JP3633773B2 - Polymerization scale prevention method - Google Patents
Polymerization scale prevention method Download PDFInfo
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- JP3633773B2 JP3633773B2 JP02189498A JP2189498A JP3633773B2 JP 3633773 B2 JP3633773 B2 JP 3633773B2 JP 02189498 A JP02189498 A JP 02189498A JP 2189498 A JP2189498 A JP 2189498A JP 3633773 B2 JP3633773 B2 JP 3633773B2
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- polymerization
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- 238000006116 polymerization reaction Methods 0.000 title claims description 66
- 238000000034 method Methods 0.000 title claims description 15
- 230000002265 prevention Effects 0.000 title claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000002455 scale inhibitor Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 4
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Landscapes
- Polymerisation Methods In General (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は水を媒体とする重合において生成する重合スケールの改良された防止法である。詳しくは、重合スケール防止剤をアルカリ性水溶液に溶解し、これを重合器の内壁面等に塗布し、乾燥後、酸性化合物水溶液で処理した後、重合する事を特徴とする重合スケール防止法である。
【０００２】
【従来の技術】
重合スケール防止剤は一般には非水溶性と水溶性に大別できるが、水を媒体とする重合においては、水溶性の重合スケール防止剤はその効果は殆どない。これは水溶性の重合スケール防止剤は水媒体中に容易に溶解するためである。従って実際に使用されている重合スケール防止剤は非水溶性である。非水溶性の重合スケール防止剤は一般にメタノール、エタノール、アセトン、テトラヒドロフラン、ジメチルホルムアミド、トルエン等の有機溶剤に溶解し重合器内壁面等に塗布、乾燥してその目的に使用されている。
【０００３】
しかし、斯かる有機溶剤は重合工程中に混入し製品の悪化をきたしたり、排水水質の悪化及び大気中への拡散による大気汚染等の環境への悪影響の問題がある。特に最近では大気のハイドロカーボン規制のため有機溶剤の使用を避ける必要性がでてきた。斯かる見地から、特定の重合スケ−ル防止剤であるレゾルシノールとアセトアルデヒドまたはベンズアルデヒドの縮合物をアルカリ性水溶液にし、重合器器壁内面等へ塗布する方法（公開公報５７−５０２１６９、５７−５０２１７０）が知られている。所が、該法では、アルカリ性塗布剤が水溶性であるため、重合時水媒体に流出し持続的な重合スケール防止効果が得られないという欠点があった。
【０００４】
【本発明が解決しようとする課題】
本発明の目的は、水を媒体とする重合において、有機溶剤を全く使用しないでかつ持続性のよい重合スケール防止法を提供するものである。
【０００５】
【課題を解決するための手段】
本発明者は、上記有機溶剤の使用を避けるため鋭意検討した結果、重合スケール防止剤のアルカリ性水溶液を重合器内壁面等に塗布し、乾燥後、酸性化合物水溶液で処理すると、塗布膜が水に不溶となることを発見し本発明に至ったものである。
【０００６】
即ち、本発明は、水を媒体とする重合において重合スケール防止剤をアルカリ性水溶液に溶解し、これを重合器の内壁面等に塗布し、乾燥後、酸性化合物水溶液で処理した後、重合する事を特徴とする重合スケール防止法である。
【０００７】
【発明の実施の形態】
本発明の重合スケール防止剤とは、アルカリ性水溶液に可溶なスケール防止剤で、例えば、フェノール系化合物とアルデヒド化合物の縮合物（公開公報５７−１９２４１４、７−１８００４）、フェノール系化合物とアミン系化合物の縮合物（公開公報平７−２５９１０）、アミン系化合物の重縮合物（公開公報５４−２００８９）、アミン系化合物とキノン化合物の縮合物（公開公報平５−１１２６０２）、アジン環化合物（公開公報４９−８８９８５）、ジインドリル類化合物（公開公報５１−１３８８１）、π結合、窒素、硫黄、酸素、不対電子を持つ化合物（公開公報５１−５３５８９）等公知の重合スケール防止剤がある。
【０００８】
これらの中でも、スケール防止効果から、フェノール系化合物とアルデヒド化合物の縮合物が好ましく、更に詳しくはピロガロール／ベンズアルデヒド縮合物、ピロガロール／ホルマリン縮合物、ピロガロール／ホルマリン／レゾルシノール縮合物が好適で、これらの中の少なくとも一種以上から選んで用いることが好ましい。
【０００９】
本発明のアルカリ性水溶液は、水酸化ナトリューム、水酸化カリューム、水酸化カルシューム、水酸化マグネシューム、炭酸水素ナトリューム、炭酸水素カリューム、重炭酸ナトリューム、重炭酸カリューム、硼酸ナトリューム、硼酸カリューム等の公知のアルカリ性化合物単独或いはこれらの２種以上の混合物の水溶液である。アルカリ性水溶液のアルカリ性化合物濃度は特に限定はないが０．００５規定から５規定位がよい。
【００１０】
本発明では前記で得られたアルカリ性水溶液を重合器の内壁面等に塗布するが、塗布法としては刷毛、スプレー等公知の方法で塗布すればよい。次いで、塗布した重合器の内壁面等を乾燥し、水分を蒸発させる。乾燥温度は特に限定はないが５０℃から９０℃がよい。また、予め重合器の内壁面等を５０℃から９０℃に加熱しそこに塗布剤を塗布してもよい。塗布乾燥時間の短縮面から予め加熱した重合器の内壁面等に塗布する方が好ましい。
【００１１】
本発明ではアルカリ性水溶液中のスケール防止剤の濃度は０．０５重量％〜５重量％、好ましくは０．１重量％〜３重量％の範囲がよい。また、塗布量は塗布面積当たり０．０５ｇ／ｍ２〜５ｇ／ｍ２位がよい。これらは特に限定的でない。本発明の酸性化合物水溶液とは、塩酸、硫酸、硝酸、燐酸等の鉱酸、蓚酸、クエン酸等の有機酸等の酸性化合物の水溶液であるが、コスト的には鉱酸がよい。また、その水溶液濃度は０．００１規定から１規定程度が良い。
【００１２】
本発明での酸性化合物水溶液の処理とは、該水溶液を乾燥塗布膜面に接触させる事で、塗布膜を中和させ、スケール防止剤を水不溶にする事である。具体的には、塗布膜上に酸性化合物水溶液を刷毛で塗布するかスプレー等で吹き付ける、或いは、塗布膜を酸性化合物水溶液に浸漬してもよい。また、処理時間、温度は特に限定は無いが、１分から３０分、２０℃から９０℃位であればよい。
【００１３】
本発明では必要に応じて塗布剤水溶液に界面活性剤を添加してもよい。これは、アルカリ性水溶液が重合器の内壁面等に塗布した時、濡れが悪い場合に使用できる。界面活性剤としてはイオン性或いはノニオン性の公知の界面活性剤がある。例えば、ドデシルベンゼンスルホン酸ナトリューム、ナフタリンスルホン酸ナトリューム、ノニルフエニルエーテル、部分鹸化ポリ酢酸ビニル等の公知の界面活性剤がある。これら単独或いは２種以上混合してもよい。その使用量は、重合スケール防止剤１００重量部あたり１から５０重量部であればよい。
【００１４】
また、本発明では塗布剤水溶液に重合スケール防止助長効果の目的に使用される公知の金属化合物を添加併用してもよい。金属化合物としては、アルミニューム、鉄、シリコン、ニッケル、チタニューム、スズ等の酸化物、水酸化物、塩化物、炭酸塩等の公知の物がある。その使用量は重合スケール防止剤１００重量部あたり３０から１５０重量部であればよい。
【００１５】
本発明での重合器の内壁面とは、重合器の内壁面並びに、重合器に付帯する邪魔板、撹拌翼、仕込配管、回収配管、リフラックス配管等重合スケールが生成する箇所をいう。
本発明は水を媒体とする重合における重合スケール防止剤として使用する。その重合する単量体としては特に限定されないが、そのスケール防止効果はビニル系単量体において大きい。ビニル系単量体としては、塩化ビニル、スチレン、アクリロニトリル、メチルメタアクリレート、ブチルアクリレート、酢酸ビニル公知のビニル系単量体があげられ、１種類の単量体による単独重合或いは２種類以上の単量体の組み合わせによる共重合いずれをも含まれる。また、本発明にいう水を媒体とする重合とは懸濁重合法、マイクロ懸濁重合法、乳化重合法等の公知の重合法をいう。
【００１６】
【実施例】
以下に本発明の実施例、比較例を例示するが、これらは何ら本発明を限定するものではない。
「実施例１−５」「比較例１−５」「参考例１」
重合スケール防止剤５ｇを０．１規定の水酸化ナトリューム１００ｍＬに溶解した。ここに水４００ｍＬ添加し希釈後、該アルカリ性水溶液を１．５ｍ３重合器内壁面にスプレー塗布し、７０℃で３０分乾燥した。次いで重合器内を、０．０１規定塩酸水溶液で満たし、５０゜Ｃで２０分間処理した後、処理水を排出した。
【００１７】
次いで、次に示す重合法で連続５バッチ重合した。その時の各バッチ後のスケール防止効果を表１に示す。
また、比較のために、酸性化合物水溶液で処理しなかった場合、並びに、参考例として該スケール防止剤５ｇを有機溶剤メタノール５００ｍＬに溶解した場合のスケール防止効果も併せて表１に示した。
（重合法：塩化ビニルの懸濁重合）
内容積１．５ｍ３の重合器に部分鹸化ポリ酢酸ビニル３３０ｇを溶解した水７００ｋｇ、塩化ビニル５５０ｋｇ、ジー２−エチルヘキシルパーオキシジカーボネート２２０ｇを仕込み、５７゜Ｃで７時間重合を行った。
重合容器内壁面等に塗布乾燥したスケール付着状態を目視にて観察し、下記の基準に従い判定した。
【００１８】
○：壁面全体にスケールの付着が認められない
△：壁面の一部にスケールの付着が認められる
×：壁面の全部にスケールの付着が認められる
【００１９】
【表１】
表１から、重合スケール防止剤のアルカリ性水溶液を塗布し、酸性化合物水溶液で処理すれば、連続５バッチ以上のスケール防止持続効果がある事が判る。一方、酸性化合物水溶液の処理がない場合はスケール防止効果が弱く、持続効果はない事が判る。
【００２１】
【発明の効果】
以上のように、本発明は全く有機溶剤を使用しなく、かつ、有効な重合スケール防止持続効果を得られる事ができる方法であり、工業的に価値ある事が判る。[0001]
BACKGROUND OF THE INVENTION
The present invention is an improved method of preventing polymerization scale produced in water-based polymerization. Specifically, this is a polymerization scale prevention method characterized in that a polymerization scale inhibitor is dissolved in an alkaline aqueous solution, applied to the inner wall surface of the polymerization vessel, dried, treated with an acidic compound aqueous solution, and then polymerized. .
[0002]
[Prior art]
In general, polymerization scale inhibitors can be broadly classified into water-insoluble and water-soluble, but in polymerization using water as a medium, water-soluble polymerization scale inhibitors have little effect. This is because a water-soluble polymerization scale inhibitor is easily dissolved in an aqueous medium. Therefore, the polymerization scale inhibitor actually used is water-insoluble. Water-insoluble polymerization scale inhibitors are generally used for this purpose after being dissolved in an organic solvent such as methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide, toluene, etc., coated on the inner wall of the polymerization vessel, and the like.
[0003]
However, such an organic solvent is mixed during the polymerization process to cause deterioration of the product, and there is a problem of adverse effects on the environment such as deterioration of drainage water quality and air pollution due to diffusion into the atmosphere. In recent years, there has been a need to avoid the use of organic solvents due to atmospheric hydrocarbon regulations. From such a standpoint, there is a method (open publications 57-502169, 57-502170) in which a condensate of resorcinol and acetaldehyde or benzaldehyde, which is a specific polymerization scale inhibitor, is made into an alkaline aqueous solution and applied to the inner surface of the polymerization vessel wall or the like. Are known. However, in this method, since the alkaline coating agent is water-soluble, it has a drawback that it does not flow out into an aqueous medium during polymerization and a continuous polymerization scale preventing effect cannot be obtained.
[0004]
[Problems to be solved by the present invention]
An object of the present invention is to provide a method for preventing polymerization scale that does not use any organic solvent and has good durability in polymerization using water as a medium.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to avoid the use of the organic solvent, the present inventors applied an alkaline aqueous solution of a polymerization scale inhibitor to the inner wall surface of the polymerization vessel, etc., and after drying, treated with an acidic compound aqueous solution, It was discovered that it became insoluble, and the present invention was achieved.
[0006]
That is, in the present invention, in polymerization using water as a medium, a polymerization scale inhibitor is dissolved in an alkaline aqueous solution, applied to the inner wall surface of the polymerization vessel, dried, treated with an acidic compound aqueous solution, and then polymerized. Is a method for preventing polymerization scale.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The polymerization scale inhibitor of the present invention is a scale inhibitor that is soluble in an alkaline aqueous solution. For example, a condensation product of a phenolic compound and an aldehyde compound (publication publications 57-192414, 7-18044), a phenolic compound and an amine compound. Compound condensate (publication publication No. 7-25910), polycondensation product of amine compound (publication publication 54-20089), condensation product of amine compound and quinone compound (publication publication No. 5-112602), azine ring compound ( There are known polymerization scale inhibitors such as JP-A-49-88985), diindolyl compounds (JP-A-51-13881), compounds having a π bond, nitrogen, sulfur, oxygen, and unpaired electrons (JP-A-51-53589).
[0008]
Among these, a condensate of a phenolic compound and an aldehyde compound is preferable in view of scale prevention effect, and more specifically, pyrogallol / benzaldehyde condensate, pyrogallol / formalin condensate, and pyrogallol / formalin / resorcinol condensate are preferable. It is preferable to use at least one selected from the above.
[0009]
The alkaline aqueous solution of the present invention is a known alkaline compound such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydrogen carbonate, hydrogen carbonate sodium, sodium bicarbonate, bicarbonate calorium, sodium borate, boric acid calum, etc. It is an aqueous solution of one kind or a mixture of two or more of these. The concentration of the alkaline compound in the alkaline aqueous solution is not particularly limited, but is preferably 0.005 to 5 normal.
[0010]
In the present invention, the alkaline aqueous solution obtained as described above is applied to the inner wall surface of the polymerization vessel and the like. Next, the inner wall surface of the applied polymerization vessel is dried to evaporate the water. The drying temperature is not particularly limited, but 50 ° C. to 90 ° C. is preferable. Alternatively, the inner wall surface of the polymerization vessel may be heated in advance from 50 ° C. to 90 ° C. and the coating agent may be applied thereto. From the aspect of shortening the coating and drying time, it is preferable to apply to the inner wall surface of a preheated polymerization vessel.
[0011]
In the present invention, the concentration of the scale inhibitor in the alkaline aqueous solution is in the range of 0.05 wt% to 5 wt%, preferably 0.1 wt% to 3 wt%. The coating amount is preferably about 0.05 g / m 2 to 5 g / m 2 per coated area. These are not particularly limited. The acidic compound aqueous solution of the present invention is an aqueous solution of an acidic compound such as a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as oxalic acid or citric acid, but a mineral acid is preferable in terms of cost. The aqueous solution concentration is preferably about 0.001 to 1 normal.
[0012]
The treatment of the acidic compound aqueous solution in the present invention is to neutralize the coating film by bringing the aqueous solution into contact with the dry coating film surface and to make the scale inhibitor insoluble in water. Specifically, the acidic compound aqueous solution may be applied onto the coating film with a brush or sprayed with a spray or the like, or the coating film may be immersed in the acidic compound aqueous solution. The treatment time and temperature are not particularly limited, but may be from 1 minute to 30 minutes and from 20 ° C. to 90 ° C.
[0013]
In the present invention, a surfactant may be added to the aqueous coating agent solution as necessary. This can be used when wetness is poor when the alkaline aqueous solution is applied to the inner wall surface of the polymerization vessel. As the surfactant, there are known ionic or nonionic surfactants. For example, there are known surfactants such as sodium dodecylbenzenesulfonate, sodium naphthalenesulfonate, nonylphenyl ether, and partially saponified polyvinyl acetate. You may mix these individually or in mixture of 2 or more types. The amount used may be 1 to 50 parts by weight per 100 parts by weight of the polymerization scale inhibitor.
[0014]
In the present invention, a known metal compound used for the purpose of promoting the prevention of polymerization scale may be added to the aqueous coating agent solution. Examples of the metal compound include known substances such as oxides such as aluminum, iron, silicon, nickel, titanium, and tin, hydroxides, chlorides, and carbonates. The amount used may be 30 to 150 parts by weight per 100 parts by weight of the polymerization scale inhibitor.
[0015]
The inner wall surface of the polymerization vessel in the present invention refers to a portion where a polymerization scale is generated such as the inner wall surface of the polymerization vessel, baffles attached to the polymerization vessel, stirring blades, charging piping, recovery piping, reflux piping and the like.
The present invention is used as a polymerization scale inhibitor in water-based polymerization. The monomer to be polymerized is not particularly limited, but the scale-preventing effect is great for vinyl monomers. Examples of vinyl monomers include vinyl chloride, styrene, acrylonitrile, methyl methacrylate, butyl acrylate, vinyl acetate, and known vinyl monomers, such as homopolymerization with one monomer or two or more monomers. Any copolymerization by a combination of monomers is included. The polymerization using water as a medium in the present invention refers to a known polymerization method such as a suspension polymerization method, a micro suspension polymerization method or an emulsion polymerization method.
[0016]
【Example】
Examples of the present invention and comparative examples are illustrated below, but these do not limit the present invention.
"Example 1-5""Comparative Example 1-5""Reference Example 1"
5 g of a polymerization scale inhibitor was dissolved in 100 mL of 0.1 N sodium hydroxide. After 400 mL of water was added and diluted, the alkaline aqueous solution was spray-coated on the inner wall surface of a 1.5 m 3 polymerization vessel and dried at 70 ° C. for 30 minutes. Next, the inside of the polymerization vessel was filled with a 0.01 N hydrochloric acid aqueous solution, treated at 50 ° C. for 20 minutes, and the treated water was discharged.
[0017]
Subsequently, continuous 5 batch polymerization was carried out by the following polymerization method. The scale prevention effect after each batch at that time is shown in Table 1.
For comparison, Table 1 also shows the scale prevention effect when not treated with an acidic compound aqueous solution, and when 5 g of the scale inhibitor is dissolved in 500 mL of an organic solvent methanol as a reference example.
(Polymerization method: suspension polymerization of vinyl chloride)
A polymerization vessel having an internal volume of 1.5 m 3 was charged with 700 kg of water in which 330 g of partially saponified polyvinyl acetate was dissolved, 550 kg of vinyl chloride, and 220 g of g-2-ethylhexyl peroxydicarbonate, and polymerized at 57 ° C. for 7 hours.
The scale adhesion state applied and dried on the inner wall surface of the polymerization vessel was visually observed and judged according to the following criteria.
[0018]
○: No scale adherence to the entire wall surface Δ: Scale adherence to a part of the wall surface ×: Scale adherence to the entire wall surface [0019]
[Table 1]
From Table 1, it can be seen that if an alkaline aqueous solution of a polymerization scale inhibitor is applied and treated with an acidic compound aqueous solution, there is a continuous scale prevention effect of 5 batches or more. On the other hand, when there is no treatment of the acidic compound aqueous solution, the scale prevention effect is weak and it can be seen that there is no sustaining effect.
[0021]
【The invention's effect】
As described above, it can be seen that the present invention is an industrially valuable method that does not use an organic solvent at all, and can obtain an effective effect of preventing and preventing polymerization scale.
Claims (5)
とする請求項１〜４記載の重合スケール防止法The method for preventing polymerization scale according to claim 1, wherein the monomer to be polymerized is a vinyl monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02189498A JP3633773B2 (en) | 1998-02-03 | 1998-02-03 | Polymerization scale prevention method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02189498A JP3633773B2 (en) | 1998-02-03 | 1998-02-03 | Polymerization scale prevention method |
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| Publication Number | Publication Date |
|---|---|
| JPH11217403A JPH11217403A (en) | 1999-08-10 |
| JP3633773B2 true JP3633773B2 (en) | 2005-03-30 |
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| JP02189498A Expired - Fee Related JP3633773B2 (en) | 1998-02-03 | 1998-02-03 | Polymerization scale prevention method |
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| JPH11217403A (en) | 1999-08-10 |
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