JPS5978202A - Production of hydrophilic group-containing vinyl polymer - Google Patents
Production of hydrophilic group-containing vinyl polymerInfo
- Publication number
- JPS5978202A JPS5978202A JP57188354A JP18835482A JPS5978202A JP S5978202 A JPS5978202 A JP S5978202A JP 57188354 A JP57188354 A JP 57188354A JP 18835482 A JP18835482 A JP 18835482A JP S5978202 A JPS5978202 A JP S5978202A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl monomer
- containing vinyl
- hydrophilic group
- vinyl
- temperature
- 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】
本発明は親水基含有ビニルモノマーを使用して９懸濁重
合法により、親水基含有ビニル重合体を製造する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a hydrophilic group-containing vinyl polymer by a 9-suspension polymerization method using a hydrophilic group-containing vinyl monomer.
親水基含有ビニル重合体９例えばヒドロキシル基含有ビ
ニル重合体やカルボキシル基含有ビニル重合体は塗料用
樹脂、電子写真現像用トナ−、静電記録用トナーのバイ
ンダー樹脂、粉体塗料用樹脂などとして広範囲な用途を
もち１種々の重合法により製造されている。なかでも懸
濁重合法は、溶液重合法に比べ溶剤を使用しない点にお
いて、また、塊状重合法に比べ反応制御が容易であり１
粒状重合体が得られるなどの点において優れている。そ
こで、懸濁重合法による親水基含有ビニル重合体の製造
が従来から検討されている。Hydrophilic group-containing vinyl polymers 9 For example, hydroxyl group-containing vinyl polymers and carboxyl group-containing vinyl polymers are widely used as paint resins, toners for electrophotographic development, binder resins for electrostatic recording toners, resins for powder coatings, etc. It has many uses and is produced by various polymerization methods. Among these, the suspension polymerization method does not use a solvent compared to the solution polymerization method, and it is easier to control the reaction than the bulk polymerization method.
It is excellent in that granular polymers can be obtained. Therefore, production of hydrophilic group-containing vinyl polymers by suspension polymerization has been studied.
従来、懸濁重合法としては、デンプン、ゼラチン、ポリ
ビニルアルコール、リン酸三カル／ラムなとの懸濁剤を
溶解した水中に９重合開始剤を含むモノマーを一度に添
加し１反応が急速に進行しない温度、いわゆる常温下で
油滴状に懸濁した後、懸濁液を反応温度に昇温し、同温
度で２〜８時間保温して反応を完結させる方法が行なわ
れている。しかし、この方法は、水に不溶、難溶なモノ
マーの重合については適した方法であるが、ヒドロキシ
ル基、カルボキシル基等の親水基含有モノマーを多量に
含む系にこの方法を適用しようとすると１反応開始後間
もなく粒子状で懸濁していた半重合体が互いに融着して
大きな塊に生長（以下、餅状化現象と呼ぶ）してしまい
、目的とする粒状重合体が得られなかった。親水基含有
ビニルモノマーを使用した場合に餅状化しやすい原因と
しては、モノマーが親水性であるため油層（モノマー）
と水層の境界が明確でなく９反応の進行とともに粘着性
を帯びた粒子が攪拌中に接触、融着して塊になるものと
思われる。Conventionally, in the suspension polymerization method, a monomer containing a polymerization initiator is added at once to water in which a suspending agent such as starch, gelatin, polyvinyl alcohol, and trical phosphate/rum is dissolved, and one reaction is rapidly carried out. A method is used in which the suspension is suspended in the form of oil droplets at a temperature that does not allow the reaction to proceed, so-called room temperature, and then the suspension is heated to the reaction temperature and kept at the same temperature for 2 to 8 hours to complete the reaction. However, although this method is suitable for polymerizing monomers that are insoluble or sparingly soluble in water, it is difficult to apply this method to systems containing large amounts of monomers containing hydrophilic groups such as hydroxyl groups and carboxyl groups. Immediately after the start of the reaction, the half-polymers that had been suspended in particulate form fused together and grew into large lumps (hereinafter referred to as a cake-like phenomenon), making it impossible to obtain the desired particulate polymer. The reason why hydrophilic group-containing vinyl monomers tend to become cake-like is because the monomers are hydrophilic, the oil layer (monomer)
It is thought that the boundary between the water layer and the aqueous layer is not clear, and as the reaction progresses, the sticky particles come into contact and fuse together during stirring, forming a lump.
を含有するビニル系モノマーの懸濁重合において、該ビ
ニル系モノマーの重合可能な温度に加熱した水中に９該
ビニル系モノマーを滴下して添加し、懸濁重合させるこ
とを特徴とする親水基含有ビニル重合体の製造法に関す
る。In the suspension polymerization of a vinyl monomer containing a hydrophilic group, the vinyl monomer is added dropwise to water heated to a temperature at which the vinyl monomer can be polymerized, and suspension polymerization is carried out. This invention relates to a method for producing vinyl polymers.
本発明のビニル系モノマーは、親水基含有ビニルモノマ
ーまたは親水基含有ビニルモノマーと共重合可能な他の
ビニルモノマーとの混合物からなる。親水基含有ビニル
モノマーの懸濁重合法としては１本発明の方法が１重合
中の餅状化を防止する上で好ましいがこの特長は、親水
基含有ビニルモノマーの使用量が多い場合、特に１本発
明のビニル系モノマー中に、親水基含有ビニルモノマー
の割合が１０重重量板上の場合に顕著である。The vinyl monomer of the present invention consists of a hydrophilic group-containing vinyl monomer or a mixture of the hydrophilic group-containing vinyl monomer and another copolymerizable vinyl monomer. As a suspension polymerization method for hydrophilic group-containing vinyl monomers, the method of the present invention is preferable in terms of preventing cake-like formation during one polymerization. The proportion of the hydrophilic group-containing vinyl monomer in the vinyl monomer of the present invention is remarkable when it is on a 10-weight plate.
上記親水基含有ビニルモノマーとしてはアクリル酸β−
ヒドロキシエチル、アクリル酸ヒドロキシグロピル、メ
タクリル酸β−ヒドロキシエチル、メタクリル酸ヒドロ
キシプロピルなどのヒドロキシル基含有ビニルモノマー
やアクリ単独でまたは２種以上併用して使用される。The hydrophilic group-containing vinyl monomer is acrylic acid β-
Hydroxyl group-containing vinyl monomers such as hydroxyethyl, hydroxyglopyl acrylate, β-hydroxyethyl methacrylate, and hydroxypropyl methacrylate, and acrylates can be used alone or in combination of two or more.
親水基含有ビニルモノマーと共重合可能な他のビニル系
ノマートシては、スチレン、ビニルトルエン、ｐ−タロ
ルスチレン、ｐ−ブロモスチレン、ビニルナフタレンの
ような芳香族ビニル化合物、酢酸ビニル、プロピオン酸
ビニル９酪酸ヒニル、安息香酸ビニルのようなビニルエ
ステル、アクリル酸メチル、アクリル酸エチル。Other vinyl compounds that can be copolymerized with the hydrophilic group-containing vinyl monomer include styrene, vinyltoluene, p-thalolstyrene, p-bromostyrene, aromatic vinyl compounds such as vinylnaphthalene, vinyl acetate, vinyl propionate 9-butyric acid Vinyl esters such as vinyl benzoate, methyl acrylate, and ethyl acrylate.
アクリル酸（ｎ −、ｉｓｏ＋、ｔｅｒｔ−）ブチル、
アクリル酸ドデシル、アクリル酸ｎ−オクチル、アクリ
ル酸２−クロルエチル、アクリル酸グリシジル、アクリ
ル酸フェニル、アクリル酸ベンジル等のメタクリル酸エ
ステル、メタクリル酸メチル、メタクリル酸エチル、メ
タクリル酸（ｎ−。(n-, iso+, tert-)butyl acrylate,
Methacrylic acid esters such as dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid (n-.
ｉｓｏ、 ｔｅｒｔ−）ブチル、メタクリル酸ドデシル
。iso, tert-)butyl, dodecyl methacrylate.
メタクリル酸ｎ−オクチル、メタクリル酸２−クロルエ
チル、メタクリル酸グリシジル、メタクリル酸ベンジル
、メタクリル酸フェニル等のメタクリル酸エステル、ビ
ニルメチルエーテル。Methacrylic acid esters such as n-octyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, benzyl methacrylate, and phenyl methacrylate, and vinyl methyl ether.
ビニルイノブチルエーテル、ビニルエチルエーテルのよ
うなビニルエーテル、ビニルメチルケトン、ビニルへキ
シルケトン、ビニルイソプロペニルケトンのようなビニ
ルケトン、塩化ビニル、塩化ビニリデン、フッ化ビニリ
デンのようなエチレンのハロゲン（ｆ［、アクリロニト
リル。Vinyl ethers such as vinyl inobutyl ether, vinyl ethyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone, ethylene halogens (f[, acrylonitrile) such as vinyl chloride, vinylidene chloride, vinylidene fluoride.
アクリルアミド、Ｎ−メチロールアクリルアミド、ジア
セトンアクリルアミド、メタクリロニトリル、メタクリ
ルアミド、Ｎ−メチロールメタクリルアミド、ジアセト
ンメタクリルアミド等の窒素原子含有ビニルモノマーな
どがある。Examples include nitrogen atom-containing vinyl monomers such as acrylamide, N-methylol acrylamide, diacetone acrylamide, methacrylonitrile, methacrylamide, N-methylol methacrylamide, and diacetone methacrylamide.
重合開始剤としては、過酸化アセチル、過酸化デカノイ
ル、過酸化ラウロイル、過酸化ベンゾイル、過酸化ｐ−
クロロベンゾイル、過酸化２．４−ジクロロベンゾイル
、過ジ炭酸ジイノプロヒル、過ジ炭酸シー ２− エチ
／Ｉ／ −ヘ−’Ｐ ’／ ル。As a polymerization initiator, acetyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-peroxide
Chlorobenzoyl, 2,4-dichlorobenzoyl peroxide, diinoproyl perdicarbonate, 2-ethyl/I/-H-'P'/le perdicarbonate.
アセチルシクロヘキサンスルホニルペルオキシド、過酢
酸ｔｅｒｔ−ブチル、過イソ酪酸ｔｅｒｔ−ブチル、ア
ゾビスイソブチロニトリル９過２−エチルヘキナン酸ｔ
ｅｒｔ−ブチル、過安息香酸のが好ましい。Acetyl cyclohexane sulfonyl peroxide, tert-butyl peracetate, tert-butyl perisobutyrate, azobisisobutyronitrile 9-per-2-ethylhexanoate
Preference is given to ert-butyl and perbenzoic acid.
本発明において１分散剤としては、ゼラチン。In the present invention, one dispersant is gelatin.
トラガカントゴム、テンプン、メチルセルロース、カル
ボキシメチルセルロース、ポリビニルｒルコール、ｉ＝
、ＩＩ分ケン化ポリビニルアルコール。Gum tragacanth, starch, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, i=
, II-minute saponified polyvinyl alcohol.
ポリアクリル酸等の水溶性高分子、アルギン酸塩等の有
機分散剤、硫酸バリウム、硫酸カルシウム。Water-soluble polymers such as polyacrylic acid, organic dispersants such as alginate, barium sulfate, calcium sulfate.
炭酸バリウム、炭酸バリウム、炭酸マグネシウム、リン
酸三カルシウム、タルク、ベントナイト。Barium carbonate, barium carbonate, magnesium carbonate, tricalcium phosphate, talc, bentonite.
ケイソウ土、粘土等の難溶性の無機分散剤等が使用され
る。使用するビニル系モノマーの全量に対して有機分散
剤は、ＩＸＩＦ’〜４重ｔＬ無機分散剤は、０．０１〜
３重量係使用される。Slightly soluble inorganic dispersants such as diatomaceous earth and clay are used. The organic dispersant is IXIF' to 4-tL based on the total amount of vinyl monomer used, and the inorganic dispersant is 0.01 to
3 weights are used.
また１分散助剤として、ドデシルベンゼンスルホン酸ノ
ーダ等のアルキルベンゼンスルホン酸塩、アルキル基に
直接５ＯａＮａが結合したアルキルスルホン酸塩、β−
テトラヒドロナフタリンスルホン酸塩、Ｎ−イソプロピ
ルシクロへキシルアシドスルー−ソーダ等のアシドスル
ホン酸塩、オレイン酸ソーダ等の高級脂肪酸塩等の陰イ
オン界面活性剤を上記分散剤と併用することができる。In addition, as dispersion aids, alkylbenzene sulfonates such as dodecylbenzenesulfonate, alkyl sulfonates in which 5OaNa is directly bonded to the alkyl group, β-
Anionic surfactants such as tetrahydronaphthalene sulfonate, acid sulfonate such as N-isopropylcyclohexyl acid through-soda, and higher fatty acid salt such as sodium oleate can be used in combination with the above-mentioned dispersant.
特に分散剤として無機分散剤を使用するときは１分散助
剤を併用するのが好ましい。分散助剤は使用するビニル
系モノマー全量に対してｌＸｌ０−’〜０．０１重（ｉ
ｌｌ使用される。In particular, when an inorganic dispersant is used as a dispersant, it is preferable to use a dispersion aid in combination. The dispersion aid should be used in an amount of lXl0-' to 0.01 weight (i
ll used.
本発明において、懸濁重合の媒体としては。In the present invention, as a medium for suspension polymerization.
水が使用される。この媒体には予め９分散剤および必妥
に応じて分散助剤が添加されている。water is used. A dispersant and, if necessary, a dispersion aid are added to this medium in advance.
この媒体中に、」二記ビニル系モノマーが滴下して、添
加されるが、この時、すでに該媒体は。Into this medium, the vinyl monomer 2 is added dropwise, but at this time the medium is already present.
上記ビニル系モノマーが重合可能な温度に加熱されてい
る。ここで１重合可能な温度とは、使用される重合開始
剤の分解開始温度以上である。The vinyl monomer is heated to a temperature at which it can be polymerized. The temperature at which one polymerization is possible is equal to or higher than the decomposition starting temperature of the polymerization initiator used.
この温度は使用する１に合間始剤によって異なるが１例
えば、過酸化ベンゾイル、過２−エチルヘキサン酸ｔｅ
ｒｔ−ブチル等を用いた場合は、５０℃以上、過ジ炭酸
ジイノグロビル、過ジ炭酸ジー２−エチルヘキシルの場
合は３０℃以上である。ビニル系モノマーの重合可能な
温度に加熱されていない媒体中に、ビニ五ツマ−が滴下
された場合、従来の方法のように、Ｉｆ状化が起こる。This temperature varies depending on the initiator used, but for example, benzoyl peroxide, per2-ethylhexanoate, etc.
In the case of using rt-butyl etc., the temperature is 50°C or higher, and in the case of diinoglobil perdicarbonate or di-2-ethylhexyl perdicarbonate, the temperature is 30°C or higher. If vinyl monomers are dropped into a medium that has not been heated to a temperature at which vinyl monomers can be polymerized, If-formation occurs, as in conventional methods.
使用されるビニル系モノマーの全量（Ａ）と水の使用１
−ＦＢ＋については特に制限はないが（Ａｌ／７５／２
５以下が好ましく、特に６０／４０以ニル系モノマーお
よび水の総量ＩＫｇ当り、平均して１６．７７ｙ分以下
にされるのが好捷しい。Total amount of vinyl monomer used (A) and use of water 1
-There are no particular restrictions on FB+ (Al/75/2
It is preferably 5 or less, and particularly preferably 16.77 y minutes or less on average per IKg of the total amount of the 60/40 or higher monomer and water.
この添加速度（単位：１ｙ分・Ｋ、ｌ ）は、ビニル系
七ツマ−の滴下速度（単位：１ｙ分）を使用されるビニ
ル系モノマーおよび水の総量（単位：Ｋｐ）で除したも
のである。添加速度が平均して１６，７１ｙ分、 Ｋｐ
を越えると重合途中で餅状化をおこあるのが好１し、い
が、変動してもよい。この場合添加速度が１６．７ｙ−
／分・Ｋｇを越えないの力；好ましい。この添加速度は
、水性媒体とビニル系モノマーの量比、これらの使用量
を種々変えたときも、共通して適用できる。This addition rate (unit: 1y min.K, l) is calculated by dividing the dropping rate of vinyl monomer (unit: 1y min) by the total amount of vinyl monomer and water used (unit: Kp). be. Addition rate averaged 16,71y minutes, Kp
It is preferable that if it exceeds this amount, cake-like formation occurs during the polymerization, but it may vary. In this case, the addition rate was 16.7y-
Force not exceeding /min·Kg; preferred. This addition rate can be commonly applied even when the ratio of the aqueous medium to the vinyl monomer and the amounts used thereof are varied.
次に１本発明の実施例を示す。Next, an example of the present invention will be shown.
実施例１
（１）媒体
水 １ｏｏｏ
ｙ（２）滴下液
スチレン ５００ｙ−メタク
リル酸ｎ−ブチル １００Ｊメタクリル酸β−
ヒドロキシエチル ４０ｏｚ過酸化ベンゾイル
３０ｙ−上記（１）の組成からなる媒体
を反応容器に入れ液温を９０℃に昇温した後、上記（２
）に示す組成の滴下液を均一な速度で１．５時間かけて
滴下し、同温度で４時間保持した。得られた重合体は、
直径１〜２１ｍの粒状物であった。収量は、９９係であ
った。この例における添加速度は５．６５４／分・縁で
あった。なお、ビニル系モノマーの滴下速度は。Example 1 (1) Medium water 1ooo
y(2) Dropped liquid styrene 500y-n-butyl methacrylate 100J β-methacrylate
Hydroxyethyl 40oz benzoyl peroxide
30y-Pour the medium having the composition of (1) above into a reaction vessel, raise the liquid temperature to 90°C, and then
) was added dropwise at a uniform rate over 1.5 hours, and maintained at the same temperature for 4 hours. The obtained polymer is
The particles were 1 to 21 m in diameter. The yield was 99. The addition rate in this example was 5.654/min.edge. Furthermore, what is the dropping speed of the vinyl monomer?
ｉｔ、ｉｙ−７分であった。it, iy - 7 minutes.
実施例２
（１） 媒体
水 １００
０Ｐ（２）滴下液
スチレン ６００７アクリル
酸ｎ−ブチル １００７メタクリル
酸β−ヒドロキシエチル ３００ｆｉ’過酸化ベン
ゾイル ５０Ｐ上記（１）の組成の媒
体を反応容器に入れ、液温を９５℃に昇（島した後、上
記（２）の組成の滴下液を均一な速度で１時間かけて滴
下し、同温度で４時間保持した。得られた重合体は直径
約２ｒｒａｎの粒状物であった。収眉二は９９チであっ
た。この例における添加速度は８．３ｙ−７分・Ｋｇで
あった。なお、ビニル系モノマーの滴下速度は１６．７
ｙ−７分であった。Example 2 (1) Medium water 100
0P (2) Dropped liquid Styrene 6007 n-butyl acrylate 1007 β-hydroxyethyl methacrylate 300 fi' benzoyl peroxide 50P A medium having the composition of (1) above was placed in a reaction vessel, and the liquid temperature was raised to 95°C. After that, the dropping solution having the composition of (2) above was added dropwise at a uniform rate over 1 hour and maintained at the same temperature for 4 hours.The obtained polymer was a granular material with a diameter of about 2 rran. was 99 cm.The addition rate in this example was 8.3y-7min·Kg.The dropping rate of the vinyl monomer was 16.7cm.
It was y-7 minutes.
実施例３
（１）媒体
水 １２０
ｏｙ−ポリビニルアルコール（ゴーセ ６
？ノールＧＨ−２０）
（２）滴■液
スチレン ４５０！ｉｒ−メ
タクリル酸エチル １００１アクリル酸
ｎ−ブチル １０１メタクリル酸β−ヒド
ロキシエチル １５０ψメタクリル酸
２００グ・過酸化ベンゾイル
５０Ｊ上記（１）の組成の媒体を反化容器に入れ、液
温を９０°Ｃに昇温した後、上記（２，）の組成の滴下
液を均一な速度で１時間かけて滴下し、同温度で５時間
保持した。得られた重合体は、この例における添加速度
は７．６９−７分・Ｋｇであった。なお、ビニル系モノ
マーの滴下速度はｔａ７Ｐ／分であった１゜直径約１．
、５ ｍの粒状物であった。収量は９８係であった。Example 3 (1) Medium water 120
oy-polyvinyl alcohol (Gose 6
? Nord GH-20) (2) Drop ■Liquid styrene 450! ir-ethyl methacrylate 1001 n-butyl acrylate 101 β-hydroxyethyl methacrylate 150ψ methacrylic acid
200g benzoyl peroxide
50J Put the medium with the composition in (1) above into an incubation container, raise the temperature of the liquid to 90 ° C, then drop the dripping liquid with the composition in (2,) above at a uniform rate over 1 hour, It was maintained at the same temperature for 5 hours. The resulting polymer had an addition rate of 7.69-7 min.Kg in this example. The dropping rate of the vinyl monomer was ta7P/min.
, 5 m of granules. The yield was 98 units.
比較例１ 実施例１と全く同じ懸濁液、ビニルモノマーを用いた。Comparative example 1 Exactly the same suspension and vinyl monomer as in Example 1 were used.
まず懸濁液を反応容器に入れ、常温下で攪拌しながらビ
ニルモノマーを短時間で滴下、懸濁後、液温を９０℃に
昇温しで反応を進めたがなかった。First, the suspension was placed in a reaction container, and the vinyl monomer was added dropwise in a short time while stirring at room temperature. After suspension, the temperature of the solution was raised to 90° C. to proceed with the reaction, but the reaction did not proceed.
比較例２
実施例３と全く同じ材料を用い、比較例１と同じ工程で
反応を進めたところやはりモチ化現象が起こり９粒状物
は得られなかった。実施例１と比較例１及び実施例３と
比較例２は全く同じ材料を使用して、製造方法をかえた
ものであるが０本発明による製造法では餅状化現象が起
こらず極めて優れた懸濁重合法であることがわかる。Comparative Example 2 When the same materials as in Example 3 were used and the reaction was carried out in the same steps as in Comparative Example 1, a waxy phenomenon also occurred and no granules were obtained. Example 1 and Comparative Example 1 and Example 3 and Comparative Example 2 were made using exactly the same materials and using different manufacturing methods, but the manufacturing method according to the present invention did not cause the cake-like phenomenon and was extremely excellent. It can be seen that it is a suspension polymerization method.
以上より明らかなように１本発明によれば、親水基含有
ビニルモノマーを含むビニル系モノマーを使用して、懸
濁重合法により、効率よく親水基含有ビニル重合体を製
造することができる。As is clear from the above, according to the present invention, a hydrophilic group-containing vinyl polymer can be efficiently produced by a suspension polymerization method using a vinyl monomer containing a hydrophilic group-containing vinyl monomer.
Claims (1)
マーの懸濁重合において、該ビニル系モノマーの重合可
能な温度に加熱した水中に、該ビニル系モノマーを滴下
して添加し。 懸濁重合させることを特徴とする親水基含有ビニル重合
体の製造法。 ２、 ビニル系モノマーの添加速度が、平均して１６．
７Ｐ／分・匂〔ビニルモノマーの滴下速度（ｙ−７分）
を使用されるビニル系モノマーと水の総量（Ｋｇ）で除
したもの〕以下である特許請求の範囲第１項記載の親水
基含有ビニル重合体の製造法。 ３、 ヒ、＝−ル系モ／マーが親水基含有ビニルモノ
マーを１０重量係以上含有する特許請求の範囲第１項ま
たは第２項記載の親水基含有ビニル重合体の製造法。 ４、親水基含有ビニルモノマーが、ヒドロキシル基含有
ビニルモノマーである特許請求の範囲第１項、第２項ま
たは第３項記載の親水基含有ビニル重合体の製造法。 ５、親水基含有ビニルモノマーが、カルボキシル基含有
ビニルモノマーである特許請求の範囲第１項、第２項ま
たは第３項記載の親水基含有ビニル重合体の製造法。 ６、親水基含有ビニルモノマーとしてヒドロキシル基含
有ビニルモノマー及びカルボキシル基含有ビニルモノマ
ーを使用する特許請求の範囲第１項、第２項または第３
項記載の親水基含有ビニル重合体の製造法。[Claims] 1. In suspension polymerization of a vinyl monomer containing a hydrophilic group-containing vinyl monomer, the vinyl monomer is added dropwise to water heated to a temperature at which the vinyl monomer can be polymerized. . A method for producing a hydrophilic group-containing vinyl polymer, which comprises suspension polymerization. 2. The average vinyl monomer addition rate is 16.
7P/min・odor [dropping rate of vinyl monomer (y-7 minutes)
divided by the total amount (Kg) of vinyl monomer and water used] The method for producing a hydrophilic group-containing vinyl polymer according to claim 1. 3. The method for producing a hydrophilic group-containing vinyl polymer according to claim 1 or 2, wherein the H,=-R type mo/mer contains a hydrophilic group-containing vinyl monomer at a weight ratio of 10 or more. 4. The method for producing a hydrophilic group-containing vinyl polymer according to claim 1, 2 or 3, wherein the hydrophilic group-containing vinyl monomer is a hydroxyl group-containing vinyl monomer. 5. The method for producing a hydrophilic group-containing vinyl polymer according to claim 1, 2 or 3, wherein the hydrophilic group-containing vinyl monomer is a carboxyl group-containing vinyl monomer. 6. Claims 1, 2 or 3 in which a hydroxyl group-containing vinyl monomer and a carboxyl group-containing vinyl monomer are used as the hydrophilic group-containing vinyl monomer.
A method for producing a hydrophilic group-containing vinyl polymer as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57188354A JPS5978202A (en) | 1982-10-27 | 1982-10-27 | Production of hydrophilic group-containing vinyl polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57188354A JPS5978202A (en) | 1982-10-27 | 1982-10-27 | Production of hydrophilic group-containing vinyl polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5978202A true JPS5978202A (en) | 1984-05-07 |
| JPH0155642B2 JPH0155642B2 (en) | 1989-11-27 |
Family
ID=16222155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57188354A Granted JPS5978202A (en) | 1982-10-27 | 1982-10-27 | Production of hydrophilic group-containing vinyl polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5978202A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190402A (en) * | 1984-03-12 | 1985-09-27 | Hitachi Chem Co Ltd | Production of vinyl polymer |
| JPH01202760A (en) * | 1988-02-09 | 1989-08-15 | Tomoegawa Paper Co Ltd | Positive toner |
| JPH01267565A (en) * | 1988-04-19 | 1989-10-25 | Mita Ind Co Ltd | Production of electrostatic charge image developing toner |
| JPH02254468A (en) * | 1989-03-29 | 1990-10-15 | Tomoegawa Paper Co Ltd | Manufacture of polymerized toner |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962197A (en) * | 1973-07-18 | 1976-06-08 | Eastman Kodak Company | Suspension polymerization process |
-
1982
- 1982-10-27 JP JP57188354A patent/JPS5978202A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962197A (en) * | 1973-07-18 | 1976-06-08 | Eastman Kodak Company | Suspension polymerization process |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190402A (en) * | 1984-03-12 | 1985-09-27 | Hitachi Chem Co Ltd | Production of vinyl polymer |
| JPH0536442B2 (en) * | 1984-03-12 | 1993-05-31 | Hitachi Chemical Co Ltd | |
| JPH01202760A (en) * | 1988-02-09 | 1989-08-15 | Tomoegawa Paper Co Ltd | Positive toner |
| JPH01267565A (en) * | 1988-04-19 | 1989-10-25 | Mita Ind Co Ltd | Production of electrostatic charge image developing toner |
| JPH02254468A (en) * | 1989-03-29 | 1990-10-15 | Tomoegawa Paper Co Ltd | Manufacture of polymerized toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0155642B2 (en) | 1989-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4352916A (en) | Use of hydrophobically modified water soluble polymers in suspension polymerization | |
| US4271281A (en) | Process for preparing styrenic polymer particles | |
| JP4633987B2 (en) | Method for producing thermally expandable microcapsules | |
| NO172967B (en) | PROCEDURE FOR ENCAPPING OR TO AA STAND UP A PRODUCT CONTAINING A LARGE SET OF CONTINUOUS PHASE AND LOST OR SUSPENDED SUBSTANCES | |
| JP3412320B2 (en) | Suspending agent-containing slurry, method for producing the same, and suspension polymerization method using the same | |
| JPS6232205B2 (en) | ||
| JPS5978202A (en) | Production of hydrophilic group-containing vinyl polymer | |
| US4011283A (en) | Polymerization process | |
| JPS6410004B2 (en) | ||
| US2886559A (en) | Clay thickened suspension polymerization process with plug flow | |
| CA2065110A1 (en) | Anti-blocking suspension polymers | |
| JPH0155643B2 (en) | ||
| JPS6195003A (en) | Production of hydrophilic group-containing vinyl polymer | |
| JPS60120702A (en) | Production of particulate resin | |
| JPH0144722B2 (en) | ||
| JPH06136006A (en) | Production of polymeric particle | |
| JP5331366B2 (en) | Method for preventing blocking of styrene elastomer resin pellets | |
| JPH03273014A (en) | Production of modified polyolefin particle | |
| JP2020164578A (en) | Method for production of emulsified polymer | |
| US5272228A (en) | Preparation of (co)polymers soluble in their (co)monomer compositions | |
| JPH09316139A (en) | Vinyl chloride resin and its production | |
| JP2800314B2 (en) | Method for suspension polymerization of styrene resin with low scale formation | |
| JP2559833B2 (en) | Continuous production method of powdery and granular polymer and method of controlling particle size of the polymer | |
| JP2010195968A (en) | Method for producing styrenic elastomer resin pellets | |
| JP2009073930A (en) | Blocking prevention method for styrenic elastomer resin pellet |