JPH05310814A - Method of recovering vinyl monomer - Google Patents
Method of recovering vinyl monomerInfo
- Publication number
- JPH05310814A JPH05310814A JP13564792A JP13564792A JPH05310814A JP H05310814 A JPH05310814 A JP H05310814A JP 13564792 A JP13564792 A JP 13564792A JP 13564792 A JP13564792 A JP 13564792A JP H05310814 A JPH05310814 A JP H05310814A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- monomer
- vinyl monomer
- recovery
- 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.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】
【構成】水媒体を使用したビニル系単量体の重合後の未
反応ビニル単量体を回収する方法において、水溶性重合
禁止剤の存在下で回収操作を行うことを特徴とするビニ
ル系単量体の回収法。
【効果】回収モノマ−の配管及び機器内での、スケ−リ
ング、閉塞に伴う生産性の低下を防止する。(57) [Summary] [Structure] In a method for recovering unreacted vinyl monomer after polymerization of vinyl monomer using an aqueous medium, recovery operation is performed in the presence of a water-soluble polymerization inhibitor. Characteristic vinyl monomer recovery method. [Effect] It is possible to prevent a decrease in productivity due to scaling and blockage in the piping and equipment of the recovery monomer.
Description
【０００１】[0001]
【産業上の利用分野】本発明は水媒体を使用したビニル
系単量体（以下モノマ−と称する）の重合後の未反応モ
ノマ−を回収する方法において、回収モノマ−の配管及
び機器（以下回収設備と称する）内での、スケ−リン
グ、閉塞に伴う生産性の低下を防止するモノマ−の回収
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering unreacted monomers after polymerization of vinyl monomers (hereinafter referred to as "monomers") using an aqueous medium. The present invention relates to a method for recovering a monomer that prevents a decrease in productivity due to scaling and blockage in a recovery facility).
【０００２】[0002]
【従来の技術】通常モノマ−の重合は水媒体とともに、
乳化剤若しくは懸濁剤、重合開始剤等の存在下で行われ
る。そしてモノマ−の転化率が所定値になった時点で、
重合反応を停止し、未反応モノマ−を回収した後、重合
生成物をブロ−ダウンタンク、脱モノマ−塔、乾燥機を
経て乾燥した重合物を得る。BACKGROUND OF THE INVENTION Polymerization of monomers is usually carried out with an aqueous medium.
It is carried out in the presence of an emulsifier or suspending agent, a polymerization initiator and the like. And when the conversion rate of the monomer reaches a predetermined value,
After the polymerization reaction is stopped and the unreacted monomer is recovered, the polymerization product is dried through a blowdown tank, a demonomer tower and a dryer to obtain a dried polymer.
【０００３】この工程の中で、未反応モノマ−は重合
器、ブロ−ダウンタンク及び脱モノマ−塔から回分若し
くは連続で、ガスホルダ−、直接圧縮液化装置若しくは
冷却液化装置により回収される。この回収モノマ−は直
接、不要成分を除去した後若しくは特定の成分を分離し
た後、重合器にて再使用される。In this process, unreacted monomers are recovered from the polymerization vessel, the blow-down tank and the demonomer column in batch or continuously by a gas holder, a direct compression liquefier or a cooling liquefier. This recovered monomer is directly reused in the polymerization vessel after removing unnecessary components or after separating specific components.
【０００４】しかしながら、この一連のモノマ−回収工
程の中で、モノマ−の重合反応が起こり、回収設備内で
スケ−リング若しくは閉塞に起因する生産性の低下、保
全費の増大、あるいは安全性の低下等が製造上の大きな
問題となっていた。However, during this series of monomer recovery steps, a polymerization reaction of the monomers occurs, resulting in a decrease in productivity due to scaling or blockage in the recovery facility, an increase in maintenance costs, or a safety problem. Degradation has become a major manufacturing problem.
【０００５】かかる問題を解決するため、重合開始能を
持つ物質の除去若しくは条件の回避もあるが、その効果
が完全でないばかりでなく、多額の設備費を要する等実
用的でない。In order to solve such a problem, a substance having a polymerization initiating ability may be removed or conditions may be avoided, but not only the effect is not perfect, and a large amount of equipment cost is required, which is not practical.
【０００６】また、特開昭５１−９０３８１号公報には
塩化ビニルの重合禁止剤としてＮ−ニトロソフェニルヒ
ドロキシアミン又はその塩などが記載されているが、こ
れらの中で水溶性のない重合禁止剤は、本発明の目的で
ある未反応モノマ−回収装置における未反応モノマ−の
重合禁止に役立たない。Further, JP-A-51-90381 discloses N-nitrosophenylhydroxyamine or a salt thereof as a vinyl chloride polymerization inhibitor. Among these, a water-insoluble polymerization inhibitor is used. Does not serve to inhibit the polymerization of unreacted monomers in the unreacted monomer recovery unit, which is the object of the present invention.
【０００７】その他、特開昭４８−８９９９０，５１−
６１５９１，５２−３６８１，５８−１７１０６，６４
−６６２０６号公報等の、重合器での重合停止若しくは
禁止の方法や、特開昭４７−３４５８４，５０−７２９
８４，５０−７３９９０号公報等の、重合器でのスケ−
ル付着防止の方法は、本発明の目的である、未反応モノ
マ−の回収中に生ずる重合反応防止の方法としては効果
がなく、不適当である。In addition, Japanese Patent Laid-Open No. 48-89990,51-
61591, 52-3681, 58-17106, 64
-66206 and other methods for stopping or inhibiting polymerization in a polymerization vessel, and JP-A-47-34584, 50-729.
84,50-73990, etc.
The method for preventing the adhesion of the polymer is not effective and is unsuitable as the method for preventing the polymerization reaction which occurs during the recovery of the unreacted monomer, which is the object of the present invention.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、水媒
体を使用したモノマ−重合後の未反応モノマ−の回収
を、回収設備内でのスケ−リング、閉塞を生じさせるこ
となく行う方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to carry out recovery of an unreacted monomer after polymerization of a monomer using an aqueous medium without causing scaling or clogging in a recovery facility. To provide.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、これらの
問題を解決し、回収設備内での重合防止を図るべく鋭意
検討した結果、回収設備内に水溶性重合禁止剤を存在さ
せることで、上記問題を解決できることを見出し、本発
明に至った。すなわち本発明は、水媒体を使用したモノ
マ−の重合後の未反応モノマ−を回収する方法おいて、
水溶性重合禁止剤の存在下で回収操作を行うことを特徴
とするモノマ−の回収法である。Means for Solving the Problems The inventors of the present invention have made diligent studies to solve these problems and prevent polymerization in the recovery facility. As a result, the presence of a water-soluble polymerization inhibitor in the recovery facility. Then, they have found that the above problems can be solved, and have reached the present invention. That is, the present invention is a method for recovering an unreacted monomer after polymerization of a monomer using an aqueous medium,
This is a method for recovering a monomer, wherein the recovery operation is performed in the presence of a water-soluble polymerization inhibitor.
【００１０】以下、本発明をさらに詳細に説明する。The present invention will be described in more detail below.
【００１１】本発明に使用される重合禁止剤としては水
溶性があれば充分であり、使用条件下で、１ｇ／１００
ｇ−水以上の溶解度があれば好適である。水溶性重合禁
止剤として具体的な例をあげるとハイドロキノン、Ｐ−
メトキシフェノ−ル等のフェノ−ル類、Ｐ−ベンゾキノ
ン等のキノン類、Ｎ−ニトロソフェニルヒドロキシアミ
ンのアンモニウム塩等のニトロソ類などがあげられる。It is sufficient for the polymerization inhibitor used in the present invention to be water-soluble, and 1 g / 100 under the conditions of use.
It is suitable if it has a solubility of at least g-water. Specific examples of the water-soluble polymerization inhibitor include hydroquinone and P-
Examples thereof include phenols such as methoxyphenol, quinones such as P-benzoquinone, and nitroso such as ammonium salt of N-nitrosophenylhydroxyamine.
【００１２】水への溶解度の低い重合禁止剤は、液体モ
ノマ−中若しくは通常の重合器内での重合反応において
重合禁止効果はあっても、回収モノマ−ガス若しくはそ
の一部が凝縮する回収装置内では重合禁止効果が見られ
ない。A polymerization inhibitor having a low solubility in water has a polymerization inhibition effect in a polymerization reaction in a liquid monomer or in a usual polymerization vessel, but a recovery device in which a recovery monomer gas or a part thereof is condensed. There is no polymerization inhibition effect inside.
【００１３】この水溶性重合禁止剤の注入する方法は、
重合反応後の未反応モノマ−回収装置内において、未反
応モノマ−の重合しやすい場所の上流側に、未反応モノ
マ−に対して１ｐｐｍ〜１重量％注入すれば充分であ
る。また、注入場所は例えば重合器、ブロ−ダウンタン
ク又は脱モノマ−塔などの未反応モノマ−出口が挙げら
れる。The method of injecting this water-soluble polymerization inhibitor is as follows:
In the unreacted monomer recovery device after the polymerization reaction, it is sufficient to inject 1 ppm to 1% by weight of the unreacted monomer on the upstream side of the place where the unreacted monomer is easily polymerized. In addition, the injection location may be, for example, an unreacted monomer outlet such as a polymerization vessel, a blowdown tank or a demonomer tower.
【００１４】本発明におけるビニル系単量体としては、
塩化ビニルの他に塩化ビニリデン、フッ化ビニル等のハ
ロゲン化ビニル、酢酸ビニル、プロピオン酸ビニル等の
ビニルエステル、アクリル酸、メタクリル酸及びそれら
のエステル又は塩、スチレン、α−メテルスチレン等の
スチレン誘導体、上記のビニル系単量体の１種以上含み
若しくはビニル系単量体を主成分とする共重合可能なブ
タジエン、クロロプレン、イソプレンなどのジエン系単
量体を含んでもよい。The vinyl-based monomer in the present invention includes
In addition to vinyl chloride, vinyl halides such as vinylidene chloride and vinyl fluoride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, methacrylic acid and their esters or salts, styrene derivatives such as styrene and α-methyl styrene. Further, it may contain one or more of the above vinyl-based monomers or may contain a diene-based monomer such as copolymerizable butadiene, chloroprene, or isoprene containing a vinyl-based monomer as a main component.
【００１５】上記ビニル系単量体と水媒体を使用する以
外、特に重合反応に添加する乳化剤、若しくは懸濁剤、
重合開始剤等、使用する原料、モノマ−回収の条件及び
使用する装置材質に特に制約はない。An emulsifier or a suspending agent to be added to the polymerization reaction other than the above vinyl monomer and an aqueous medium.
There are no particular restrictions on the raw materials used such as the polymerization initiator, the conditions for monomer recovery, and the equipment materials used.
【００１６】[0016]
【実施例】以下実施例によって本発明を説明するが、本
発明はこれらに限定されない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.
【００１７】実施例１ 重合器に脱イオン水１５０部、モノマ−として塩化ビニ
ル９５部、酢酸ビニル５部、重合開始剤としてｔ−ブチ
ルパ−オキシネオデカネ−ト０．０２部、部分ケン化ポ
リビニルアルコ−ル０．１部を仕込み、撹伴、昇温後、
５７℃で重合反応を行い、缶内圧が２．０ｋｇ／ｃｍ２
低下した時点で、重合反応を終了し、未反応モノマ−の
回収を行い、缶内圧が２ｋｇ／ｃｍ２Ｇになった時、生
成重合液（スラリ−）をブロ−ダウンタンクに移送後、
連続的に生成重合液を脱モノマ−塔、遠心脱水器、乾燥
へ送り乾燥ポリ塩化ビニルを得た。Example 1 150 parts of deionized water in a polymerization vessel, 95 parts of vinyl chloride as a monomer, 5 parts of vinyl acetate, 0.02 part of t-butyl peroxyneodedecaneate as a polymerization initiator, partially saponified polyvinyl alcohol. 0.1 part was charged, and after stirring and heating,
Polymerization reaction is carried out at 57 ° C and the internal pressure of the can is 2.0 kg / cm 2.
At the time of decrease, the polymerization reaction was terminated, unreacted monomers were recovered, and when the internal pressure of the can reached 2 kg / cm 2 G, after transferring the produced polymerization liquid (slurry) to the blowdown tank,
The produced polymerization liquid was continuously sent to a demonomer tower, a centrifugal dehydrator and a drying machine to obtain dried polyvinyl chloride.
【００１８】一方、未反応モノマ−は、重合器より回分
式で、ブロ−ダウンタンク及び、脱モノマ−塔から連続
的に回収された。On the other hand, the unreacted monomer was continuously recovered from the blowdown tank and the demonomer column from the polymerization reactor in a batch system.
【００１９】重合器の未反応モノマ−出口に、水溶性重
合禁止として、ハイドロキノンを回収モノマ−に対し、
１０ｐｐｍになるように２重量％水溶液の状態で注入し
た。At the outlet of the unreacted monomer of the polymerization vessel, hydroquinone is recovered from the recovered monomer to inhibit water-soluble polymerization.
It was injected in the state of a 2 wt% aqueous solution so as to have a concentration of 10 ppm.
【００２０】この操作を継続して１０バッチ後、重合器
未反応モノマ−出口の配管を分解して、付着スケ−ル量
を測定した結果を表１の実験Ｎｏ．１０１に示す。After this operation was continued for 10 batches, the pipe at the outlet of the unreacted monomer in the polymerization reactor was disassembled and the amount of the attached scale was measured. 101 is shown.
【００２１】実施例２ 重合器への仕込みモノマ−の種類、重合禁止剤の種類若
しくは添加量を変える以外、実施例１と同様の方法での
結果を表１の実験Ｎｏ．１０２からＮｏ．１０４に示
す。Example 2 The results of the same procedure as in Example 1 except that the type of monomer charged to the polymerization vessel, the type of polymerization inhibitor or the addition amount thereof were changed are shown in Table 1. 102 to No. Shown at 104.
【００２２】比較例１ 重合禁止剤を注入しない以外は実施例１と同様の方法で
実施した結果を表１の実験Ｎｏ．２０１に示す。Comparative Example 1 The results of the same procedure as in Example 1 except that the polymerization inhibitor was not injected are shown in Table 1. Shown at 201.
【００２３】非水溶性重合禁止剤をアセトン溶液で注入
すること以外は実施例１と同様の方法で実施した結果を
表１の実験Ｎｏ．２０２〜２０３に示す。The results of experiment No. 1 in Table 1 were carried out in the same manner as in Example 1 except that the water-insoluble polymerization inhibitor was injected as an acetone solution. Shown at 202-203.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】以上述べたとおり、本発明によれば未反
応モノマ−の回収を回収設備内でスケ−リング、閉塞を
生じさせることなく行うことができ、これに伴いビニル
系重合体を生産性良く製造することができる。As described above, according to the present invention, the unreacted monomer can be recovered in the recovery facility without causing scaling or clogging, and the vinyl polymer is produced accordingly. It can be manufactured with good properties.
Claims (2)
の未反応ビニル単量体を回収する方法において、水溶性
重合禁止剤の存在下で回収操作を行うことを特徴とする
ビニル系単量体の回収法。1. A method for recovering an unreacted vinyl monomer after polymerization of a vinyl monomer using an aqueous medium, characterized in that the recovery operation is carried out in the presence of a water-soluble polymerization inhibitor. Method of recovering system monomers.
００ｇ−水以上である重合禁止剤の水溶液で使用する請
求項１記載のビニル系単量体の回収法。2. The solubility in water under the conditions of use is 1 g / 1.
The method for recovering a vinyl-based monomer according to claim 1, wherein the method is used as an aqueous solution of a polymerization inhibitor of at least 00 g-water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13564792A JP3232651B2 (en) | 1992-04-30 | 1992-04-30 | Recovery method for vinyl monomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13564792A JP3232651B2 (en) | 1992-04-30 | 1992-04-30 | Recovery method for vinyl monomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05310814A true JPH05310814A (en) | 1993-11-22 |
| JP3232651B2 JP3232651B2 (en) | 2001-11-26 |
Family
ID=15156693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13564792A Expired - Fee Related JP3232651B2 (en) | 1992-04-30 | 1992-04-30 | Recovery method for vinyl monomers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3232651B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001233914A (en) * | 2000-02-21 | 2001-08-28 | Nippon Synthetic Chem Ind Co Ltd:The | Manufacturing method of vinyl acetate polymer |
| JP2003089706A (en) * | 2001-09-19 | 2003-03-28 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing vinyl acetate polymer and saponified product thereof |
| JP2003089741A (en) * | 2001-09-19 | 2003-03-28 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing vinyl acetate polymer and saponified product thereof |
| CN105273111A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Method for reducing fouling of steam stripping apparatus during polyvinyl chloride production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3808184A (en) | 1972-06-14 | 1974-04-30 | Universal Pvc Resins | Method of reducing polymerization of vinyl chloride in a monomer recovery system |
-
1992
- 1992-04-30 JP JP13564792A patent/JP3232651B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001233914A (en) * | 2000-02-21 | 2001-08-28 | Nippon Synthetic Chem Ind Co Ltd:The | Manufacturing method of vinyl acetate polymer |
| JP2003089706A (en) * | 2001-09-19 | 2003-03-28 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing vinyl acetate polymer and saponified product thereof |
| JP2003089741A (en) * | 2001-09-19 | 2003-03-28 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing vinyl acetate polymer and saponified product thereof |
| CN105273111A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Method for reducing fouling of steam stripping apparatus during polyvinyl chloride production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3232651B2 (en) | 2001-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3278506A (en) | Water-soluble polymers and copolymers | |
| US3954910A (en) | Process for removal and recovery of unreacted monomers from resinous polymers | |
| JPH05310814A (en) | Method of recovering vinyl monomer | |
| KR20000062683A (en) | Method for production of (meth)acrylic acid and/or (meth)acrylic esters | |
| JP3177860B2 (en) | Recovery method for vinyl monomers | |
| JPH0481601B2 (en) | ||
| JPS582962B2 (en) | Manufacturing method of vinyl chloride resin | |
| JPS5928575B2 (en) | Method for continuously removing monomer contaminants from aqueous dispersions of homo- and copolymers of vinyl chloride | |
| DE2141770A1 (en) | METHOD AND APPARATUS FOR THE PRODUCTION OF POLYMERIZED OR COPOLYMERIZED BY VINYL CHLORIDE BY CONTINUOUS BULK POLYMERIZATION | |
| US4015064A (en) | Manufacture of polyvinyl chloride of low vinyl chloride monomer content | |
| US3998655A (en) | Method for cleansing vinyl chloride polymerization reactors | |
| JPH0350762B2 (en) | ||
| EP1420034B1 (en) | Process for recovery of residual ethylene from the production of vinylester-ethylene copolymers | |
| JPH0118082B2 (en) | ||
| SU426369A3 (en) | ||
| US5187245A (en) | Method of addition of polymerization initiator | |
| JP3972427B2 (en) | Apparatus and method for recovering unreacted monomer in vinyl chloride polymerization facility | |
| JP2574077B2 (en) | Method for producing vinyl chloride polymer | |
| JPH01249813A (en) | Production of vinyl chloride-based resin | |
| JP3197146B2 (en) | Polymerization vessel effective for preventing adhesion of polymer scale and method for producing polymer using the same | |
| JPS5940842B2 (en) | Method for producing cationic polymer | |
| JPS6220512A (en) | Production of deodorized ethylene copolymer | |
| JP3440646B2 (en) | Method for producing vinyl chloride polymer | |
| JP2002060416A (en) | Method for producing vinyl chloride polymer and apparatus for recovering the same | |
| JPH01158008A (en) | Production of vinyl chloride based polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070921 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080921 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 7 Free format text: PAYMENT UNTIL: 20080921 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080921 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 7 Free format text: PAYMENT UNTIL: 20080921 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080921 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20090921 |
|
| LAPS | Cancellation because of no payment of annual fees |