55135114A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55135114A (en) | 1980-10-21 |
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