JPS6187659A - Aqueous suspension containing organic peroxide - Google Patents
Aqueous suspension containing organic peroxideInfo
- Publication number
- JPS6187659A JPS6187659A JP20992084A JP20992084A JPS6187659A JP S6187659 A JPS6187659 A JP S6187659A JP 20992084 A JP20992084 A JP 20992084A JP 20992084 A JP20992084 A JP 20992084A JP S6187659 A JPS6187659 A JP S6187659A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous suspension
- peroxide
- organic peroxide
- stirring
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
・ 〔産業上の利用分野〕
本発明はポリスチレン、ポリメチルメタクリレートスチ
レンアクリロニトリル共重合物、 〔ＡＢＳ共重合物等
の懸濁重合の重合開始剤として使用される有機過酸化物
含有水性懸濁液に関する。[Detailed Description of the Invention] - [Industrial Application Field] The present invention relates to an organic peroxide used as a polymerization initiator for suspension polymerization of polystyrene, polymethyl methacrylate styrene acrylonitrile copolymer, [ABS copolymer, etc.] The present invention relates to aqueous suspensions containing substances.
スチレン系及びアクリル系モノマーの懸濁重合には一般
に重合開始剤としてベンゾイルパーオキサイド（以下Ｂ
ＰＯと略す）が使用されているが、ＢＰＯが粉状である
ため、他の液状の開始剤と異なりポンプ等を利用した自
動仕込みができず、これらのポリマーの製造作業の省力
化をはばむネックとなっている。Benzoyl peroxide (hereinafter referred to as B) is generally used as a polymerization initiator for suspension polymerization of styrenic and acrylic monomers.
However, since BPO is in powder form, unlike other liquid initiators, it cannot be automatically charged using a pump, etc., which is a bottleneck that hinders labor-saving manufacturing operations for these polymers. It becomes.
この点を改善し、ポンプによる自動仕込みを可能にする
ため、ＢＰＯの水性懸濁液の配合が試みられて（特開昭
５ｌ−１２５３０２）おり、ＢＰＯの分散安定剤として
メチルセルロース、ＨＬＢ＝１５とＨＬＢ＝１０の非イ
オン系乳化剤との組合せによりＢＰＯを５０％含むポン
プ輸送可能な水性懸濁液が得られたとしている。In order to improve this point and enable automatic preparation using a pump, attempts have been made to formulate an aqueous suspension of BPO (Japanese Unexamined Patent Publication No. 51-125302). In combination with a nonionic emulsifier with HLB=10, a pumpable aqueous suspension containing 50% BPO was obtained.
発明を解決しよ５とする問題点〕
しかし、この配合物は長期の分散安定性に欠け、長期に
わたって貯蔵した場合、底に泥状に沈積する。又、−担
沈積したＢＰＯは容易なことでは再分散しない。それよ
りも、このＢＰＯ懸濁液の根本的問題点は、このものの
目的であるポンプによる輸送安定性に欠けることであφ
。ポンプによる輸送を開始した当初はスムースに送液さ
れるが、その内、ポンプ内や配管の一部が詰まり、輸送
を不能にする。こうした理由により、ＢＰＯを中心にし
た粉状有機過酸化物は水性懸濁液は実用に至っていない
。Problems to be Solved by the Invention 5] However, this formulation lacks long-term dispersion stability, and when stored for a long period of time, it settles in the form of mud on the bottom. Moreover, -supported and deposited BPO is not easily redispersed. Rather, the fundamental problem with this BPO suspension is that it lacks stability in transport by pumps, which is the purpose of this suspension.
. Initially, the liquid is transferred smoothly, but eventually the inside of the pump or some of the piping becomes clogged, making transportation impossible. For these reasons, aqueous suspensions of powdered organic peroxides, mainly BPO, have not been put to practical use.
本発明者らは、ＢＰＯを主とした粉状重合開始剤の問題
にかんがみ、水を媒体とした、長期の分散安定性を有し
、ポンプによる仕込みにおいてもポンプや配管が詰まら
ない粉状重合開始剤の配合物の配合及び製造法を鋭意研
究の結果、本目的にかなう水媒体の懸濁液を見出すこと
に成功し、本発明を完成するに至った。即ち本発明はリ
ン酸三カルシウムを配合したことを特徴とする有機過酸
化物含有水性懸濁液である。The present inventors have considered the problem of powdered polymerization initiators, mainly BPO, and have developed powdered polymerization that uses water as a medium, has long-term dispersion stability, and does not clog pumps or piping even when pumped. As a result of extensive research into the formulation and manufacturing method of initiator formulations, the inventors succeeded in finding an aqueous suspension that satisfies this purpose, leading to the completion of the present invention. That is, the present invention is an organic peroxide-containing aqueous suspension characterized by containing tricalcium phosphate.
本発明は、例えば次のようにして容易に実施することが
できる。The present invention can be easily implemented, for example, as follows.
即ち、所定量の水に、分散剤としてのリン酸三カルシウ
ムを必要量投入、攪拌下に分散させ、さらに、必要に応
じて、分散安定化助剤を添加し、攪拌下に分散させ、そ
こに所定量の水湿粉体ＢＰＯを投入し、所定時間攪拌す
るだけで、目的とするＢＰＯの水性懸濁液が得られる。That is, a required amount of tricalcium phosphate as a dispersant is added to a predetermined amount of water, and dispersed with stirring.Additionally, if necessary, a dispersion stabilizing agent is added, dispersed with stirring, and then The desired aqueous suspension of BPO can be obtained by simply adding a predetermined amount of wet powder BPO into the container and stirring for a predetermined period of time.
本発明の水性懸濁液は長期にわたって常温貯蔵する場合
には、時々見かけ上水相とＢＰＯ固体固体層分離するこ
ともあるが、そのような場合でも、軽く振と５するか、
又はゆるやかな攪拌をほどこすだけで、均一分散化させ
ることが可能である。従来法により製造されたＢＰＯの
水性懸濁液は、そのＢＰＯ自体の大きい密度（１，３３
／２５℃）のために、長期貯蔵中に、層分離し、引き続
いて徐々に沈澱固化してしまい、再度、軽い振とうやゆ
るやかな攪拌を与えるだけでは分散均一化が難しかった
のが実情である。When the aqueous suspension of the present invention is stored at room temperature for a long period of time, it may sometimes appear that the aqueous phase and the BPO solid layer separate, but even in such cases, shake it gently or
Alternatively, it is possible to achieve uniform dispersion by simply applying gentle stirring. Aqueous suspensions of BPO produced by conventional methods have a high density of BPO itself (1,33
/25°C), during long-term storage, the layers separated and then gradually solidified, making it difficult to homogenize the dispersion by simply applying light shaking or gentle agitation. .
本発明になる水性懸濁液は、上述の如く、驚くべきこと
に５たとえ一部層分離現象を示しても、容易に均一分散
化させられるので、懸案であったポンプ輸送、即ちポン
プによる自動仕込方式の採用実現化を一歩前進させるこ
とができる。Surprisingly, as mentioned above, the aqueous suspension of the present invention can be easily uniformly dispersed even if it exhibits a partial layer separation phenomenon. It is possible to take a step forward in realizing the adoption of the preparation method.
本発明に使用する有機過酸化物として、粉粒体のＢＰＯ
を例示しているが、このＢＰＯに限らず、この他に、ラ
ウロイルパーオキサイド、０−メチルベンゾイルパーオ
キサイド、０−クロルベンゾイルパーオキサイド、ｐ−
クロルベンゾイルパーオキサイド、２．４−ジクロルベ
ンゾイルパーオキサイド、さらにはジーｔ−プチルパー
オキシヘキサハイドロテレフタンート、ジ−ｔ−ブチル
パーオキシテレフタレート等の常温（約２０℃）で固体
状ノものが使用され、本発明を広く適用する事に支障は
全くない。これらは純品でもよく、又は後者の使用が好
都合である。また、有機過酸化物は、１種単独使用に限
らず、２種以上の混合物であっても全くさしつかえはな
い。使用する有機過酸化物の総量は純品換算で５〜７０
重量％が好ましく、さらに好ましくは５５重量％以下で
ある。As the organic peroxide used in the present invention, powdery BPO
However, it is not limited to this BPO, and in addition, lauroyl peroxide, 0-methylbenzoyl peroxide, 0-chlorobenzoyl peroxide, p-
Those that are solid at room temperature (approximately 20°C) such as chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butylperoxyhexahydroterephthanate, and di-t-butylperoxyterephthalate. is used, and there is no problem in widely applying the present invention. These may be pure or the latter may be advantageously used. Moreover, the organic peroxides are not limited to the use of one type alone, and there is no problem even if a mixture of two or more types is used. The total amount of organic peroxide used is 5 to 70% in terms of pure product.
It is preferably 55% by weight or less, more preferably 55% by weight or less.
本発明に使用するリン酸三カルシウムの添加量は本水性
懸濁液の０．５〜２０％が好ましく、さらに好ましくは
１〜１０％である。The amount of tricalcium phosphate used in the present invention is preferably 0.5 to 20%, more preferably 1 to 10% of the aqueous suspension.
又、必要に応じて分散安定性効果を高めるために、分散
安定化助剤として、ポリビニルアルコール、ポリエチレ
ンオキシド等の合成高分子、メチルセルロース、カルボ
キシメチルセルロース等のセルロース誘導体、膠、ゼラ
チン等の動物性たんばく質、アラビアゴム、キサンタン
ガム等の植物性物質、アルギン酵等の海藻由来物、その
他デン粉類、茄エデン粉類力を使用され、さらには、炭
酸カルシウム、硫酸バリウム等の固体微粒子の添加も効
果を示す。また、ドデシルベンゼンスルホン酸ナトリウ
ム、オレイン酸ナトリウム等のアニオン系界面活性剤、
カオキン系、ノニオン系の界面活性剤が使用される。こ
れらは、上述の分散剤と、１種又はそれ以上との任意の
組み合わせによっても使用することができる。In addition, in order to enhance the dispersion stability effect as necessary, synthetic polymers such as polyvinyl alcohol and polyethylene oxide, cellulose derivatives such as methyl cellulose and carboxymethyl cellulose, animal protein such as glue and gelatin may be used as dispersion stabilizing aids. Bacterium, vegetable substances such as gum arabic and xanthan gum, seaweed-derived substances such as alginic ferment, other starches, and eggplant powder are used, and solid fine particles such as calcium carbonate and barium sulfate are also added. Show effectiveness. In addition, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium oleate,
Kaoquin and nonionic surfactants are used. These can also be used in any combination of one or more of the above-mentioned dispersants.
また使用する水としては、上水でも良いが通常イオン交
換水または蒸留水が望ましく、その水量は３０〜９５重
量％が好ましい。The water used may be tap water, but ion-exchanged water or distilled water is usually preferable, and the amount of water is preferably 30 to 95% by weight.
水性懸濁液の不凍化を目的として、水溶性有機物質を水
に溶解させることも可能である。It is also possible to dissolve water-soluble organic substances in water for the purpose of antifreezing aqueous suspensions.
ここで水溶性有機物質とは、メチルアルコール、エチル
アルコール、イソプロピルアルコール、エチレングリコ
ール等の１価又は２価の低級アルコールである。もちろ
ん常に水に水溶性有機物質を溶解する必要はない。Here, the water-soluble organic substance is a monovalent or divalent lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and ethylene glycol. Of course, it is not always necessary to dissolve water-soluble organic substances in water.
以下、実施例、比較例によって、本発明の水性）い濁化
をさらに説明する。Hereinafter, the aqueous turbidity of the present invention will be further explained with reference to Examples and Comparative Examples.
実施例１゜
通常のホモミキサーと温度計を備えた５００ｙｎｌのト
ールビーカーにイオン交換水１０７．５ｇ−（４３重量
％）を入れ、続いて、リン酸三カルシウム７、５ Ｐ
（３重量％）を投入、攪拌下に、予め秤量しておいたＢ
ＰＯの７５％水湿物、１３５．０ｇ−（５４重量％）を
徐々に投入、２０’Ｃ以下に保ちつつ２０分間攪拌を続
けて、白色の水性懸濁液を得た。このものの粘度は２５
０ ｃｐｓ／２０℃であった。また約２０日間の分散安
定性を示した。２０日後において、怪い振とうを与える
と再び安定な懸濁液を得た。Example 1 Into a 500ynl tall beaker equipped with a conventional homomixer and a thermometer, 107.5 g of ion-exchanged water (43% by weight) was added, followed by 7,5 P of tricalcium phosphate.
(3% by weight) was added, and while stirring, the pre-weighed B
135.0 g (54% by weight) of 75% water wet PO was gradually added, and stirring was continued for 20 minutes while keeping the temperature below 20'C to obtain a white aqueous suspension. The viscosity of this product is 25
It was 0 cps/20°C. It also showed dispersion stability for about 20 days. After 20 days, a stable suspension was again obtained with gentle shaking.
実施例２゜
実施例１に於て、リン酸三カルシウムが１０重ｔ％の場
合について水性懸濁化を試みた。このものの粘度は３０
０ｃｐｓ、３０日間の分散安定性を示した。３０日後に
おいて、軽い振と５を与えると再び安定な懸濁液を得た
。Example 2 In Example 1, aqueous suspension was attempted in the case where tricalcium phosphate was 10% by weight. The viscosity of this product is 30
It showed dispersion stability of 0 cps for 30 days. After 30 days, a stable suspension was again obtained with gentle shaking and 5°C.
実施例３゜
実施例１に於て、さらに分散安定化助剤としてドテシル
ベンゼンスルホン酸ソーダを０．４重ｔ％添加して水性
懸濁化を試みた。粘度は２７０ ｃｐｓ、４０日間の分
散安定性を示した。４０日後において、＠い振と５によ
り再び安定な１゛ヌ濁液を得た。Example 3 In Example 1, aqueous suspension was attempted by adding 0.4% by weight of sodium dotecylbenzenesulfonate as a dispersion stabilizing aid. The viscosity was 270 cps, and the dispersion was stable for 40 days. After 40 days, a stable 100ml suspension was again obtained by shaking the mixture.
実施例４゜
実施例１に於て、さらに分散安定化助剤としてポリビニ
ルアルコールを添加して水性懸濁液を得実施例５゜
実姉例４に於て、不凍化剤としてメタノールを用いて水
性懸濁化を試みて水性懸濁液を得た。Example 4゜In Example 1, polyvinyl alcohol was further added as a dispersion stabilizing agent to obtain an aqueous suspension.Example 5゜Sister Example 4, methanol was used as an antifreeze agent. Aqueous suspension was attempted and an aqueous suspension was obtained.
実施例６゜
実！（！１１１３に於て、有機過酸化物として、ラウロ
イルパーオキサイド（ＬＰＯ）を用いて水性懸濁化を試
みて水性懸濁液を得た。Example 6゜Actual! (!1113, an aqueous suspension was obtained using lauroyl peroxide (LPO) as an organic peroxide.
９ｖ施１り１１７゜
実施りＩＩ ３に於て、有機過酸化物として、ジーを一
ブチルパーオキシヘキサハイドロチレフタレ−） （Ｈ
ＴＰ）を用いて水性）け濁化を試みて水性懸濁液を得た
。In 9v application 1 and 117° implementation II 3, di was used as the organic peroxide, monobutylperoxyhexahydrothylephthalate) (H
An aqueous suspension was obtained by attempting turbidity using TP).
比較例１゜
実ｍ１ｆｌｌｌにおいて、分散剤としてのリン酸三カル
シウム無添加の系において、水性）ぬ濁化を試みて水性
懸濁液を得た。Comparative Example 1 In a practical example of 1 flllll, an aqueous suspension was obtained in a system without the addition of tricalcium phosphate as a dispersant.
比較例２゜
実施列１において、分散剤としてリン酸三カルシウムの
代りにオレイン酸ソーダを使用して水性ｉ′Ｗ濁化を試
みて水性懸濁液を得た。Comparative Example 2 In Example 1, an aqueous suspension was obtained by using sodium oleate instead of tricalcium phosphate as a dispersant to try to make the aqueous i'W turbid.
比較例３゜
特開昭５１−１２５３０２の実施例１の組成およびその
ときの水性！°ヌ濁液の特性を引用した。Comparative Example 3 Composition and aqueous composition of Example 1 of JP-A-51-125302! ° The characteristics of the suspension are cited.
実姉例１〜７および比較例１〜３につきまとめて表１に
示した。Actual examples 1 to 7 and comparative examples 1 to 3 are summarized in Table 1.
応用例１゜
上述の実施例および比較例で示した。水性懸濁液のポン
プ輸送の可能性を、ダイヤフラム式ポンプ（イッキＨＤ
Ｐ型）を用いて、常温（２０へ３０℃）で、水性懸濁液
の連続循環運転を行った。Application Example 1゜ As shown in the above-mentioned Examples and Comparative Examples. The diaphragm pump (Ikki HD) offers the possibility of pumping aqueous suspensions.
A continuous circulation operation of the aqueous suspension was carried out at room temperature (20 to 30° C.) using the P type.
所定時間運転後、ポンプを分解して、ボールパルプ近辺
に固型物の付着残留があるかどうかを観察することより
評価を行った。結果を表２にまとめた。After operating for a predetermined period of time, the pump was disassembled and evaluated by observing whether there was any solid matter remaining in the vicinity of the ball pulp. The results are summarized in Table 2.
本発明により、今まで不可能であった粉状有機過酸化物
をポンプ等を用いて送ることが可能となり、スチレン系
、アクリル系等のモノマーの懸濁重合において、ＢＰＯ
等の粉状有機過酸化物をマンホールを経て投入しなけれ
ばならないため、不可能であった、これらの重合プラン
トのクロズド化への道を拓くことができる。The present invention has made it possible to transport powdered organic peroxides using a pump, which has not been possible until now.
This opens the door to closed polymerization plants, which was not possible because powdered organic peroxides such as powders had to be injected through manholes.
Claims (1)
酸化物含有水性懸濁液Organic peroxide-containing aqueous suspension characterized by containing tricalcium phosphate
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20992084A JPS6187659A (en) | 1984-10-08 | 1984-10-08 | Aqueous suspension containing organic peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20992084A JPS6187659A (en) | 1984-10-08 | 1984-10-08 | Aqueous suspension containing organic peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6187659A true JPS6187659A (en) | 1986-05-06 |
Family
ID=16580851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20992084A Pending JPS6187659A (en) | 1984-10-08 | 1984-10-08 | Aqueous suspension containing organic peroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6187659A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02200666A (en) * | 1989-01-30 | 1990-08-08 | Sanken Kako Kk | Aqueous suspension of solid organic peroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125302A (en) * | 1975-03-14 | 1976-11-01 | Akzo Nv | Manufacture of aqueous suspension containing organic peroxide |
| JPS5922902A (en) * | 1982-07-29 | 1984-02-06 | Daicel Chem Ind Ltd | Suspension polymerization process |
| JPS59120606A (en) * | 1982-12-27 | 1984-07-12 | ゼロツクス・コ−ポレ−シヨン | Formation of styrene and butadiene copolymer |
-
1984
- 1984-10-08 JP JP20992084A patent/JPS6187659A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125302A (en) * | 1975-03-14 | 1976-11-01 | Akzo Nv | Manufacture of aqueous suspension containing organic peroxide |
| JPS5922902A (en) * | 1982-07-29 | 1984-02-06 | Daicel Chem Ind Ltd | Suspension polymerization process |
| JPS59120606A (en) * | 1982-12-27 | 1984-07-12 | ゼロツクス・コ−ポレ−シヨン | Formation of styrene and butadiene copolymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02200666A (en) * | 1989-01-30 | 1990-08-08 | Sanken Kako Kk | Aqueous suspension of solid organic peroxide |
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