JPS61241310A - Production of emulsion of crosslinked polymer - Google Patents
Production of emulsion of crosslinked polymerInfo
- Publication number
- JPS61241310A JPS61241310A JP8337885A JP8337885A JPS61241310A JP S61241310 A JPS61241310 A JP S61241310A JP 8337885 A JP8337885 A JP 8337885A JP 8337885 A JP8337885 A JP 8337885A JP S61241310 A JPS61241310 A JP S61241310A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- emulsion
- methyl methacrylate
- parts
- monomer
- 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
Abstract
Description
【発明の詳細な説明】
本発明はメチルメタクリレート系の架橋電合体粒子を含
有する水性エマルジョンの製造法に関するものであって
、さらに詳しくは、界面活性剤を全く使用しない所鯖ソ
ープフリー乳化重合法にて、メチルメタクリレートモノ
マー又はメチルメタクリレートを含有するビニルモノマ
ーと、架橋性モノマーとを共重合させることにより、架
橋１合体粒子の安定なエマルジョンを製造する方法に係
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an aqueous emulsion containing methyl methacrylate-based crosslinked electropolymer particles, and more specifically to a soap-free emulsion polymerization method that does not use any surfactant. The present invention relates to a method for producing a stable emulsion of crosslinked aggregate particles by copolymerizing a methyl methacrylate monomer or a vinyl monomer containing methyl methacrylate with a crosslinkable monomer.
メチルメタクリレートをソープフリー乳化重合法にて、
他のビニルモノマーと共重合させることは、他のモノマ
ーが架橋性でない限り比較的容易であって、事実、従来
技術にもその実例を多数見ることができる。ところが、
メチルメタクリレートに反応させしめるモノマーが架橋
性七ツマ−である場合、ソープフリー乳化重合法では七
ツマ−並びに生長過程にあるポリマーの分散が不光分で
あることに起因して架橋重合体が凝塊となりやすく、こ
の傾向は架橋性モノマーの使用量の増加に伴って一層増
長されるので、ソープフリー乳化重合法では架橋電合体
粒子の安定なエマルジョンを製造できないのが通例であ
る。Methyl methacrylate is produced using soap-free emulsion polymerization method.
Copolymerization with other vinyl monomers is relatively easy unless the other monomers are crosslinkable, and in fact, many examples can be found in the prior art. However,
When the monomer reacted with methyl methacrylate is a crosslinkable heptamer, in the soap-free emulsion polymerization method, the crosslinked polymer coagulates due to the non-luminous dispersion of the heptad and the polymer in the growth process. This tendency is further exacerbated as the amount of crosslinking monomer used increases, so it is generally not possible to produce a stable emulsion of crosslinked electropolymer particles using the soap-free emulsion polymerization method.
従って、メチルメタクリレートと架橋性七ツマ−を乳化
重合させる場合には、七ツマ−並びに生成ポリマーの分
散を良好ならしめる目的で反応系に界面活性剤を添加し
、状況によってはさらに分散安定剤として水浴性高分子
を添加して重合を行わせる方法が一般に慣用されており
。Therefore, when emulsion polymerizing methyl methacrylate and a crosslinkable heptamer, a surfactant is added to the reaction system in order to improve the dispersion of the heptamer and the resulting polymer, and depending on the situation, a surfactant may be added as a dispersion stabilizer. A commonly used method is to perform polymerization by adding a water bath polymer.
この方法によれば、一応満足できる均質性と安定性を備
えた架橋１合体のエマルジョ／を得ることができる。し
かしながら、エマルジョンに界面活性剤が含まれている
ことは１次の点で好ましくない。According to this method, it is possible to obtain a cross-linked monomer emulsion with satisfactory homogeneity and stability. However, the inclusion of a surfactant in the emulsion is undesirable for the following reasons.
すなわち、架橋重合体のエマルジョンは、これを例えば
噴霧乾燥などの手段で乾燥し、さらにジェット粉砕など
の適宜な手段で一次粒子に解砕して、顔料、フィラーな
どに用いられるが。That is, an emulsion of a crosslinked polymer is dried by means such as spray drying, and further crushed into primary particles by an appropriate means such as jet pulverization, and used for pigments, fillers, etc.
エマルジョンに界面活性剤が含まれていると。If the emulsion contains a surfactant.
−次粒子への解砕が困難になるばかりでなく、たとえ解
砕できても粒子に界面活性剤が付着しているため、粒子
の使゛途によっては、界面活性剤の影＊ｔ−ｍ念しなけ
ればならないのである。- Not only is it difficult to disintegrate into secondary particles, but even if the particles are disintegrated, surfactant is still attached to the particles, so depending on the purpose of the particles, the shadow of the surfactant*t-m We must keep this in mind.
而して本発明は界面活性剤を全く便用しないソープフリ
ー乳化重合法で、架ａｉＭ合体粒子の安定なエマルジョ
ンｔ−製造する方法を提供するものであり、その方法は
メチルメタクリレート単独又はメチルメタクリレ−）ｔ
−を有するビニルモノマーを界面活性剤の不存在下に乳
化重合せしめ、そのム合率が１〜４０％の範囲に到達し
た時点で、少なくとも２個のビニル基を有する架橋性モ
ノマーを連続的又は間欠的に反応系に添加して重合を続
行させ、前記の１合率が５５〜９０チの範囲に到達した
時点で、架橋性モノマーの添加を終了し、しかる後１合
反応を完結させることを％−徴とする。Therefore, the present invention provides a method for producing a stable emulsion of aggregated aiM particles using a soap-free emulsion polymerization method that does not use any surfactant. Ray)t
A vinyl monomer having - is emulsion polymerized in the absence of a surfactant, and when the emulsion ratio reaches a range of 1 to 40%, a crosslinking monomer having at least two vinyl groups is continuously or Add it intermittently to the reaction system to continue the polymerization, and when the 1% ratio reaches the range of 55 to 90%, stop adding the crosslinking monomer, and then complete the 1% reaction. Let be the %-sign.
本発明の方法によれば、乳化重合は界面活性剤及び架橋
性七ツマ−が一切存在しない条件下で、メチルメタクリ
レート又はメチルメタクリレートｔ−含有ｊるビニルモ
ノマーによって開始され、ｉ金触媒（開始剤）としては
、通常の乳化重合の場合と同様、有機過酸化物、アゾ化
合物、過硫酸塩などが使用される。反応開始時に使用さ
れる七ツマ−はメチルメタクリレート単独であっても差
支えないが、呆４ｉ１１能を持たない限り他のビニルモ
ノマーも併用可能であって。According to the method of the present invention, emulsion polymerization is initiated by methyl methacrylate or a vinyl monomer containing methyl methacrylate in the absence of any surfactants and crosslinking monomers, and the emulsion polymerization is initiated by a gold catalyst (initiator). ), organic peroxides, azo compounds, persulfates, etc. are used as in the case of ordinary emulsion polymerization. Methyl methacrylate alone may be used as the monomer used at the start of the reaction, but other vinyl monomers can also be used in combination as long as they do not have the 4i11 ability.
ソウシたビニルモノマーにはスチレン、酢ｉ［ビニル、
アクリル酸、メタクリル酸、アクリル酸アルキル、メタ
クリル激アルキル、アクリル酸アミド、メタクリル敵ア
ミド、アクリロニトリル、Ｎ−メチロールアクリルアミ
ドなどが包含される。これらビニルモノマーを併用する
場合。Styrene, vinegar i [vinyl,
Acrylic acid, methacrylic acid, alkyl acrylate, radical alkyl methacrylate, acrylamide, methacrylamide, acrylonitrile, N-methylolacrylamide, and the like are included. When using these vinyl monomers together.
その使用量は任意に選ぶことができるが、一般にはメチ
ルメタクリレート量の５０％以下程度とするのが通例で
ある。本発明は界面活性剤を全く含まない条件下で乳化
重合を実施することｆ、要件とするか１分散安定剤とし
て機能する水溶性高分子の使用までをも排除するもので
はなく、冥用上（工むしろ水浴性高分子を使用する方が
好ましい。この場合、水浴性高分子の使用量は１本発明
で使用するモノマー金貸の１重量−以下程度とすること
を可とし、水溶性高分子としてはぼりビニルアルコール
、ポリアクリル酸アルカリ金属塩、ポリメタクリル酸ア
ルカリ金属、高重合度ポリエチレングリコール、ヒドロ
キシエチルセルロース、カルゼキシメチルセルロース、
メチルセルロース、ポリスチレンスルホン酸アルカリ金
属塩などが使用可能である。The amount used can be arbitrarily selected, but it is generally about 50% or less of the amount of methyl methacrylate. The present invention requires that emulsion polymerization be carried out under conditions that do not contain any surfactant, and does not exclude the use of a water-soluble polymer that functions as a dispersion stabilizer; (It is preferable to use a water-based polymer rather than a water-based polymer. In this case, the amount of the water-based polymer used can be approximately 1 weight or less of the monomer used in the present invention. Molecules include vinyl alcohol, alkali metal polyacrylate, alkali metal polymethacrylate, highly polymerized polyethylene glycol, hydroxyethyl cellulose, calxoxymethyl cellulose,
Methyl cellulose, polystyrene sulfonic acid alkali metal salts, etc. can be used.
反応系への架橋性モノマーの添加は、上記したメチルメ
タクリレート単独又はメチルメタクリレート含有ビニル
モノマーの１合率が１〜４０チの範囲に到達した時点で
開始され、５５〜９０チの範囲に到達した時点で梃子さ
れる。つまり、架橋性七ツマ−は東金反応が進行しつつ
ある反応系に、連続的又は間欠的に添加され、−挙に添
加されることはない。本発明で使用される架橋性モノマ
ーは、ジビニルベンゼン、ジビニルトルエン、エチレン
グリコールジメタ−／ ！Ｊ Ｖ −ト、トリメタクリ
ル酸トリメチロールプロパン、アリルメタクリレートな
どで例示される如べ。Addition of the crosslinking monomer to the reaction system was started when the proportion of methyl methacrylate alone or the vinyl monomer containing methyl methacrylate reached a range of 1 to 40 inches, and reached a range of 55 to 90 inches. leveraged at the point. In other words, the crosslinking 7mer is added continuously or intermittently to the reaction system in which the Togane reaction is progressing, but is not added all at once. The crosslinking monomers used in the present invention include divinylbenzene, divinyltoluene, ethylene glycol dimeta-/! Examples include JV-t, trimethylolpropane trimethacrylate, and allyl methacrylate.
１分子中に少なくとも２個のビニル基を有する％／ママ
−あって、典を的にはジビニルベンゼン及びエチレング
リコールジメタクリレートが使用される。架橋性モノマ
ーの使用量は本発明で使用する非架橋性七ツマー全量（
重量）と同量以下の範四で任意に選ぶことができる。上
記した通り１本発明の方法では架橋性七ツマ−が連続的
又は間欠的に反応系に添加されるが、この場合、架橋性
モノマーを非架橋性七ツマ−又は酢酸エチル、トルエン
などの有機溶剤で稀釈しておくことができ、こうするこ
とは、添加する架橋性モノマーが少量である場合とか、
固体である場合に有効である。架橋性モノマーの添加終
了後は、系内の未反志モノマーが消費されるまで反応を
継続してこれを完結させることにより１本発明の目的生
成物たる架橋重合体粒子のエマルジョンを得ることがで
きる。With at least two vinyl groups per molecule, divinylbenzene and ethylene glycol dimethacrylate are typically used. The amount of crosslinking monomer used is the total amount of non-crosslinking monomer used in the present invention (
(weight) can be arbitrarily selected within the range of the same amount or less. As mentioned above, in the method of the present invention, a crosslinking monomer is added continuously or intermittently to the reaction system. It can be diluted with a solvent, and this is useful when a small amount of crosslinking monomer is added,
Effective when solid. After the addition of the crosslinking monomer is completed, the reaction is continued until the unreacted monomer in the system is consumed, and by completing the reaction, an emulsion of crosslinked polymer particles, which is the target product of the present invention, can be obtained. can.
以上の通り、本発明の方法は界面活性剤を全く使用しな
い所謂ソープフリー乳化１合法に、架橋性七ツマ−を関
与させるが、関与の時期はメタクリレートモノマー又ヲ
エメチルメタクリレート含有ビニルモノマーの重合が成
る程度進行し、その重合率が１〜４０％に到達する以後
、５５〜９０％に到達する以前であり、しかも架橋性モ
ノマーは一挙に添加されることがないので、本発明によ
れば架ＩＩＩＬ合体粒子の安定なエマルジョンを製造す
ることができる。そして本発明で得られるエマルジョン
は、これを乾燥後−次粒子に解砕すれば、得られる微粉
末は界面活性剤の影響を全く心配することなく、顔料、
フィラーなどに利用することができる。As described above, the method of the present invention involves the use of a crosslinking 7-mer in the so-called soap-free emulsification method that does not use any surfactant. According to the present invention, the crosslinking monomer is not added all at once, after the polymerization rate reaches 1 to 40% and before it reaches 55 to 90%. Stable emulsions of IIIL coalescing particles can be produced. If the emulsion obtained in the present invention is dried and then crushed into secondary particles, the fine powder obtained can contain pigments, without worrying about the influence of surfactants.
It can be used as filler, etc.
次に実施例を比較例と共に示して本発明の効果を具体的
に説明するが、実謁例及び比較例に示す「部」はすべて
「重量部」を意味する。EXAMPLES Next, the effects of the present invention will be specifically explained by showing examples together with comparative examples. All "parts" shown in the practical examples and comparative examples mean "parts by weight."
実施例１
還流冷却器、温度計、窒素吹き込み管、滴下ロート及び
すり合わせ方式のかきまぜ装置を付したｌｌの５０フラ
スコに、蒸留水４００部、ポリエチレングリコールα５
部、チオ硫酸ナトリウム０．５部、メタクリレート２０
０部を入れ、窒素気流下、一定のかきまぜ速度（４０Ｏ
ｒｐｍ）に保ちながら５０℃に昇温する。続いて５０℃
になった時点で過硫酸カリウム１部を加え１合を開始さ
せる。重合を開始させてから１時間経過後、重合率が１
０％になったところでスチレン３０部、エチレングリコ
ールジメタ／ ！ｊ Ｌ／ −ドア０部、酢酸エチル５
０ｇの混合物を滴下し始め１重合率が７０チになった時
点で滴下を終える様にする。滴下終了後、５０部３℃で
３時間反応を継続して反応を完結させる。Example 1 400 parts of distilled water and polyethylene glycol α5 were placed in a 50 liter flask equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device.
parts, sodium thiosulfate 0.5 parts, methacrylate 20 parts
0 parts and stirred at a constant stirring speed (40O
RPM) and raise the temperature to 50°C. followed by 50℃
When the temperature is reached, add 1 part of potassium persulfate and start 1 cup. One hour after starting polymerization, the polymerization rate was 1.
When it reaches 0%, 30 parts of styrene, ethylene glycol dimeta/! j L/-door 0 parts, ethyl acetate 5
Start dropping 0g of the mixture and stop dropping when the polymerization rate reaches 70g. After completion of the dropwise addition, the reaction was continued for 3 hours at 3°C in 50 parts to complete the reaction.
こうして得られたエマルジョンは安定で凝集生成物はほ
とんどなく、分散粒子の平均粒径は０．４５μであった
。The emulsion thus obtained was stable and contained almost no agglomerated products, and the average particle size of the dispersed particles was 0.45μ.
実施例２
還流冷却器、温度計、窒素吹き込み管、滴下ロート及び
すり合わせ方式のかきまぜ装置を付した１ノの５０フラ
スコに、蒸留水４００部、ポリメタクリル酸ソーダ０．
５部、チオ硫酸ナトリウム０．５７ｆｌｌ、メチルメタ
クリレート２００部を入れ、窒素気流下、一定のかきま
ぜ速度（４００ｒｐｍ）Ｋ保ちながら５０℃に昇温する
。Example 2 400 parts of distilled water and 0.0 parts of polysodium methacrylate were placed in a 1-50 flask equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device.
5 parts of sodium thiosulfate, 0.57 flll of sodium thiosulfate, and 200 parts of methyl methacrylate were added, and the temperature was raised to 50°C under a nitrogen stream while maintaining a constant stirring speed (400 rpm).
続いて５０℃になった時点で過硫酸カリウム１部を加え
重合を開始させる。重合を開始させてから３０分経過後
の重合率５チになったところで、メチルメタクリレ−）
２０部とジビニルベンゼン８０部の混合物を崗下し始め
１重合率が６０％になった時点″：ｒ：滴下を終える様
にする。Subsequently, when the temperature reached 50°C, 1 part of potassium persulfate was added to initiate polymerization. When the polymerization rate reached 5% after 30 minutes had passed from the start of polymerization, methyl methacrylate)
A mixture of 20 parts of divinylbenzene and 80 parts of divinylbenzene was started to be added down, and the dropwise addition was stopped when the 1 polymerization rate reached 60%.
滴下を終えてから５０部３℃で３時間反応を継続して反
応を完結させる。こうして得られたエマルジョンは非常
に安定で、凝集生成物や攪拌バネへの付着もほとんど認
められず１分散粒子の平均粒経は０．５５μであった。After the addition was completed, the reaction was continued for 3 hours at 3°C in 50 parts to complete the reaction. The emulsion thus obtained was very stable, with hardly any agglomerated products or adhesion to the stirring spring, and the average particle diameter of one dispersed particle was 0.55 μm.
実施例３
還流冷却器、温度計、窒素吹き込み１＃、滴下ロート及
びすり合わせ方式のかきまぜ装置を付した１１の５０フ
ラスコに、蒸留水４００部。Example 3 400 parts of distilled water was placed in an 11-50 flask equipped with a reflux condenser, a thermometer, a 1# nitrogen blower, a dropping funnel, and a grinding type stirring device.
ポリエチレングリコール１部、亜硫酸水素ナトリウム１
部、メチルメタクリレート１００部、スチレン５０ｓを
入れ、ｍｋ気流下、一定のかきまぜ速度（４０Ｏｒｐｍ
）に保ちながら５５℃に昇温する。続いて５５℃になっ
た時点で過硫酸カリウム２部を加え１合を開始させる。1 part polyethylene glycol, 1 part sodium bisulfite
100 parts of methyl methacrylate and 50 seconds of styrene were added, and stirred at a constant stirring speed (40 rpm) under mk air flow.
) and raise the temperature to 55°C. Subsequently, when the temperature reached 55°C, 2 parts of potassium persulfate was added to start 1 cup.
重合を開始させてから１時間後の重合率１２％になった
ところで、ジビニルベンゼン１５０１ｔｉとトルエン５
０部の混合物を滴下し始め、重合率が８０チになった時
点で滴下を終える様にする。One hour after starting the polymerization, when the polymerization rate reached 12%, divinylbenzene 1501ti and toluene 5
Start dropping 0 parts of the mixture and stop dropping when the polymerization rate reaches 80 parts.
滴下を終えてから５５±３℃で３時間反応を継続し、反
応を完結させる。こうして得たエマルジョンは安定であ
り、凝集生成物がほとんどなく、分散粒子の平均粒径は
０．６５μであった。After finishing the dropwise addition, the reaction was continued for 3 hours at 55±3°C to complete the reaction. The emulsion thus obtained was stable, with almost no agglomeration products, and the average particle size of the dispersed particles was 0.65μ.
実施例４
還流冷却器、温度計、窒素吹き込み管１滴下ロート及び
すり合わせ方式のかきまぜ装置を付したＩＪの５０フラ
スコに、蒸留水４００部。Example 4 400 parts of distilled water was placed in an IJ 50 flask equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device.
ポリエチレングリコール１部、亜硫酸水素ナトリウム１
部、メチルメタクリレート１５０ｉ１Ｓ。1 part polyethylene glycol, 1 part sodium bisulfite
part, methyl methacrylate 150i1S.
メチルアクリレート５０ｓ、アクリロニトリル５０部を
入れ、窒素気流下、一定のかきまぜ速度（３０Ｏｒｐｍ
）に保ちながら５５℃に昇温する。Add 50s of methyl acrylate and 50 parts of acrylonitrile, and stir at a constant stirring speed (30 rpm) under a nitrogen stream.
) and raise the temperature to 55°C.
続いて５５℃になった時点で過硫酸カリウム２部を加え
て重合を開始させる。重合を開始させてから４５分後の
重合率２８％になった時点でジビニルベンゼン５０部の
部下を開始し、重合率が８５％になった時点で滴下を糾
える様にする。架橋性モノマーの滴下を終えてから５５
±３℃で３時間反応を継続し反応を完結させる。Subsequently, when the temperature reached 55°C, 2 parts of potassium persulfate was added to initiate polymerization. When the polymerization rate reaches 28%, 45 minutes after starting the polymerization, 50 parts of divinylbenzene is added, and the dropwise addition is stopped when the polymerization rate reaches 85%. 55 minutes after finishing dropping the crosslinking monomer
Continue the reaction at ±3°C for 3 hours to complete the reaction.
こうして得たエマルジョンは安定であり凝集物がほとん
どなく、分散粒子の平均粒径は０．３５μであった。The emulsion thus obtained was stable and had almost no aggregates, and the average particle size of the dispersed particles was 0.35μ.
比較例１
実施例１において滴下用架橋性モノマー混合物を重合初
期からフラスコ内に入れて一括仕込の重合方法で行なっ
たところ、触媒を添加してから８０分後に粘度が著しく
上昇しフラスコ内容物が流動しない状態になった。Comparative Example 1 In Example 1, the cross-linking monomer mixture for dropping was put into the flask from the initial stage of polymerization and the polymerization was carried out by charging all at once. However, 80 minutes after the addition of the catalyst, the viscosity increased significantly and the contents of the flask It became immobile.
比較例２
実施例２において添加用架橋性モノマー混合物を重合初
期からフラスコ内に入れて一括仕込の重合方法で行なっ
たところ、触媒を加えて９０分後に粘度が著しく上昇し
フラスコ内容物が流動しない状態になり重合の継続は不
可能であった。Comparative Example 2 In Example 2, the crosslinking monomer mixture for addition was put into the flask from the initial stage of polymerization and the polymerization was carried out using a batch charging method. However, 90 minutes after adding the catalyst, the viscosity increased significantly and the contents of the flask did not flow. It became impossible to continue the polymerization.
比較例３
実施例４において重合率３５％でジビニルベンゼンを一
度に加えて重合を６時間継続したところ、フラスコ内の
エマルジョンは凝集生成物が多り、シかもフラスコ、攪
拌バネへのスケール付着も著しく多かった。この凝集生
成物とスケール付着物を削って２００メツシユの金網で
ｆ過し、乾燥した後、その重量を測定したところ仕込モ
ノマーの４５％が凝集生成及びスケール付着物になって
いることが分った。Comparative Example 3 In Example 4, when divinylbenzene was added at once at a polymerization rate of 35% and polymerization was continued for 6 hours, the emulsion in the flask contained a lot of agglomerated products, and there was also scale adhesion to the flask and stirring spring. There were significantly more. The agglomerated products and scale deposits were scraped off, passed through a 200-mesh wire mesh, dried, and then weighed, and it was found that 45% of the monomer charged was agglomerated products and scale deposits. Ta.
比較例４
還流冷却器、温度計、窒素吹き込み管、滴下ロート及び
すり合わせ方式のかきまぜ装置を付したｌｌの５０フラ
スコＫ、蒸留水４００５゜ポリエチレングリコール１部
、亜硫酸水系ナトリクム１１１．メチルメタクリレート
２８５部、ジビニルベンゼン１５部を入れ、窒素気流下
、一定のかきまぜ速度（４００ｒｐｍ）Ｋ保ちながら５
５℃に昇温する。続いて５５℃になった時点で過硫酸カ
リウム２部を加えて重合を開始させる。５５±３℃で８
時間保ち反応を完結させる。Comparative Example 4 A 50-liter flask K equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device, 4005° distilled water, 1 part polyethylene glycol, 111% aqueous sodium sulfite. Add 285 parts of methyl methacrylate and 15 parts of divinylbenzene, and stir under a nitrogen stream while maintaining a constant stirring speed (400 rpm).
Raise the temperature to 5°C. Subsequently, when the temperature reached 55°C, 2 parts of potassium persulfate was added to initiate polymerization. 8 at 55±3℃
Keep time to complete reaction.
こうして得られたエマルジョンは凝集生成物が非常に多
（、凝集生成物とスケール付着物をげずって、２００メ
ツシユの金網でｆ過し、乾燥した後、その重量を測定し
たところ、仕込モノマーの４８俤が凝集生成物及びスケ
ール付着物になっている事が分った。The emulsion thus obtained contained a very large amount of agglomerated products (the agglomerated products and scale deposits were removed, the emulsion was passed through a 200-mesh wire mesh, dried, and its weight was measured. It was found that 48 tons were agglomerated products and scale deposits.
比較例５
実施例４においてジビニルベンゼンのＭ下開始を重合率
７０％のところで行なったところジビニルベンゼンの滴
下中に反応系内の増粘が起こり、フラスコ内の攪拌が出
来ない状態になった。Comparative Example 5 In Example 4, when divinylbenzene was started under M at a polymerization rate of 70%, the reaction system increased in viscosity during the dropwise addition of divinylbenzene, and stirring in the flask became impossible.
Claims (1)
トを含有するビニルモノマーを界面活性剤の不存在下に
乳化重合させ、その重合率が１〜４０％の範囲に到達し
た時点で、少なくとも２個のビニル基を有する架橋性モ
ノマーを連続的又は間欠的に添加して反応を続行し、前
記の重合率が５５〜９０％の範囲に到達した時点で、架
橋性モノマーの添加を終了し、しかる後反応を完結させ
ることを特徴とする架橋重合体エマルジョンの製造法。 ２、前記の乳化重合を水溶性高分子の存在下で行う特許
請求の範囲第１項記載の方法。 ３、前記の架橋性モノマーがエチレングリコールジメタ
クリレート又はジビニルベンゼンである特許請求の範囲
第１項記載の方法。[Claims] 1. Emulsion polymerization of methyl methacrylate alone or a vinyl monomer containing methyl methacrylate in the absence of a surfactant, and when the polymerization rate reaches a range of 1 to 40%, at least 2. The reaction is continued by continuously or intermittently adding a crosslinkable monomer having vinyl groups, and when the polymerization rate reaches the range of 55 to 90%, the addition of the crosslinkable monomer is terminated, A method for producing a crosslinked polymer emulsion, which comprises completing the reaction after a certain period of time. 2. The method according to claim 1, wherein the emulsion polymerization is carried out in the presence of a water-soluble polymer. 3. The method according to claim 1, wherein the crosslinking monomer is ethylene glycol dimethacrylate or divinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8337885A JPS61241310A (en) | 1985-04-18 | 1985-04-18 | Production of emulsion of crosslinked polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8337885A JPS61241310A (en) | 1985-04-18 | 1985-04-18 | Production of emulsion of crosslinked polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61241310A true JPS61241310A (en) | 1986-10-27 |
| JPH0463082B2 JPH0463082B2 (en) | 1992-10-08 |
Family
ID=13800752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8337885A Granted JPS61241310A (en) | 1985-04-18 | 1985-04-18 | Production of emulsion of crosslinked polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61241310A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952651A (en) * | 1988-03-30 | 1990-08-28 | Japan Synthetic Rubber Co., Ltd. | Highly crosslinked polymer particles and process for producing the same |
| JPH02300204A (en) * | 1989-05-15 | 1990-12-12 | Japan Synthetic Rubber Co Ltd | Production of reactive microgel |
| JP2001131214A (en) * | 1999-09-30 | 2001-05-15 | Xerox Corp | Method for manufacturing latex polymer |
| JP2012188553A (en) * | 2011-03-10 | 2012-10-04 | Nippon Shokubai Co Ltd | Polymer particle |
| WO2014119595A1 (en) * | 2013-02-04 | 2014-08-07 | 日本エクスラン工業株式会社 | Aggregated composite resin particles, and composition containing said particles |
| WO2015012371A1 (en) * | 2013-07-24 | 2015-01-29 | 日本エイアンドエル株式会社 | Method for manufacturing copolymer latex, and copolymer latex |
| JPWO2017022423A1 (en) * | 2015-07-31 | 2018-05-17 | 綜研化学株式会社 | (Meth) acrylic crosslinked particles and production method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3936544B2 (en) * | 2000-09-11 | 2007-06-27 | 三菱化学株式会社 | Toner for developing electrostatic image, method for producing toner for developing electrostatic image, and method for fixing toner |
-
1985
- 1985-04-18 JP JP8337885A patent/JPS61241310A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952651A (en) * | 1988-03-30 | 1990-08-28 | Japan Synthetic Rubber Co., Ltd. | Highly crosslinked polymer particles and process for producing the same |
| JPH02300204A (en) * | 1989-05-15 | 1990-12-12 | Japan Synthetic Rubber Co Ltd | Production of reactive microgel |
| JP2001131214A (en) * | 1999-09-30 | 2001-05-15 | Xerox Corp | Method for manufacturing latex polymer |
| JP2012188553A (en) * | 2011-03-10 | 2012-10-04 | Nippon Shokubai Co Ltd | Polymer particle |
| WO2014119595A1 (en) * | 2013-02-04 | 2014-08-07 | 日本エクスラン工業株式会社 | Aggregated composite resin particles, and composition containing said particles |
| JPWO2014119595A1 (en) * | 2013-02-04 | 2017-01-26 | 日本エクスラン工業株式会社 | Composite aggregated resin particles and composition containing the particles |
| WO2015012371A1 (en) * | 2013-07-24 | 2015-01-29 | 日本エイアンドエル株式会社 | Method for manufacturing copolymer latex, and copolymer latex |
| JPWO2017022423A1 (en) * | 2015-07-31 | 2018-05-17 | 綜研化学株式会社 | (Meth) acrylic crosslinked particles and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0463082B2 (en) | 1992-10-08 |
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