JPH0725809B2 - Cleaning method for polymer substances - Google Patents
Cleaning method for polymer substancesInfo
- Publication number
- JPH0725809B2 JPH0725809B2 JP18122686A JP18122686A JPH0725809B2 JP H0725809 B2 JPH0725809 B2 JP H0725809B2 JP 18122686 A JP18122686 A JP 18122686A JP 18122686 A JP18122686 A JP 18122686A JP H0725809 B2 JPH0725809 B2 JP H0725809B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer substance
- solvent
- cleaning
- group
- present
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、芳香族ビニル−アクリロニトリル共重合体の
製造又は成形装置に付着する高分子物質の洗浄方法に関
する。TECHNICAL FIELD The present invention relates to a method for producing an aromatic vinyl-acrylonitrile copolymer or a method for cleaning a polymer substance attached to a molding apparatus.
芳香族ビニル−アクリロニトリル共重合体の製造又は成
形時に、単量体や重合溶媒に不溶若しくは難溶な高分子
物質が、装置内に付着することが知られている。It is known that a polymer substance that is insoluble or hardly soluble in a monomer or a polymerization solvent adheres to the inside of an apparatus during the production or molding of an aromatic vinyl-acrylonitrile copolymer.
この高分子物質は、反応槽内や伝熱装置等の壁面に付着
し、伝熱性能の低下や配管の閉塞を起こす。これに伴な
い、反応の制御性の低下、生産性の低下が起こり、安定
操業の大きな障害となっている。また更には、付着する
高分子物質の一部が製品中へ混入い、製品外観や色相の
悪化が発生する。このためしばしば操業を停止してこの
高分子物質を除去する必要があった。This polymer substance adheres to the inside of the reaction tank and the wall surface of the heat transfer device, etc., and causes deterioration of heat transfer performance and blockage of piping. Along with this, the controllability of the reaction and the productivity are reduced, which is a major obstacle to stable operation. Furthermore, a part of the adhered polymer substance is mixed into the product, which deteriorates the appearance and hue of the product. For this reason, it was often necessary to stop the operation to remove this polymeric substance.
この高分子物質の除去方法としては、入力による除去作
業も実施されているが多大な人手と時間とを要し、また
装置の破損や作業者の残存化学物質による汚染等も発生
し、好ましい方法とは言えない。As a method for removing this polymer substance, removal work by input is also carried out, but it requires a great deal of manpower and time, and the device is damaged and contamination by residual chemical substances of the worker occurs, which is a preferable method. It can not be said.
また高圧流体を用いて剥離除去する方法も知られている
が、装置の構造上高圧流体を直接吹き付けられない個所
が存在する場合や、強度が不足している場合には適用で
きない。A method of peeling and removing using a high-pressure fluid is also known, but it cannot be applied when there is a portion where the high-pressure fluid cannot be directly sprayed due to the structure of the apparatus or when the strength is insufficient.
このため、溶剤による洗浄除去方法が一般に行なわれて
いる。単量体での洗浄は、低温では溶解能力が劣り、高
温では単量体の重合が起こりやすく洗浄の効果が小さい
ので、重合体を溶解し得る溶媒が用いられる。Therefore, a cleaning and removing method using a solvent is generally performed. In the case of washing with a monomer, the solvent has a poor dissolving ability at a low temperature, and the monomer is easily polymerized at a high temperature, and the washing effect is small. Therefore, a solvent capable of dissolving the polymer is used.
ジメチルホルムアマイドなどのアルキルアマイド及びジ
メチルスルホキシドなどのアルキルスルホキシドは、芳
香族ビニル−アクリロニトリル共重合体に対して良好な
溶媒であるが、製造装置内に付着する高分子物質は架橋
若しくは変性により溶解の不能なものもあるため、これ
ら溶媒を用いて製造装置の洗浄を行なっても完全には溶
解除去することはできない。この除去できない高分子物
質が装置内に少量残ると、これが核となって新たに高分
子物質が生成付着する原因となることが知られている。Alkyl amides such as dimethylformamide and alkyl sulphoxides such as dimethylsulfoxide are good solvents for aromatic vinyl-acrylonitrile copolymers, but polymeric substances that adhere to the manufacturing equipment are dissolved by crosslinking or modification. Since some of them are impossible, even if the manufacturing apparatus is washed with these solvents, they cannot be completely dissolved and removed. It is known that if a small amount of this non-removable polymer substance remains in the device, it becomes a nucleus and causes new polymer substance to be attached.
高ニトリル樹脂製造時のゲル化物に対しては、アルカリ
金属及びアルカリ土類金属の水酸化物等を含有する溶媒
を用いて溶解除去する方法が知られている（特公昭55−
8087号）。しかし、この方法は低ニトリル樹脂製造時に
生成する高分子物質に適用しても溶解力が劣ることが判
明した。A method of dissolving and removing the gelled product during the production of the high nitrile resin using a solvent containing a hydroxide of an alkali metal or an alkaline earth metal is known (Japanese Patent Publication No. 55-
No. 8087). However, it has been found that this method is inferior in dissolving power even when it is applied to a polymer substance produced during the production of a low nitrile resin.
この低ニトリル含量の芳香族ビニル−アクリロニトリル
共重合体の製造時または成形時に装置内に付着する高分
子物質の洗浄方法として特公昭59−50244号公報がある
が短時間に除去できる方法とは言い難くいっそうの改良
が望まれていた。There is JP-B-59-50244 as a method for cleaning the polymer substance that adheres to the inside of the apparatus during the production or molding of this low nitrile content aromatic vinyl-acrylonitrile copolymer, but it is said that it can be removed in a short time. It was difficult and much desired to be improved.
本発明の目的は低ニトリル含量の芳香族ビニル−アクリ
ロニトリル共重合体の製造時または成形時に装置内に付
着する高分子物質を、従来法よりも短時間に、容易かつ
完全に洗浄除去する方法を提供することにある。An object of the present invention is to provide a method for easily and completely washing and removing a polymer substance attached to an apparatus during production or molding of an aromatic vinyl-acrylonitrile copolymer having a low nitrile content in a shorter time than the conventional method. To provide.
本発明者らは上記の目手を達成するため種々検討を行な
った結果特定のジアマイドと金属アルコレートとを共用
することにより、従来法に比較し大巾に短い時間で高分
子物質を洗浄除去する方法を見出し、これに基いて本発
明を完成した。The present inventors have conducted various studies to achieve the above-mentioned measures, and as a result, by using a specific diamide and a metal alcoholate in common, the polymer substance is removed by washing in a significantly shorter time than in the conventional method. The present invention has been completed based on the finding method.
すなわち、本発明は、芳香族ビニル−アクリロニトリル
共重合体の製造又は成形時に装置内に付着する高分子物
質を洗浄するについて、＞Ｎ−CO−Ｎ＜の構造を有する
ジアマイドを含む溶媒及び少くとも一種の金属アルコレ
ートを同時に用いることを特徴とする高分子物質の洗浄
方法である。That is, the present invention relates to cleaning a polymer substance that adheres to the inside of an apparatus during the production or molding of an aromatic vinyl-acrylonitrile copolymer, and a solvent containing at least a diamide having a structure of> N-CO-N <and at least This is a method for cleaning a polymer substance, which is characterized by simultaneously using one kind of metal alcoholate.
本発明を適用しうる芳香族ビニル−アクリロニトリル共
重合体は、重合体中にアクリロニトリルを５重量％以上
含むもので含有量の高いほど有効であるが特に60重量％
以下において従来法に優るものである。またアクリロニ
トリルの代りにメタアクリロニトリルなどのニトリル単
量体を含むものでも良く、芳香族ビニル単量体としては
スチレン、α−メチルスチレン等が挙げられ、製造方法
としては懸濁重合、溶液重合、塊状重合等の方法にも適
用が可能である。The aromatic vinyl-acrylonitrile copolymer to which the present invention can be applied contains 5% by weight or more of acrylonitrile in the polymer, and the higher the content, the more effective it is.
The following is superior to the conventional method. Further, instead of acrylonitrile, those containing a nitrile monomer such as methacrylonitrile may be used, examples of the aromatic vinyl monomer include styrene and α-methylstyrene, and the production method includes suspension polymerization, solution polymerization, and bulk. It can also be applied to methods such as polymerization.
本発明で使用されるジアマイドは＞Ｎ−CO−Ｎ＜の構造
を有するジアマイド化合物である。本発明のジアマイド
化合物を用いることにより特公昭59−50244号に示され
る、アルキルアマイドを溶媒とする従来技術に対して後
述の実施例、比較例で明らかな様に、大幅な改良が可能
となった。The diamide used in the present invention is a diamide compound having a structure of> N-CO-N <. By using the diamide compound of the present invention, as shown in Japanese Examined Patent Publication No. 59-50244, it is possible to make a significant improvement as will be apparent from the examples and comparative examples described below with respect to the conventional technique using an alkyl amide as a solvent. It was
上記のジアマイド化合物としては鎖式化合物としてテト
ラメチル尿素、環式化合物として1,3−ジメチル−２−
イミダゾリジノンなどがあげられ特に1,3−ジメチル−
２−イミダゾリジノンが好ましい。As the above-mentioned diamide compound, tetramethylurea as a chain compound, 1,3-dimethyl-2- as a cyclic compound
Imidazolidinone and the like, especially 1,3-dimethyl-
2-Imidazolidinone is preferred.
上記溶媒には他のアルキルアマイド、アルキルスルホキ
シドが混合されていても良く、これはさらにアクリロニ
トリルがメタアクリロニトリル、スチレン、α−メチル
スチレンなどの単量体、ベンゼン、トルエン、エチルベ
ンゼンなどの芳香族炭化水素またはアセトン、メチルエ
チルケトンなどの他の溶媒を若干含有してもよい。The above solvent may be mixed with other alkyl amides and alkyl sulfoxides, and acrylonitrile is further acrylonitrile, styrene, α-methylstyrene and other monomers, benzene, toluene, ethylbenzene and other aromatic hydrocarbons. Alternatively, some other solvent such as acetone or methyl ethyl ketone may be contained.
溶媒に共存する水には特に制限はないが水の含有量が多
くなると高分子物質の溶解能力が低下し好ましくない。Water coexisting in the solvent is not particularly limited, but if the content of water increases, the dissolving ability of the polymer substance decreases, which is not preferable.
また、上記溶媒と同時に存在させる金属アルコレート
は、式（Ｉ）で表わされる化合物である。Further, the metal alcoholate that is present at the same time as the solvent is a compound represented by the formula (I).
（Ｒ−Ｏ）XM ……（Ｉ） 但し、Ｒはメチル基、エチル基、プロピル基又はブチル
基等のアルキル基であり、ＸはＭに結合する（Ｒ−Ｏ）
の数を表わしＭはＸが１のときアルカリ金属、Ｘが２の
ときアルカリ土類金属、Ｘが３のときアルミニウムであ
り、Ｘが２又は３の場合にはＲは異種のアルキル基であ
ってもよい。(RO) X M (I) However, R is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and X is bonded to M (RO).
M is an alkali metal when X is 1, an alkaline earth metal when X is 2, aluminum when X is 3, and when X is 2 or 3, R is a different alkyl group. May be.
より具体的には、ナトリウムメチラート、ナトリウムエ
チラート、カリウムメチラート、カリウムエチラート、
カリウムｔ−ブチラート、マクネシウムメチラート、マ
グネシウムエチラート及びアルミニウムエチラート等が
好適な金属アルコレートとして挙げられる。More specifically, sodium methylate, sodium ethylate, potassium methylate, potassium ethylate,
Suitable metal alcoholates include potassium t-butyrate, magnesium methylate, magnesium ethylate and aluminum ethylate.
溶媒と同時に存在させる金属アルコレートの量は１×10
-4〜1.0グラム当量／が好ましく、１×10-3〜１×10
-2グラム当量／が好適である。The amount of metal alcoholate present at the same time as the solvent is 1 x 10
-4 to 1.0 gram equivalent / preferable, 1 x 10 -3 to 1 x 10
-2 gram equivalent / is preferred.
金属アルコレートを溶媒と同時に存在させる方法として
は、予め溶媒中に添加しておく方法や、溶媒での洗浄の
途中に添加する方法などの方法を用いても良い。例え
ば、重合装置内を溶媒で満たし、その後金属アルコレー
トを添加し加温撹拌する方法が行なわれる。また洗滌に
当っては前もって付着する高分子物質の一部の単量体や
適当な溶媒で除去した後に、本発明の金属アルコレート
を含む溶媒を使用することも可能である。As the method of allowing the metal alcoholate to be present at the same time as the solvent, a method of adding it in the solvent in advance or a method of adding it during the washing with the solvent may be used. For example, a method of filling the inside of the polymerization apparatus with a solvent, then adding a metal alcoholate and stirring with heating is performed. It is also possible to use the solvent containing the metal alcoholate of the present invention after washing with a monomer or a suitable solvent to remove a part of the polymer substance to be attached in advance.
本発明の洗浄方法では、洗浄の温度には特に限定はな
く、高分子物質が付着する場所や装置に応じて選ぶこと
ができる。しかし高分子物質のガラス転移温度付近、又
はそれ以上の温度を測定することにより洗浄の効果を一
層増加することができる。In the cleaning method of the present invention, the cleaning temperature is not particularly limited and can be selected according to the place where the polymer substance is attached or the device. However, the effect of washing can be further increased by measuring the temperature around the glass transition temperature of the polymer substance or higher.
以下、実施例により本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples.
実施例 １〜５ スチレン−アクリロニトリル共重合体を製造する装置に
おいて、アクリロニトリル含有率の異なるスチレン−ア
クリロニトリル共重合体を、各々１ケ月間連続塊状重合
法で製造した。この装置内に予め3cm×3cmのステンレス
製の試験片を取付けておき、高分子物質の付着した試験
片を得た。この試験片には各々約1gの高分子物質が付着
していた。Examples 1 to 5 In a device for producing a styrene-acrylonitrile copolymer, styrene-acrylonitrile copolymers having different acrylonitrile contents were produced by a continuous bulk polymerization method for 1 month. A test piece made of stainless steel having a size of 3 cm × 3 cm was attached in advance in this apparatus to obtain a test piece having a polymer substance attached thereto. About 1 g of the polymer substance was attached to each of the test pieces.
この試験片を溶量1000mlのフラスコ内に入れ、CH3ONaを
4.0×10-3グラム当量／を含む1,3−ジメチル−２−イ
ミダゾリジノン500mlを加え、130℃で撹拌しながら洗浄
を行なった。この洗浄試験の結果を表１の実施例１〜５
に示す。Put this test piece in a flask with a dissolution volume of 1000 ml and add CH 3 ONa.
500 ml of 1,3-dimethyl-2-imidazolidinone containing 4.0 × 10 −3 gram equivalent / was added, and the mixture was washed at 130 ° C. with stirring. The results of this cleaning test are shown in Examples 1 to 5 in Table 1.
Shown in.
比較例 １〜５ 実施例１〜５と同様にして得た試験片に対し、1,3−ジ
メチル−２−イミダゾリジノンの代りにジメチルホルム
アマイドを用いた以外は実施例１〜５と同様に洗浄試験
を行なった。この結果を比較例１〜５に示す。Comparative Examples 1 to 5 Similar to Examples 1 to 5 except that dimethylformamide was used instead of 1,3-dimethyl-2-imidazolidinone for test pieces obtained in the same manner as in Examples 1 to 5. A cleaning test was conducted on the. The results are shown in Comparative Examples 1-5.
実施例 ６〜10, 比較例 ６〜10 実施例３で用いたものと同じ試験片、すなわちアクリロ
ニトリル含有量が24重量％のスチレン−アクリロニトリ
ル共重合体を製造する装置内に取付けておき得られた高
分子物質の付着した試験片を、実施例１〜５と同様の方
法により洗浄試験を行なった。溶媒として1,3−ジメチ
ル−２−イミダゾリジノンとジメチルホルムアマイド、
金属アルコレートとしてCH3ONa,（OH3）3COK,（CH2O）2
Mgを使用した。結果を表２に示す。 Examples 6 to 10 and Comparative Examples 6 to 10 The same test pieces as those used in Example 3, that is, the acrylonitrile content of 24% by weight, was obtained by being installed in an apparatus for producing a styrene-acrylonitrile copolymer. The test piece having the polymer substance attached thereto was subjected to a cleaning test by the same method as in Examples 1 to 5. 1,3-dimethyl-2-imidazolidinone and dimethylformamide as solvents,
CH 3 ONa, (OH 3 ) 3 COK, (CH 2 O) 2 as metal alcoholate
Mg was used. The results are shown in Table 2.
〔発明の効果〕 実施例及び比較例より明らかな様にジアマイドを含む溶
媒と金属アルコレートとを同時に用いる本発明の高分子
物質の洗浄方法は、従来知られていた溶剤系を使用する
方法に比較すると、溶解時間が極めて短かくてすみ、か
つ高分子物質の除去が完全にあるため、工業的規模の共
重合体製造装置あるいは成形装置の洗浄にあたっては、
多大な効果を発揮するものである。 [Effects of the Invention] As is clear from Examples and Comparative Examples, the method for washing a polymer substance of the present invention in which a solvent containing a diamide and a metal alcoholate are simultaneously used is a method using a conventionally known solvent system. By comparison, the dissolution time is extremely short, and since the removal of the polymeric substances is complete, when cleaning the industrial scale copolymer production equipment or molding equipment,
It has a great effect.
Claims (2)
の製造又は成形時に、装置に付着する高分子物質を洗浄
除去するについて、＞Ｎ−CO−Ｎ＜の構造を有するジア
マイドを含む溶媒及び少くとも一種の金属アルコレート
を同時に用いることを特徴とする高分子物質の洗浄方
法。1. A method for cleaning and removing a polymeric substance adhering to a device during the production or molding of an aromatic vinyl-acrylonitrile copolymer, wherein a solvent containing at least a diamide having a structure of> N—CO—N <and at least A method for cleaning a polymer substance, which comprises simultaneously using one kind of metal alcoholate.
れる特許請求の範囲第１項記載の方法。 （Ｒ−Ｏ）XM ……（Ｉ） 但し、Ｒはメチル基、エチル基、プロピル基又はブチル
基などのアルキル基であり、ＸはＭに結合する（Ｒ−
０）の数を表わし、ＭはＸが１のときアルカリ金属、Ｘ
が２ときアルカリ土類金属、Ｘが３のときアルミニウム
であり、Ｘが２または３の場合には、Ｒは異種のアルキ
ル基であってもよい。2. The method according to claim 1, wherein the metal alcoholate is represented by the general formula (I). (RO) X M (I) However, R is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and X is bonded to M (R-
0), where M is an alkali metal when X is 1, X
When 2 is an alkaline earth metal, when X is 3 is aluminum, and when X is 2 or 3, R may be a different alkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18122686A JPH0725809B2 (en) | 1986-08-02 | 1986-08-02 | Cleaning method for polymer substances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18122686A JPH0725809B2 (en) | 1986-08-02 | 1986-08-02 | Cleaning method for polymer substances |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6339907A JPS6339907A (en) | 1988-02-20 |
| JPH0725809B2 true JPH0725809B2 (en) | 1995-03-22 |
Family
ID=16097014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18122686A Expired - Fee Related JPH0725809B2 (en) | 1986-08-02 | 1986-08-02 | Cleaning method for polymer substances |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725809B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240028312A (en) | 2022-08-24 | 2024-03-05 | 몬테피브레 마에 테크놀로지스 에스.알.엘. | Process for the recovery and recycling of unreacted monomer in a single-step process for the production of a carbon-fiber precursor |
-
1986
- 1986-08-02 JP JP18122686A patent/JPH0725809B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6339907A (en) | 1988-02-20 |
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