JP2000239315A - Production of polymer - Google Patents
Production of polymerInfo
- Publication number
- JP2000239315A JP2000239315A JP11037868A JP3786899A JP2000239315A JP 2000239315 A JP2000239315 A JP 2000239315A JP 11037868 A JP11037868 A JP 11037868A JP 3786899 A JP3786899 A JP 3786899A JP 2000239315 A JP2000239315 A JP 2000239315A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- tank
- latex
- coagulation
- weight
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は重合体の製造方法に
関し、詳しくは乳化重合法でグラフト重合して得られた
重合体ラテックスから、微粒子が少なく嵩比重の高い優
れた粉体特性を有するグラフト重合体粒子を凝固させて
得る重合体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer, and more particularly, to a polymer latex obtained by graft polymerization using an emulsion polymerization method, which has excellent fine powder characteristics with a small amount of fine particles and a high bulk specific gravity. The present invention relates to a method for producing a polymer obtained by coagulating polymer particles.
【０００２】[0002]
【従来の技術】ジエン系ゴム状重合体に芳香族ビニルと
シアン化ビニルを含む単量体混合物を乳化重合法でグラ
フト重合すると、安定な乳濁液である重合体ラテックス
が得られる。重合体ラテックスからグラフト重合体粒子
を得るには、ラテックスに酸または塩等の電解質や酸無
水物等の凝固剤を接触させて、グラフト重合体を凝固さ
せ凝固物を含むスラリーとし、その後脱水、乾燥を行っ
てグラフト重合体粒子を得る方法が一般的に行われてい
る。この方法においては、グラフト重合体を凝固させる
工程の凝固温度や添加する凝固剤濃度等の条件が、得ら
れるグラフト重合体粒子の粒度分布や密度等の粉体特性
に影響を与えることがわかっている。そこで、凝固温度
や凝固剤濃度等の凝固工程に関する条件検討が広く行わ
れている。2. Description of the Related Art When a monomer mixture containing aromatic vinyl and vinyl cyanide is graft-polymerized to a diene rubber-like polymer by an emulsion polymerization method, a stable emulsion latex polymer latex is obtained. To obtain the graft polymer particles from the polymer latex, the latex is brought into contact with an electrolyte such as an acid or a salt or a coagulant such as an acid anhydride to coagulate the graft polymer to form a slurry containing the coagulated material, followed by dehydration. A method for obtaining graft polymer particles by drying is generally performed. In this method, it has been found that conditions such as a coagulation temperature and a coagulant concentration to be added in a step of coagulating the graft polymer affect powder characteristics such as a particle size distribution and a density of the obtained graft polymer particles. I have. In view of this, conditions for the coagulation process such as coagulation temperature and coagulant concentration have been widely studied.
【０００３】凝固工程においては、その後の各工程で凝
固物の滞留や凝固物による閉塞等のトラブルが起こらな
い安定した工業生産を行えるように、微粒子が少なく嵩
比重が高い優れた粉体特性を有する粉体を生成させるこ
とが重要である。微粒子が多い粉体は、生産上のトラブ
ルの他、脱水されにくいため脱水工程の生産性を低下さ
せる。また、その後の乾燥工程や製品として得られた後
においても粉塵を発生して作業環境を悪化させたり、貯
蔵中に微粒子同志が固結するブロッキング現象を引き起
こして流動性を低下させたりする等問題がある。特にＡ
ＢＳ重合体等では、工業的に処理量が大きいため、製造
元だけでなく、使用者側も巨大な貯蔵施設を用いている
場合が多く、粒子の耐ブロッキング性はきわめて重要視
される。また、嵩比重が低い粒子は、粒子内が粗である
ために粒子の強度が不十分で、凝固工程後の各工程で破
壊されて微粉を生じたり、製品として得られた後も、か
さ高いために輸送コストを増大させたり、貯蔵中に微粉
を生じてブロッキング現象を起こす等、製品の品質にも
影響を及ぼし、工業的に非常に問題がある。In the coagulation step, excellent powder characteristics with a small amount of fine particles and a high bulk specific gravity are used in each subsequent step so that stable industrial production without troubles such as stagnation of the coagulate and blockage due to the coagulate can occur. It is important to produce a powder that has Powder having many fine particles is difficult to be dehydrated in addition to troubles in production, so that the productivity of the dehydration step is reduced. In addition, even after the subsequent drying step or after being obtained as a product, dust is generated, thereby deteriorating the working environment, and causing a blocking phenomenon in which the fine particles solidify during storage, thereby lowering the fluidity. There is. Especially A
In the case of a BS polymer or the like, since the amount of treatment is industrially large, not only the manufacturer but also the user often uses a huge storage facility, and the blocking resistance of the particles is extremely important. In addition, particles having a low bulk specific gravity have insufficient strength due to the coarseness of the inside of the particles, and are broken in each step after the solidification step to produce fine powder, and even after being obtained as a product, they are bulky. For this reason, the quality of the product is affected, for example, the transportation cost is increased, and a fine powder is generated during storage to cause a blocking phenomenon, which is very industrially problematic.
【０００４】そこで、微粒子が少なく嵩比重が高い優れ
た粉体特性を有する重合体粒子を得るために、凝固工程
における凝固温度、凝固剤濃度、攪拌速度を規定して凝
固させる方法（特開平７−１３８３１４号公報、特開平
８−４８７１７号公報、特開平９−２８６８１５号公
報）が提案されている。Therefore, in order to obtain polymer particles having excellent powder properties with few fine particles and high bulk specific gravity, a method of coagulation by regulating the coagulation temperature, coagulant concentration and stirring speed in the coagulation step (Japanese Patent Laid-Open No. JP-138314, JP-A-8-48717, and JP-A-9-286815) have been proposed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
の方法は主にゴム状重合体含有量の低いグラフト重合体
については有効であるが、よりブロッキング現象を起こ
しやすいゴム状重合体含有量の高いグラフト重合体につ
いては期待する効果が得られにくい。また、ゴム状重合
体含有量の高いグラフト重合体を嵩比重の高い粒子とし
て得る方法としては、低速で流れる凝固剤水溶液流中に
内径数ｍｍのガラス管を多数浸漬させ、そのガラス管か
ら凝固剤水溶液の流速と同程度の速さで重合体ラテック
スを吐出しグラフト重合体を凝固させることによって、
過剰な剪断場での凝固をさけ、微粒子が少なく嵩比重が
高い粉体特性を有するグラフト重合体粒子を得る方法
（特開昭５７−１８７３２２号公報、特公平４−６０１
２５号公報）が報告されている。しかし、この方法では
ガラス管内で凝固が進行し、ガラス管が閉塞しやすいと
いう問題がある。このようなノズル内部での閉塞を抑制
するためには、低レイノルズ数の重合体ラテックス流に
加圧流体を添加して重合体ラテックスのひずみ速度を制
御し凝固する方法（特開平６−２３４８６４号公報）が
提案されているが、加圧流体が添加されるために重合体
ラテックスの流れを乱し、その結果グラフト重合体粒子
の水中への拡散が促進され、粒度分布、特に微粒子量を
少なく抑えることが難しい。以上のように、通常の攪拌
槽等のような単純な設備で安定に、微粒子が少なく嵩比
重の高い優れた粉体特性を有するグラフト重合体粒子を
得る方法は未だ見いだされていない。However, these methods are effective mainly for a graft polymer having a low rubber-like polymer content, but are high for a graft polymer having a high content of a rubber-like polymer which tends to cause a blocking phenomenon. It is difficult to obtain the expected effects for polymers. Further, as a method for obtaining a graft polymer having a high rubber-like polymer content as particles having a high bulk specific gravity, a large number of glass tubes having an inner diameter of several mm are immersed in a coagulant aqueous solution flowing at a low speed, and solidified from the glass tubes. By discharging the polymer latex at the same speed as the flow rate of the agent aqueous solution and coagulating the graft polymer,
A method of avoiding coagulation in an excessive shearing field and obtaining a graft polymer particle having powder characteristics having a small amount of fine particles and a high bulk specific gravity (JP-A-57-187322, JP-B-4-601).
No. 25) has been reported. However, this method has a problem that solidification progresses in the glass tube and the glass tube is easily clogged. In order to suppress such clogging inside the nozzle, a method of adding a pressurized fluid to a polymer latex stream having a low Reynolds number to control the strain rate of the polymer latex and coagulate (Japanese Patent Laid-Open No. 6-234864). However, the addition of a pressurized fluid disturbs the flow of the polymer latex, and as a result, the diffusion of the graft polymer particles into water is promoted, and the particle size distribution, particularly the amount of fine particles, is reduced. Difficult to control. As described above, a method for stably obtaining a graft polymer particle having a small amount of fine particles and a high bulk specific gravity and having excellent powder characteristics with a simple facility such as a usual stirring tank has not yet been found.
【０００６】本発明は前記事情に鑑みてなされたもの
で、重合体ラテックスから微粒子が少なく嵩比重の高い
優れた粉体特性を有するグラフト重合体粒子を安定に得
る方法を提供するものである。The present invention has been made in view of the above circumstances, and provides a method for stably obtaining a graft polymer particle having a small amount of fine particles, a high bulk specific gravity, and excellent powder properties from a polymer latex.
【０００７】[0007]
【課題を解決するための手段】本発明者らは鋭意検討し
た結果、凝固工程において微粒子が少なく嵩比重が高い
粉体特性を有するグラフト重合体粒子を得るためには、
重合体ラテックスを攪拌槽内に、吐出部断面積がある程
度大きな浸漬ノズルから低線速度で吐出して凝固剤と接
触させ、グラフト重合体を急速凝固させスラリー溶液を
得て、次いでそのスラリー溶液を固化する方法が有効で
あることを見いだした。Means for Solving the Problems As a result of intensive studies, the present inventors have found that, in order to obtain a graft polymer particle having powder characteristics having a small number of fine particles and a high bulk specific gravity in a coagulation step,
The polymer latex is discharged from the immersion nozzle having a relatively large discharge section cross section at a low linear velocity into the stirring tank and brought into contact with a coagulant to rapidly coagulate the graft polymer to obtain a slurry solution. The solidification method was found to be effective.
【０００８】すなわち本発明の要旨は、ジエン系ゴム状
重合体に、芳香族ビニルとシアン化ビニルを含む単量体
混合物をグラフト重合して得られる重合体ラテックス
に、凝固剤を接触させてグラフト重合体粒子を得る重合
体の製造方法において、重合体ラテックスを、攪拌槽内
に、吐出部断面積が４０ｍｍ2 以上であって吐出方向が
攪拌槽内の流れと同じ向きになるように設けられた浸漬
ノズルから、ノズル出口の線速度が５０〜２００ｍｍ／
ｓの速度となるように吐出して凝固剤と接触させ、グラ
フト重合体を凝固させスラリー溶液を得る凝析工程と、
次いで、得られたスラリー溶液を７０〜１００℃に保
ち、凝固したグラフト重合体を固化させる固化工程とを
有する重合体の製造方法に存する。グラフト重合体中の
ジエン系ゴム状重合体の含有量は３０〜８０重量％であ
ることが好ましい。凝析工程における攪拌槽内スラリー
中のグラフト重合体固形分濃度が１５〜３０重量％であ
ることが好ましい。凝析工程における攪拌槽の液温は５
０〜８０℃であることが好ましい。また、凝析工程にお
ける攪拌槽内の攪拌は、攪拌翼の先端を４００〜４００
０ｍｍ／ｓの周速で回転させて行うことが好ましい。さ
らに、攪拌槽は密閉式連続攪拌槽であることが好まし
い。That is, the gist of the present invention is that a coagulant is brought into contact with a polymer latex obtained by graft-polymerizing a monomer mixture containing aromatic vinyl and vinyl cyanide onto a diene rubber-like polymer. In the method for producing a polymer for obtaining polymer particles, a polymer latex is provided in a stirring tank such that a discharge section cross-sectional area is 40 mm 2 or more and a discharge direction is the same as a flow in the stirring tank. From the immersion nozzle, the linear velocity at the nozzle outlet is 50 to 200 mm /
a coagulation step of discharging the slurry so as to have a speed of s and contacting it with a coagulant, coagulating the graft polymer to obtain a slurry solution,
Then, the obtained slurry solution is maintained at 70 to 100 ° C., and a solidifying step of solidifying the solidified graft polymer is included in the method for producing a polymer. The content of the diene rubbery polymer in the graft polymer is preferably 30 to 80% by weight. It is preferable that the solid concentration of the graft polymer in the slurry in the stirring tank in the coagulation step is 15 to 30% by weight. The liquid temperature of the stirring tank in the coagulation process is 5
The temperature is preferably from 0 to 80 ° C. In addition, the stirring in the stirring tank in the coagulation step is performed by setting the tip of the stirring blade to 400 to 400.
It is preferable that the rotation is performed at a peripheral speed of 0 mm / s. Further, the stirring tank is preferably a closed type continuous stirring tank.
【０００９】[0009]
【発明の実施の形態】以下、本発明を詳しく説明する。
本発明における重合体ラテックスとしては、ジエン系ゴ
ムを含有するゴム状重合体に、少なくとも芳香族ビニル
とシアン化ビニルを含む硬質重合体形成性単量体を、乳
化重合法でグラフト重合して得られる乳濁液であって、
水中にグラフト重合体が安定に分散しているものであ
る。ジエン系ゴムとしてはポリブタジエン、ポリイソプ
レン、ポリクロロプレン、ブタジエン−スチレン共重合
体（ＳＢＲ）、ブタジエン−ブチルアクリレート共重合
体、ブタジエン−アクリロニトリル共重合体等であって
特に制限はない。ジエン系ゴム状重合体はこれらのジエ
ン系ゴムを含有するものである。芳香族ビニルはスチレ
ン、α−メチルスチレン、ｐ−メチルスチレン、ビニル
ナフタレン等であって、これらは１種類単独で用いても
よいし、２種類以上混合して用いてもよい。シアン化ビ
ニルはアクリロニトリル、メタクリロニトリル、シアン
化ビニリデン等であって、これらは１種類単独で用いて
もよいし、２種類以上混合して用いてもよい。本発明に
おいては、製造するグラフト重合体中のジエン系ゴム状
重合体の含有量は特に制限はないが、特に、ジエン系ゴ
ム状重合体を３０〜８０重量％含有するグラフト重合体
の製造に効果がある。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As the polymer latex in the present invention, a rubber-like polymer containing a diene rubber is obtained by graft-polymerizing a hard polymer-forming monomer containing at least aromatic vinyl and vinyl cyanide by an emulsion polymerization method. The emulsion being
The graft polymer is stably dispersed in water. Examples of the diene rubber include polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer (SBR), butadiene-butyl acrylate copolymer, and butadiene-acrylonitrile copolymer, and are not particularly limited. The diene rubbery polymer contains these diene rubbers. The aromatic vinyl is styrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene and the like, and these may be used alone or in combination of two or more. Vinyl cyanide is acrylonitrile, methacrylonitrile, vinylidene cyanide and the like, and these may be used alone or in combination of two or more. In the present invention, the content of the diene rubber-like polymer in the graft polymer to be produced is not particularly limited. In particular, the content of the diene rubber-like polymer is preferably 30 to 80% by weight. effective.
【００１０】乳化剤は、乳化重合法で通常使用されるも
のであり、特に制限はないが、通常、オレイン酸、ステ
アリン酸、ロジン酸、アルキルコハク酸等の弱酸系のカ
ルボン酸ナトリウム塩やカルボン酸カリウム塩等であ
る。これらの乳化剤には、アルキル硫酸エステル塩、ア
ルキルベンゼンスルホン酸塩等のカルボン酸塩以外の乳
化剤を少量添加して使用してもよい。乳化剤は通常、重
合体ラテックス中のグラフト重合体固形分１００重量部
に対して３．０重量部以下になるように添加される。The emulsifier is usually used in an emulsion polymerization method, and is not particularly limited. Usually, a weak acid carboxylic acid sodium salt such as oleic acid, stearic acid, rosin acid, or alkyl succinic acid or carboxylic acid is used. Potassium salt and the like. These emulsifiers may be used by adding a small amount of an emulsifier other than a carboxylate such as an alkyl sulfate or an alkylbenzene sulfonate. The emulsifier is usually added so as to be 3.0 parts by weight or less based on 100 parts by weight of the solid content of the graft polymer in the polymer latex.
【００１１】凝固剤は通常使用される塩酸、硫酸、硝酸
等の無機酸、ギ酸、酢酸等の有機酸、塩化カルシウム、
硫酸マグネシウム、硫酸アルミニウム等の無機塩、酢酸
カルシウム、酢酸アルミニウム等の有機酸塩等であっ
て、これらを溶解し水溶液としたものが一般に使用され
る。これらの凝固剤はグラフト重合体を急速凝固させる
ために十分な量が使用され、その量は重合体ラテックス
中の乳化剤の種類や含有量、または凝固剤の種類等によ
って異なるが、通常、グラフト重合体に対して２．５重
量％以上であり、好ましくは３．０重量％以上である。
また、特に酸系凝固剤を使用する場合には、凝集槽内の
スラリー溶液のｐＨが３．０以下、さらには２．０以下
になるような量が添加されることが好ましい。これは、
凝固剤の使用量が２．５重量％未満か、あるいは酸系凝
固剤を使用した場合のスラリー溶液のｐＨが３を超える
と、重合体を十分凝固させることができず、得られた重
合体粒子中の微粉の割合の増加や嵩比重の低下がみら
れ、また、湿粉水分率が大きくなり乾燥工程での生産性
が低下するためである。The coagulants are usually used inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid and acetic acid, calcium chloride,
Inorganic salts such as magnesium sulfate and aluminum sulfate, and organic acid salts such as calcium acetate and aluminum acetate, etc., which are dissolved and made into an aqueous solution, are generally used. These coagulants are used in an amount sufficient to rapidly coagulate the graft polymer, and the amount varies depending on the type and content of the emulsifier in the polymer latex or the type of the coagulant. It is at least 2.5% by weight, preferably at least 3.0% by weight, based on the coalescence.
Further, particularly when an acid-based coagulant is used, it is preferable to add an amount so that the pH of the slurry solution in the flocculation tank becomes 3.0 or less, and more preferably 2.0 or less. this is,
If the amount of the coagulant used is less than 2.5% by weight, or if the pH of the slurry solution exceeds 3 when an acid-based coagulant is used, the polymer cannot be coagulated sufficiently and the resulting polymer This is because the ratio of the fine powder in the particles is increased and the bulk specific gravity is decreased, and the moisture content of the wet powder is increased, and the productivity in the drying step is reduced.
【００１２】本発明において、重合体ラテックスは、攪
拌槽内に、吐出部断面積が４０ｍｍ 2 以上であって吐出
方向が攪拌槽内の流れと同じ向きになるように設けられ
た浸漬ノズルから、吐出される。攪拌槽は連続式、バッ
チ式のいずれでも使用でき、攪拌翼を備えた１基かまた
は２基以上の攪拌槽からなるものや、２室以上に分画さ
れ、各室に攪拌装置を備えた筒状容器等でもよいが、２
基以上の攪拌槽が連続してなる密封式連続攪拌槽を使用
すると、第１槽を凝析工程を行う凝析槽とし、第２槽以
降を固化工程を行う固化槽として使用できるので、生産
性や設備コストの点から好ましい。攪拌装置はプロペラ
翼、タービン翼、パドル翼、三方後退翼、ディスク翼等
の攪拌翼を使用した回転攪拌翼が一般に用いられ、邪魔
板等の補助攪拌装置を併用してもよい。回転攪拌翼を使
用する場合、攪拌は攪拌翼先端が４００〜４０００ｍｍ
／ｓの周速で回転する条件で行われることが好ましい。
４００ｍｍ／ｓ未満の周速で攪拌すると、攪拌が不十分
で重合体ラッテクスと凝固剤が十分に混合せず、未凝固
物や微粉の発生につながるし、４０００ｍｍ／ｓを超え
ると、攪拌による剪断力過多となって微粉が増加する。[0012] In the present invention, the polymer latex is stirred.
In the mixing tank, the cross section of the discharge part is 40mm Two Above and discharge
It is provided so that the direction is the same as the flow in the stirring tank.
From the immersion nozzle. The stirring tank is continuous,
One with a stirring blade
Is composed of two or more stirred tanks or divided into two or more chambers.
A cylindrical container or the like provided with a stirrer in each chamber may be used.
Uses a sealed continuous stirring tank with more than one continuous stirring tank
Then, the first tank is used as a coagulation tank for performing the coagulation step, and the second tank and the like are used.
The production can be used as a solidification tank that performs the solidification process.
It is preferable from the viewpoint of performance and equipment cost. The stirring device is a propeller
Blades, turbine blades, paddle blades, three-way swept blades, disk blades, etc.
Rotary agitating blades using agitating blades are generally used,
An auxiliary stirring device such as a plate may be used in combination. Use rotating stirring blades
When using, the stirring blade tip is 400-4000mm
It is preferably performed under the condition of rotating at a peripheral speed of / s.
Insufficient stirring when stirring at a peripheral speed of less than 400 mm / s
The polymer latex and coagulant do not mix well and are not coagulated
Leads to the generation of objects and fine powder, and exceeds 4000 mm / s
Then, the shearing force due to the stirring becomes excessive and the fine powder increases.
【００１３】攪拌槽に設ける浸漬ノズルは、吐出部断面
積が４０ｍｍ2 以上のものであれば、その形状に特に制
限はない。例えば、重合体ラテックス吐出専用に使用さ
れる単管構造型のものや、２重管以上の多重管型で重合
体ラテックスと凝固剤水溶液をそれぞれの吐出部から吐
出できるようなもの等を使用できる。ノズル吐出部の形
状は、単に管の側面に穴を開けたものでもよいし、吐出
部から出た重合体ラテックスを槽内の流れ方向に導くた
めの側管を設けたものでもよい。浸漬ノズルは生産規模
にあわせて１本または２本以上の任意の本数を設けるこ
とができる。このようなノズルは、攪拌槽上部から液相
内に浸漬する方法や、槽壁面や槽底面から液相内に導入
する方法等で設置される。The shape of the immersion nozzle provided in the stirring tank is not particularly limited as long as it has a discharge section cross-sectional area of 40 mm 2 or more. For example, a single-tube structure type used exclusively for polymer latex discharge, a double-tube or more multi-tube type capable of discharging a polymer latex and a coagulant aqueous solution from respective discharge portions can be used. . The shape of the nozzle discharge portion may be one in which a hole is simply formed in the side surface of the tube, or one in which a side tube for guiding the polymer latex discharged from the discharge portion in the flow direction in the tank may be provided. One or more arbitrary number of immersion nozzles can be provided according to the production scale. Such a nozzle is installed by a method of dipping into the liquid phase from the top of the stirring tank, a method of introducing the nozzle into the liquid phase from the tank wall surface or the tank bottom, or the like.
【００１４】ノズル吐出部の断面積は４０ｍｍ2 以上で
あることが必要であって、４０ｍｍ 2 未満のノズルを使
用すると、ノズルが閉塞しやすくなるため長期安定な工
業生産が難しくなるし、吐出部断面積が小さいと生産規
模に応じて複数のノズルを設置することが必要となるの
で、設備コストの点からも好ましくない。また、浸漬ノ
ズルは、その吐出方向が攪拌槽内の流れと同じ向きにな
るように設けられることが重要である。例えば、三方後
退翼等の回転攪拌翼で攪拌され、回転軸を中心とする円
の円周方向の流れが主流である攪拌槽においては、吐出
方向がその円の接線方向と平行で、かつ回転軸の回転方
向と同じ向きになるようにノズルが設けられる。また、
プロペラ翼で攪拌し、軸流、すなわち翼の回転軸方向の
流れが主流である場合やタービン翼で攪拌し、輻流、す
なわち半径方向の流れが主流である場合には、それぞれ
その流れと平行で、かつ同じ向きになるようにノズルの
吐出方向が設定される。吐出方向が攪拌槽内の流れと異
なる向きになるようにノズルが設けられると、ノズルが
閉塞しやすくなり、生成する粒子も微細で嵩比重が低い
ものが増加して好ましくない。ノズルが設けられる浸漬
深さは攪拌槽の形状や攪拌方法によって異なり、特に制
限されるものではないが、攪拌槽内において比較的液流
の変動が小さい場所に吐出面が設置されることが好まし
い。例えば、攪拌翼を用いて攪拌する場合には、翼回転
部から深さ方向にある程度離れた位置が好ましい。翼回
転部に近い位置に設けると、ノズル吐出部周辺のスラリ
ー流速が大きいために吐出部付近の重合体ラテックスが
拡散し、生成する粒子の微細化や嵩比重の低下がみら
れ、また、吐出部付近を攪拌翼が通過する時に瞬間的に
スラリーの流れが変動してノズル閉塞の原因となるため
である。The sectional area of the nozzle discharge section is 40 mmTwo Above
Need to be 40mm Two Use a smaller nozzle
If used, the nozzle is likely to be blocked, so long-term stable
Production becomes difficult, and if the discharge area is small,
It is necessary to install multiple nozzles according to the model
This is not preferable from the viewpoint of equipment cost. In addition,
The spill is discharged in the same direction as the flow in the stirring tank.
It is important to be provided in such a way. For example, after three directions
A circle centered on the rotation axis, which is agitated by rotating agitating blades such as swept wings
In a stirred tank where the circumferential flow of
The direction is parallel to the tangent direction of the circle and the rotation axis
The nozzle is provided so as to be in the same direction as the direction. Also,
Stir with the propeller blades to produce axial flow,
When the flow is the main flow, or by stirring with turbine blades,
In other words, when the radial flow is the mainstream,
Set the nozzle so that it is parallel to the flow and in the same direction.
The ejection direction is set. The discharge direction is different from the flow in the stirring tank
When the nozzles are installed in a certain direction, the nozzles
Easy to block, fine particles and low bulk density
Things increase and it is not desirable. Immersion provided with nozzle
The depth depends on the shape of the stirring tank and the stirring method.
Although not limited, a relatively liquid flow
It is preferable that the discharge surface be installed in a place where
No. For example, when stirring with a stirring blade, the blade rotation
It is preferable that the position be somewhat away from the portion in the depth direction. Wing times
Slurry around the nozzle discharge section
ー Polymer latex near the discharge area due to high flow velocity
Diffusion and generation of fine particles and decrease in bulk specific gravity are seen.
Also, when the stirring blade passes near the discharge part,
Fluctuation of slurry flow may cause nozzle clogging
It is.
【００１５】重合体ラテックスはこのように設けられた
浸漬ノズルから、ノズル出口線速度が通常５０〜２００
ｍｍ／ｓの速度となるように、好ましくは５０〜１５０
ｍｍ／ｓの速度となるように吐出される。線速度が２０
０ｍｍ／ｓを超えると、ノズル吐出部付近の重合体ラテ
ックスが拡散し、生成する粒子の微細化や嵩比重の低
下、湿粉水分率の増加がみられ好ましくない。また、線
速度が５０ｍｍ／ｓ未満では、浸漬ノズルから安定に重
合体ラテックスを吐出することが難しくなり、ノズルの
閉塞を引き起こす可能性がある。一方、凝固剤はあらか
じめ攪拌槽内に供給されていてもよいし、重合体ラテッ
クスがノズルから吐出されている間に同時に槽内に添加
されてもよい。または、重合体ラテックスを槽内に導入
するノズルに２重管型のものを使用して、重合体ラテッ
クスと凝固剤を同時にそれぞれの吐出部から連続的に供
給する方法でもよい。しかし、本発明においては凝析工
程時における攪拌槽内スラリー中のグラフト重合体固形
分濃度が通常１５〜３０重量％、好ましくは、２０〜２
５重量％であることによって、より嵩比重が高く、湿粉
水分率の少ない粒子を得ることができる。したがってこ
のような条件を満たすように、凝固剤も重合体ラテック
スの吐出速度に応じて連続的に供給されることが好まし
い。グラフト重合体の固形分濃度が１５重量％未満では
嵩比重が低い粒子が得られ、固化工程でも２次凝集が起
こりにくくなり微粉が多く湿粉含水率の多い粒子が得ら
れる。一方、３０重量％を超えるとスラリー粘度が上昇
し、凝析槽の均一攪拌が困難になる。From the immersion nozzle provided in this manner, the polymer latex is supplied at a nozzle outlet linear velocity of usually 50 to 200.
mm / s, preferably 50-150
Discharge is performed at a speed of mm / s. Linear velocity is 20
If it exceeds 0 mm / s, the polymer latex in the vicinity of the nozzle discharge portion is diffused, and the resulting particles are unfavorably reduced in size, decreased in bulk specific gravity, and increased in moisture content of wet powder. If the linear velocity is less than 50 mm / s, it is difficult to stably discharge the polymer latex from the immersion nozzle, and there is a possibility that the nozzle may be blocked. On the other hand, the coagulant may be supplied to the stirring tank in advance, or may be simultaneously added to the tank while the polymer latex is being discharged from the nozzle. Alternatively, a double tube type nozzle may be used as a nozzle for introducing the polymer latex into the tank, and the polymer latex and the coagulant may be simultaneously and continuously supplied from respective discharge portions. However, in the present invention, the solid content of the graft polymer in the slurry in the stirring tank during the coagulation step is usually 15 to 30% by weight, preferably 20 to 2% by weight.
When the content is 5% by weight, particles having a higher bulk specific gravity and a lower moisture content of wet powder can be obtained. Therefore, it is preferable that the coagulant is also supplied continuously according to the discharge speed of the polymer latex so as to satisfy such a condition. When the solid content concentration of the graft polymer is less than 15% by weight, particles having a low bulk specific gravity are obtained, secondary aggregation hardly occurs even in the solidification step, and particles having a large amount of fine powder and a high moisture content in wet powder are obtained. On the other hand, if it exceeds 30% by weight, the slurry viscosity increases, and it becomes difficult to uniformly stir the coagulation tank.
【００１６】重合体ラテックスは攪拌槽内で凝固剤と接
触すると、グラフト重合体が凝固しスラリー溶液とな
る。この凝析工程における攪拌槽の液温は、グラフト重
合体の種類や、重合体ラテックスの吐出速度等によって
異なるが、通常５０℃〜８０℃、好ましくは６０〜８０
℃に保たれる。５０℃未満で凝析工程を行うと、この工
程で微粒子が多く発生し、ノズルの閉塞とそれにともな
う生産性の低下を引き起こし、得られる粒子も嵩比重が
低くブロッキングしやすいものとなりやすい。When the polymer latex comes into contact with a coagulant in a stirring tank, the graft polymer coagulates to form a slurry solution. The liquid temperature of the stirring tank in the coagulation step varies depending on the type of the graft polymer, the discharge speed of the polymer latex, and the like, but is usually 50 ° C to 80 ° C, preferably 60 to 80 ° C.
Kept at ° C. When the coagulation step is performed at a temperature lower than 50 ° C., a large amount of fine particles are generated in this step, which causes clogging of the nozzle and a reduction in productivity associated therewith, and the resulting particles tend to have low bulk specific gravity and easily block.
【００１７】上述した凝析工程で得られたスラリー溶液
は、次いで７０〜１００℃に保持され、凝固したグラフ
ト重合体は固化する。この場合の温度は、凝析工程での
スラリー温度より高温であることが好ましい。また、こ
こでは攪拌槽の液温が７０〜１００℃に保持されること
が重要であるが、より好ましくは、まず低温の７０〜９
０℃で保持され、その後高温の８０〜１００℃に加熱さ
れる２段階以上の温度設定条件下で行われる。この場
合、固化工程の最終温度は８０℃以上に設定することが
好ましい。最終温度が８０℃未満の条件で固化工程を行
うと、粒子の２次凝集が起こりにくくなり微粉が多く湿
粉水分率の高い粒子が得られ、その後の脱水、乾燥工程
でのエネルギーコストが増加し生産性が悪化する。ま
た、最終製品も微粒子が多く嵩比重の低いものとなり、
流動性が悪く、ブロッキングしやすいものとなってしま
う。The slurry solution obtained in the above coagulation step is then kept at 70 to 100 ° C. to solidify the solidified graft polymer. The temperature in this case is preferably higher than the slurry temperature in the coagulation step. Here, it is important that the temperature of the liquid in the stirring tank is maintained at 70 to 100 ° C.
This is performed under two or more temperature setting conditions in which the temperature is maintained at 0 ° C. and then heated to a high temperature of 80 to 100 ° C. In this case, the final temperature of the solidification step is preferably set to 80 ° C. or higher. When the solidification step is performed at a final temperature of less than 80 ° C., secondary aggregation of the particles is less likely to occur, and particles having a large amount of fine powder and a high moisture content in the wet powder are obtained, and the energy costs in the subsequent dehydration and drying steps increase. And the productivity deteriorates. In addition, the final product also has many fine particles and low bulk specific gravity,
It has poor fluidity and tends to block.
【００１８】以上説明したようにこのような製造方法に
よると、微粒子が少なく嵩比重の高い優れた粉体特性を
有するグラフト重合体粒子を得ることができる。また、
凝固以後の各工程において、凝固物の滞留や凝固物によ
る閉塞等のトラブルが起こらず、安定した工業生産を行
うことができる。さらに、有機溶媒を使用したり特殊な
設備を必要とすることなく、既存の設備を用いて、低い
生産コストで優れた粉体特性を有する重合体粒子が得ら
れる。As described above, according to such a production method, it is possible to obtain graft polymer particles having few fine particles and high bulk specific gravity and excellent powder characteristics. Also,
In each step after the solidification, troubles such as stagnation of the solidified matter and blockage by the solidified matter do not occur, and stable industrial production can be performed. In addition, polymer particles having excellent powder properties can be obtained at low production cost using existing equipment without using an organic solvent or special equipment.
【００１９】[0019]
【実施例】以下、本発明を実施例を示して具体的に説明
する。 〔ラテックスＡの調製〕撹拌機付耐圧反応容器にｔ−ド
デシルメルカプタン０．２重量部と牛脂酸ナトリウム
０．６重量部、デヒドロアビチエン酸カリウム１．４重
量部を含んだブタジエン９５重量部とスチレン５重量部
の単量体混合物と蒸留水１４５重量部、過硫酸カリウム
０．３重量部と無水硫酸ナトリウム０．２重量部を加え
て撹拌しながら７０℃で１０時間反応させて重合を完了
させた。このＳＢＲ重合体ラテックスをラテックスＡと
する。 〔ラテックスＢの調製〕撹拌機付反応容器にｔ−ブチル
ハイドロパーオキサイド０．５重量部を含んだメタクリ
ル酸１５重量部とブチルアクリレート８５重量部の単量
体混合物と硫酸第一鉄０．００３重量部、エチレンジア
ミン四酢酸ジナトリウム０．００９重量部、牛脂酸カリ
ウム１．８重量部、ジオクチルスルホコハク酸ナトリウ
ム３．６重量部を含む蒸留水１４５重量部を仕込み、６
３℃で４時間重合させた。この重合で得られた酸基含有
共重合体ラテックスをラテックスＢとする。 〔ラテックスＣの調製〕ラテックスＡ（重合体６０重量
部）にラテックスＢ（重合体１．３重量部）を加え、３
０分間低速撹拌を行った後、１％水酸化ナトリウム水溶
液を固形分換算で０．０９重量部添加しさらに３０分低
速撹拌保持することにより平均粒径が０．３μｍとなる
ように凝集したゴム状重合体ラテックスを得た。得られ
たゴム状重合体ラテックス１５７部（重合体６０重量
部）に３．９％Ｄ−グルコース水溶液を固形分換算で
０．４５重量部添加し、更に硫酸第一鉄０．００５重量
部とピロリン酸ナトリウム０．０１重量部を添加後、６
５℃に昇温、アクリロニトリル１１．６重量部、スチレ
ン２８．４重量部、ｔ−ドデシルメルカプタン０．７５
重量部、クメンハイドロパーオキサイド０．２重量部を
１４０分かけて滴下添加して重合を行い、滴下終了時に
クメンハイドロパーオキサイド０．０５重量部、更に３
０分後に同量のクメンハイドロパーオキサイドを添加し
て３０分重合を行いグラフト共重合体ラテックスＣ（固
形分濃度４０％）を得た。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. [Preparation of latex A] In a pressure-resistant reaction vessel equipped with a stirrer, 95 parts by weight of butadiene containing 0.2 parts by weight of t-dodecyl mercaptan, 0.6 parts by weight of sodium tallowate, and 1.4 parts by weight of potassium dehydroabithienate were added. Polymerization is completed by adding a monomer mixture of 5 parts by weight of styrene, 145 parts by weight of distilled water, 0.3 parts by weight of potassium persulfate and 0.2 parts by weight of anhydrous sodium sulfate, and reacting at 70 ° C. for 10 hours with stirring. I let it. This SBR polymer latex is referred to as Latex A. [Preparation of Latex B] In a reaction vessel equipped with a stirrer, a monomer mixture of 15 parts by weight of methacrylic acid containing 0.5 parts by weight of t-butyl hydroperoxide and 85 parts by weight of butyl acrylate, and 0.003 ferrous sulfate were used. 145 parts by weight of distilled water containing 0.009 parts by weight of disodium ethylenediaminetetraacetate, 1.8 parts by weight of potassium tallowate, and 3.6 parts by weight of sodium dioctylsulfosuccinate were added.
Polymerization was performed at 3 ° C. for 4 hours. The acid group-containing copolymer latex obtained by this polymerization is referred to as Latex B. [Preparation of latex C] Latex B (polymer 1.3 parts by weight) was added to latex A (polymer 60 parts by weight), and
After performing low-speed stirring for 0 minutes, a 0.09 part by weight of a 1% aqueous sodium hydroxide solution was added in terms of solid content, and the low-speed stirring and holding were further performed for 30 minutes to coagulate so that the average particle diameter became 0.3 μm. A polymer latex was obtained. To 157 parts (60 parts by weight of the polymer) of the obtained rubbery polymer latex, 0.45 parts by weight of a 3.9% D-glucose aqueous solution in terms of solid content was added, and further, 0.005 parts by weight of ferrous sulfate was added. After adding 0.01 parts by weight of sodium pyrophosphate, 6
The temperature was raised to 5 ° C, 11.6 parts by weight of acrylonitrile, 28.4 parts by weight of styrene, 0.75 t-dodecyl mercaptan.
Parts by weight and 0.2 parts by weight of cumene hydroperoxide were added dropwise over 140 minutes to carry out polymerization. At the end of the dropwise addition, 0.05 parts by weight of cumene hydroperoxide and 3 parts by weight were added.
0 minutes later, the same amount of cumene hydroperoxide was added and polymerization was carried out for 30 minutes to obtain a graft copolymer latex C (solid content concentration 40%).
【００２０】［実施例１］凝析槽、固化１槽、固化２槽
の全３槽構成から成る連続槽型凝固プロセス（密閉式連
続攪拌槽）を使用して、ラテックスＣの凝析および固化
を行った。凝析槽は内径１５００ｍｍの２ｍ3 オーバー
フローの丸底ガラス槽に、翼直径が８５０ｍｍの三方後
退翼を取り付けたものを使用した。この凝析槽には図１
に示すように内径ｒ1 が８０ｍｍのステンレス製パイプ
（底部１４は閉）からなる導入管１２に、長さｌ1 が３
００ｍｍ、内径ｒ2 が８０ｍｍの側管１３（吐出部１１
断面積：５０２７ｍｍ2 ）を設けた浸漬ノズル１０が、
槽上面からオーバーフロー口を起点として時計回りに９
０度と２７０度の位置に２本備えられており、この浸漬
ノズル１０を、導入管１２が液面１５に垂直で、吐出部
１１の深さｄ 1 が液面１５から４００ｍｍになるように
それぞれ設置した。吐出部１１から底部１４までの長さ
ｄ2 は１２０ｍｍであった。この際、吐出方向が撹拌槽
内の主流な流れ方向の向きになるように吐出部１１の向
きを設定した。続く固化１槽、２槽は内径２０００ｍｍ
の６ｍ3 オーバーフローの丸底ガラス槽に翼直径が９５
０ｍｍの三方後退翼を取り付けたものを使用した。次に
各槽の温度を凝析槽／固化１槽／固化２槽＝７０／７５
／８５℃に設定し、凝析槽の撹拌回転数を６５ｒｐｍ
（攪拌翼先端周速３２３３ｍｍ／ｓ）、固化１槽、固化
２槽をそれぞれ１００、１１０ｒｐｍで撹拌しながら、
上記調製したラテックスＣを５ｔ／ｈ（ラテックス線速
度＝１４３ｍｍ／ｓ）で上記の２本の浸漬ノズル１０の
吐出部１１から水平方向に吐出させ、凝固剤として１．
２％硫酸水溶液（ＤＳＡ）を５ｔ／ｈ［ラテックスＣ／
ＤＳＡ重量比＝１／１（凝析槽内重合体固形分濃度２０
重量％）］となるように凝析槽に滴下し、凝析および固
化を行った。ラテックスＣは２本のノズルから供給した
ので、１本あたりでは２．５ｔ／ｈであった。この条件
での凝固剤（ＤＳＡ）量は純分換算で重合体１００重量
部に対して３重量部であった。またこの間、３％水酸化
ナトリウム水溶液を固化１槽内に滴下し、槽内のｐＨが
２．５以下となるように調整したが、凝析槽内の実測ｐ
Ｈは１．７であった。各槽内が定常状態になった後、固
化２槽出口から凝固液スラリーをサンプリングした。サ
ンプリングしたスラリーを遠心脱水機（田辺上部排出型
Ｏ−２０型）で脱水処理（１８００ｒｐｍ：３分間）
した後、熱風温度を７０℃に設定したバッチ式流動乾燥
機を用いて乾燥した。こうして得られた重合体粒子の粉
体特性を測定した。その結果を表１に示す。なお、表１
中、凝析槽内固形分濃度の値は重量濃度である。粒度分
布の測定には日本工業規格（ＪＩＳ 第４０８号）によ
って規定されている評価機器を用いて行った。重合体粒
子の嵩比重（ｇ／ｃｍ3 ）測定はＪＩＳ−Ｋ−６７２１
に基づいて行い、粒子の流動性はこの嵩比重測定器に重
合体粒子８０ｇを入れ、ダンパーを取り外して単位時間
当たりの粒子流出量（単位：ｇ／ｓｅｃ．）を測定し
た。また、遠心脱水後の湿粉を箱形乾燥機で乾燥（１８
０℃：３０分）し、乾燥前後の重量変化から湿粉水分率
を、重合体重量部１００重量部に対した値（ｄｒｙ％）
として表した。なお、上記条件で３日間運転した後、吐
出部１１及び浸漬ノズル１０内部を確認したが、注目す
べき付着物はほとんど確認されなかった。[Example 1] Coagulation tank, solidification 1 tank, solidification 2 tank
Continuous solidification process consisting of a total of three tanks
Coagulation and solidification of latex C using continuous stirring tank)
Was done. The coagulation tank is 2m with an inner diameter of 1500mmThree over-
In the round bottom glass tank of the flow, after three sides with wing diameter of 850mm
The one with the swept wing was used. Fig. 1
Inner diameter r as shown in1 Is 80mm stainless steel pipe
(The bottom part 14 is closed) and the length l1 Is 3
00 mm, inner diameter rTwo Is 80 mm in side tube 13 (discharge unit 11
Cross-sectional area: 5027mmTwo ) Is provided,
Clockwise from the top of the tank starting from the overflow port 9
There are two at 0 and 270 degrees.
The nozzle 10 is set so that the introduction pipe 12 is perpendicular to the liquid surface 15 and
11 depth d 1 Is 400 mm from the liquid level 15
Each was installed. Length from discharge section 11 to bottom 14
dTwo Was 120 mm. At this time, the discharge direction is
Direction of the discharge unit 11 so that it is in the direction of the main flow direction inside
Was set. Subsequent solidification 1 tank, 2 tank inner diameter 2000mm
6mThree 95 wing diameter in overflow round bottom glass tank
The one equipped with a 0 mm three-way swept wing was used. next
Temperature of each tank is set to coagulation tank / solidification 1 tank / solidification 2 tank = 70/75
/ 85 ° C and the agitation speed of the coagulation tank is 65 rpm
(Circuit blade tip peripheral speed 3233 mm / s), solidification 1 tank, solidification
While stirring the two tanks at 100 and 110 rpm respectively,
5 t / h (latex linear velocity)
(Degree = 143 mm / s) of the above two immersion nozzles 10
It is discharged in the horizontal direction from the discharge part 11 and used as a coagulant.
5% t / h [Latex C /
DSA weight ratio = 1/1 (polymer solids concentration in coagulation tank 20
% By weight)] into the coagulation tank,
Was performed. Latex C was supplied from two nozzles
Therefore, it was 2.5 t / h per one. This condition
Of the coagulant (DSA) is 100 wt.
3 parts by weight per part. During this time, 3% hydroxylation
A sodium aqueous solution is dropped into one solidification tank, and the pH in the tank becomes
It was adjusted to be 2.5 or less.
H was 1.7. After the inside of each tank reaches a steady state,
The coagulation liquid slurry was sampled from the outlet of the chemical tank 2. Sa
Centrifugal dewatering machine (Tanabe upper discharge type)
O-20 type) and dehydration treatment (1800 rpm: 3 minutes)
After that, batch type fluidized drying with hot air temperature set to 70 ° C
It dried using the machine. Powder of polymer particles thus obtained
Body characteristics were measured. Table 1 shows the results. Table 1
The value of the solid concentration in the coagulation tank is the weight concentration. Particle size
According to Japanese Industrial Standards (JIS No. 408)
The evaluation was performed using an evaluation device specified as follows. Polymer particles
Bulk specific gravity (g / cmThree ) Measurement is JIS-K-6721
The fluidity of the particles is measured by this bulk density meter.
Put united particles 80g, remove the damper and unit time
Particle outflow per unit (g / sec.)
Was. The wet powder after centrifugal dehydration is dried with a box dryer (18
0 ° C: 30 minutes), and the moisture content of the wet powder is determined from the weight change before and after drying.
With respect to 100 parts by weight of the polymer (dry%)
Expressed as After driving for 3 days under the above conditions,
The outlet 11 and the inside of the immersion nozzle 10 were confirmed,
Almost no deposit was found.
【００２１】［比較例１］ラテックスＣを供給する浸漬
ノズル１０の本数を１本とし、備える位置を槽上面から
オーバーフロー口を起点として時計回りに９０度とした
以外は実施例１と同様にして、連続槽型凝固プロセスを
使用してラテックスＣの凝析および固化過程を行った。
ただし、ラテックスＣを５ｔ／ｈ［ラテックスＣ／ＤＳ
Ａ重量比＝１／１（凝析槽内重合体固形分濃度２０重量
％）］となるように１本の浸漬ノズル１０から供給した
ので、ラテックス線速度は２８５ｍｍ／ｓとした。凝析
槽内のスラリーの実測ｐＨは１．８であった。各槽内が
定常状態になった後、固化２槽出口から凝固液スラリー
をサンプリングし、実施例１と同様にして重合体粒子を
得て、粉体特性を測定した。その結果を表１に示す。な
お、上記条件で３日間運転した後、吐出部１１及び浸漬
ノズル１０内部を確認したが、注目すべき付着物はほと
んど確認されなかった。Comparative Example 1 The procedure of Example 1 was repeated, except that the number of the immersion nozzles 10 for supplying the latex C was one, and the position of the immersion nozzle was 90 degrees clockwise from the overflow port as a starting point from the upper surface of the tank. The coagulation and solidification process of latex C was performed using a continuous tank coagulation process.
However, 5 t / h of latex C [latex C / DS
A weight ratio = 1/1 (polymer solid content concentration in coagulation tank: 20% by weight)], so that the linear velocity of latex was 285 mm / s. The actually measured pH of the slurry in the coagulation tank was 1.8. After the inside of each tank was in a steady state, the coagulation liquid slurry was sampled from the outlet of the solidification tank 2, polymer particles were obtained in the same manner as in Example 1, and the powder characteristics were measured. Table 1 shows the results. After operating for 3 days under the above conditions, the inside of the discharge part 11 and the inside of the immersion nozzle 10 were checked, but almost no noticeable deposits were found.
【００２２】［実施例２］凝析槽、固化１槽、固化２槽
の全３槽構成から成る連続槽型凝固プロセス（密閉式連
続攪拌槽）を使用して、ラテックスＣの凝析および固化
を行った。凝析槽は内径１８０ｍｍの３リットルオーバ
ーフローのパイレックスガラス製丸底フラスコに、翼直
径が１２０ｍｍの三方後退翼を取り付けたものを使用し
た。この凝析槽には図２に示した、内径ｒ1 が８ｍｍの
ポリエチレン製Ｌ字管からなる浸漬ノズル１０（吐出部
１１断面積：５０ｍｍ2 ）が、槽上面からオーバーフロ
ー口を起点として時計回りに９０度の位置に１本備えら
れており、この浸漬ノズル１０を、導入管１２が液面１
５に垂直で、吐出部１１の深さｄ1 が液面１５から７０
ｍｍになるように設置した。導入管１２の中心線から吐
出部１１までの距離ｌ2 は３０ｍｍであった。この際、
吐出方向が撹拌槽内の主流な流れ方向の向きになるよう
に吐出部１１の向きを設定した。続く固化１槽、２槽は
内径１８０ｍｍの５リットルオーバーフローのパイレッ
クスガラス製丸底フラスコに、翼直径が１２０ｍｍの三
方後退翼を取り付けたものを使用した。次に各槽の温度
を凝析槽／固化１槽／固化２槽＝５５／７０／８５℃に
設定し、凝析槽の撹拌回転数を２００ｒｐｍ（攪拌翼先
端周速１２５６ｍｍ／ｓ）、固化１槽、固化２槽を２５
０ｒｐｍで撹拌しながら、上記調製したラテックスＣを
２．４ｇ／ｓ（ラテックス線速度＝５１ｍｍ／ｓ）で上
記の浸漬ノズル１０の吐出部１１から水平方向に吐出さ
せ、凝固剤として実施例１と同様の１．２％硫酸水溶液
（ＤＳＡ）を２．４ｇ／ｓ［ラテックスＣ／ＤＳＡ重量
比＝１／１（凝析槽内重合体固形分濃度２０重量％）］
となるように凝析槽に滴下し、凝析および固化を行っ
た。この条件での凝固剤（ＤＳＡ）量は純分換算で重合
体１００重量部に対して３重量部であった。またこの
間、３％水酸化ナトリウム水溶液を固化１槽内に滴下
し、槽内のｐＨが２．５以下となるように調整したが、
凝析槽内の実測ｐＨは１．８であった。各槽内が定常状
態になった後、固化２槽出口から凝固液スラリーをサン
プリングした。サンプリングした凝固液スラリーを実施
例１と同様にして処理し、得られた重合体粒子の粉体特
性を測定した。その結果を、表１に示す。なお、上記条
件で３時間運転した後、吐出部１１及び浸漬ノズル１０
内部を確認したが、ノズル１０内部についてはほとんど
確認されなかった。Example 2 Coagulation and solidification of latex C using a continuous tank-type solidification process (closed continuous stirring tank) consisting of a total of three tanks consisting of a coagulation tank, one solidification tank and two solidification tanks. Was done. The coagulation tank used was a Pyrex glass round-bottom flask having an inner diameter of 180 mm and overflowing 3 liters, fitted with a three-way sweeper blade having a blade diameter of 120 mm. In this coagulation tank, an immersion nozzle 10 (discharge section 11 cross-sectional area: 50 mm 2 ) made of a polyethylene L-shaped pipe having an inner diameter r 1 of 8 mm shown in FIG. One immersion nozzle 10 is provided at a position of 90 degrees,
5, the depth d 1 of the discharge part 11 is 70
mm. The distance l 2 from the center line of the introduction pipe 12 to the discharge section 11 was 30 mm. On this occasion,
The direction of the discharge unit 11 was set so that the discharge direction was the direction of the main flow direction in the stirring tank. The subsequent solidification tanks 1 and 2 used a 5-liter overflow Pyrex glass round bottom flask having an inner diameter of 180 mm and a three-way swept wing having a wing diameter of 120 mm. Next, the temperature of each tank was set to coagulation tank / solidification 1 tank / solidification 2 tank = 55/70/85 ° C., and the stirring rotation speed of the coagulation tank was set to 200 rpm (stirring blade tip peripheral speed 1256 mm / s). 1 tank, 2 solidification tanks 25
While stirring at 0 rpm, the prepared latex C was discharged horizontally at 2.4 g / s (latex linear velocity = 51 mm / s) from the discharge part 11 of the immersion nozzle 10 to obtain a coagulant as in Example 1. 2.4 g / s of the same 1.2% aqueous sulfuric acid solution (DSA) [weight ratio of latex C / DSA = 1/1 (polymer solid content concentration in coagulation tank: 20% by weight)]
Then, the mixture was dropped into a coagulation tank to perform coagulation and solidification. Under these conditions, the amount of the coagulant (DSA) was 3 parts by weight based on 100 parts by weight of the polymer in terms of pure content. During this period, a 3% aqueous solution of sodium hydroxide was dropped into one solidification tank to adjust the pH in the tank to 2.5 or less.
The actually measured pH in the coagulation tank was 1.8. After the inside of each tank was in a steady state, the coagulation liquid slurry was sampled from the outlet of the solidification 2 tank. The sampled coagulating liquid slurry was treated in the same manner as in Example 1, and the powder characteristics of the obtained polymer particles were measured. Table 1 shows the results. After operating for 3 hours under the above conditions, the discharge unit 11 and the immersion nozzle 10
Although the inside was confirmed, the inside of the nozzle 10 was hardly confirmed.
【００２３】［比較例２］ラテックスＣを供給する浸漬
ノズル１０を、実施例２に使用したものと同形状で、内
径ｒ1 のみが３．５ｍｍ（吐出部断面積１０ｍｍ2 ）で
あるものを使用した以外は、実施例２と同様にして凝析
および固化工程を行った。ただし、上記調製したラテッ
クスＣを２．６ｇ／ｓ（ラテックス線速度＝２６９ｍｍ
／ｓ）で上記の浸漬ノズル１０から水平方向に吐出さ
せ、ＤＳＡを２．６ｇ／ｓ［ラテックスＣ／ＤＳＡ重量
比＝１／１（凝析槽内重合体固形分濃度２０重量％）］
となるように凝析槽に滴下し、凝析および固化を行っ
た。この条件での凝固剤（ＤＳＡ）量は純分換算で重合
体１００重量部に対して３重量部であった。またこの
間、３％水酸化ナトリウム水溶液を固化１槽内に滴下
し、槽内のｐＨが２．５以下となるように調整したが、
凝析槽内の実測ｐＨは１．７であった。各槽内が定常状
態になった後、固化２槽出口から凝固液スラリーをサン
プリングし、実施例１と同様にして重合体粒子を得て、
粉体特性を測定した。その結果を表１に示す。なお、上
記条件で１時間運転した後、吐出部１１及び浸漬ノズル
１０内部を確認したが、ノズル１０内壁への凝析物の付
着状態はひどく、閉塞寸前の状態であった。[0023] Comparative Example 2 immersion nozzle 10 for supplying a latex C, and the same shape as that used in Example 2, only the inner diameter r1 use what is 3.5 mm (discharge cross-sectional area 10 mm 2) A coagulation and solidification step was performed in the same manner as in Example 2 except for the above. However, 2.6 g / s of the prepared latex C (latex linear velocity = 269 mm)
/ S) to discharge horizontally from the immersion nozzle 10 described above, DSA of 2.6 g / s [latex C / DSA weight ratio = 1/1 (polymer solids concentration in coagulation tank 20% by weight)]
Then, the mixture was dropped into a coagulation tank to perform coagulation and solidification. Under these conditions, the amount of the coagulant (DSA) was 3 parts by weight based on 100 parts by weight of the polymer in terms of pure content. During this period, a 3% aqueous solution of sodium hydroxide was dropped into one solidification tank to adjust the pH in the tank to 2.5 or less.
The measured pH in the coagulation tank was 1.7. After the inside of each tank was in a steady state, the solidification liquid slurry was sampled from the outlet of the solidification 2 tank, and polymer particles were obtained in the same manner as in Example 1.
Powder properties were measured. Table 1 shows the results. After operating for 1 hour under the above conditions, the inside of the discharge unit 11 and the immersion nozzle 10 was confirmed. However, the state of adhesion of the coagulated substance to the inner wall of the nozzle 10 was severe, and the state was just before the blockage.
【００２４】［比較例３］ラテックスＣを供給する浸漬
ノズル１０の本数を２本とし、備える位置を槽上面から
オーバーフロー口を起点として時計回りに９０度と２７
０度の位置とした以外は比較例２と同様にして、連続槽
型凝固プロセスを使用してラテックスＣの凝析および固
化過程を行った。ただし、ラテックスＣの線速度を２．
６ｇ／ｓとなるように２本の浸漬ノズル１０から供給し
たので、１本あたりでは１．３ｇ／ｓで、また、ラテッ
クス線速度は１３５ｍｍ／ｓとした。凝析槽内のスラリ
ーの実測ｐＨは１．７であった。各槽内が定常状態にな
った後、固化２槽出口から凝固液スラリーをサンプリン
グし、実施例１と同様にして重合体粒子を得て、粉体特
性を測定した。その結果を表１に示す。なお、上記条件
で１時間運転した後、吐出部１１及び浸漬ノズル１０内
部を確認したが、ノズル１０内壁への凝析物の付着状態
はひどく、１本のノズル１０が閉塞していた。[Comparative Example 3] The number of the immersion nozzles 10 for supplying the latex C was set to two, and the immersion nozzles were provided at 90 ° and 27 ° clockwise from the overflow port as a starting point from the top of the tank.
A coagulation and solidification process of latex C was carried out in the same manner as in Comparative Example 2 except that the position was set at 0 degree, using a continuous tank type coagulation process. However, the linear velocity of latex C was set at 2.
Since it was supplied from two immersion nozzles 10 so as to be 6 g / s, it was 1.3 g / s per one and the linear velocity of latex was 135 mm / s. The actually measured pH of the slurry in the coagulation tank was 1.7. After the inside of each tank was in a steady state, the coagulation liquid slurry was sampled from the outlet of the solidification tank 2, polymer particles were obtained in the same manner as in Example 1, and the powder characteristics were measured. Table 1 shows the results. After operating for 1 hour under the above conditions, the inside of the discharge unit 11 and the immersion nozzle 10 was confirmed. However, the adhesion state of the coagulated matter to the inner wall of the nozzle 10 was severe, and one nozzle 10 was closed.
【００２５】［比較例４］凝析槽に浸漬ノズル１０を設
けず、ラテックスＣを凝析槽に滴下添加し、凝析槽の撹
拌回転数を３０ｒｐｍ（攪拌翼先端周速１８８ｍｍ／
ｓ）、固化１槽、固化２槽の攪拌回転数をいずれも３０
ｒｐｍとした以外は実施例２と同様にして凝析および固
化を行った。凝析槽内のスラリーの実測ｐＨは１．９で
あった。各槽内が定常状態になった後、固化２槽出口か
ら凝固液スラリーをサンプリングし、実施例１と同様に
して重合体粒子を得て、粉体特性を測定した。その結果
を表１に示す。Comparative Example 4 Latex C was added dropwise to the coagulation tank without providing the immersion nozzle 10 in the coagulation tank, and the stirring speed of the coagulation tank was set to 30 rpm (the peripheral speed of the tip of the stirring blade was 188 mm /
s), the solidification 1 tank and the solidification 2 tank were all stirred at 30 rpm.
Coagulation and solidification were performed in the same manner as in Example 2 except that the rpm was changed to rpm. The actually measured pH of the slurry in the coagulation tank was 1.9. After the inside of each tank was in a steady state, the coagulation liquid slurry was sampled from the outlet of the solidification tank 2, polymer particles were obtained in the same manner as in Example 1, and the powder characteristics were measured. Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１から明かなように、実施例１および２
では、嵩比重が高く、平均粒径が大きく、流動性に優
れ、湿粉水分率の小さい粉体を、浸漬ノズル１０の閉塞
なしに安定に製造できる。As is clear from Table 1, Examples 1 and 2
Thus, a powder having a high bulk specific gravity, a large average particle size, excellent fluidity, and a low moisture content of wet powder can be stably produced without blocking the immersion nozzle 10.
【００２８】[0028]
【発明の効果】本発明の製造方法は、重合体ラテックス
を、吐出部断面積が４０ｍｍ2 以上であって吐出方向が
攪拌槽内の流れと同じ向きになるように設けられた浸漬
ノズルから、攪拌槽内に、ノズル出口線速度が５０〜２
００ｍｍ／ｓの速度となるように吐出して凝固剤と接触
させ、重合体を凝固させスラリー溶液を得る凝析工程
と、次いで、得られたスラリー溶液を７０〜１００℃に
保ち、固化させる固化工程とを有することを特徴とする
ものであるので、微粒子が少なく嵩比重の高い優れた粉
体特性を有するグラフト重合体粒子を安定に得ることが
できる。また、凝固以後の各工程において、凝固物の滞
留や凝固物による閉塞等のトラブルが起こらないので、
安定した工業生産を行うことができる。本発明の製造方
法はジエン系ゴム状重合体の含有量が３０〜８０重量％
であるグラフト重合体粒子に特に効果がある。凝析工程
における攪拌槽内スラリー中のグラフト重合体固形分濃
度を１５〜３０重量％とすることによって、より嵩比重
が高く、湿粉水分率の少ない粒子を得ることができる。
凝析工程における攪拌槽の液温を５０〜８０℃とするこ
とによって、各工程で閉塞等がおこらず、また、耐ブロ
ッキング性に優れた粒子を得ることができる。凝析工程
における攪拌槽内の攪拌を、攪拌翼の先端を４００〜４
０００ｍｍ／ｓの周速で回転させて行うことによって、
微粉の発生を抑えることができる。攪拌槽を密閉式連続
攪拌槽とすることによって、凝析工程と固化工程を連続
的に行えるので工業的に有利である。また、本発明の製
造方法によれば、有機溶媒等を使用せず、通常の攪拌槽
等の比較的安価な設備で製造可能であるので、低いコス
トで効率よく重合体を製造することができる。According to the production method of the present invention, the polymer latex is discharged from an immersion nozzle provided with a discharge section having a cross-sectional area of 40 mm 2 or more and the discharge direction being the same as the flow in the stirring tank. In the stirring tank, the nozzle outlet linear velocity is 50 to 2
A coagulation step of discharging at a speed of 00 mm / s and contacting with a coagulant to coagulate the polymer to obtain a slurry solution, and then to keep the obtained slurry solution at 70-100 ° C. to solidify Therefore, it is possible to stably obtain a graft polymer particle having excellent powder characteristics having few fine particles and high bulk specific gravity. In addition, in each step after coagulation, troubles such as clogging of the coagulated material due to stagnation or coagulated material do not occur.
Stable industrial production can be performed. In the production method of the present invention, the content of the diene rubber-like polymer is 30 to 80% by weight.
Is particularly effective for the graft polymer particles. By setting the graft polymer solid content concentration in the slurry in the stirring tank in the coagulation step to 15 to 30% by weight, particles having a higher bulk specific gravity and a lower moisture content in wet powder can be obtained.
By setting the liquid temperature of the stirring tank in the coagulation step to 50 to 80 ° C., it is possible to obtain particles having no blocking or the like and excellent blocking resistance in each step. The stirring in the stirring tank in the coagulation step was performed by
By rotating at a peripheral speed of 000 mm / s,
The generation of fine powder can be suppressed. When the stirring tank is a closed continuous stirring tank, the coagulation step and the solidification step can be performed continuously, which is industrially advantageous. Further, according to the production method of the present invention, a polymer can be produced efficiently at low cost without using an organic solvent or the like and can be produced with relatively inexpensive equipment such as a normal stirring tank. .
【図１】 本発明の実施例１で用いたラテックス吐出用
の浸漬ノズルを示す概略図である。FIG. 1 is a schematic view showing a immersion nozzle for discharging latex used in Example 1 of the present invention.
【図２】 本発明の実施例２で用いたラテックス吐出用
の浸漬ノズルを示す概略図である。FIG. 2 is a schematic diagram illustrating a immersion nozzle for discharging latex used in Example 2 of the present invention.
１０…浸漬ノズル、１１…吐出部 10 immersion nozzle, 11 discharge section
Claims (6)
とシアン化ビニルを含む単量体混合物をグラフト重合し
て得られる重合体ラテックスに、凝固剤を接触させてグ
ラフト重合体粒子を得る重合体の製造方法において、 重合体ラテックスを、攪拌槽内に、吐出部断面積が４０
ｍｍ2 以上であって吐出方向が攪拌槽内の流れと同じ向
きになるように設けられた浸漬ノズルから、ノズル出口
の線速度が５０〜２００ｍｍ／ｓの速度となるように吐
出して凝固剤と接触させ、グラフト重合体を凝固させス
ラリー溶液を得る凝析工程と、 次いで、得られたスラリー溶液を７０〜１００℃に保
ち、凝固したグラフト重合体を固化させる固化工程とを
有することを特徴とする重合体の製造方法。Claims: 1. A coagulant is brought into contact with a polymer latex obtained by graft-polymerizing a monomer mixture containing aromatic vinyl and vinyl cyanide onto a diene rubber-like polymer to obtain graft polymer particles. In the method for producing a polymer, a polymer latex is placed in a stirring tank and the discharge section has a cross-sectional area of 40.
from the immersion nozzle provided so as mm 2 or more at a the discharge direction is the same direction as the flow inside the stirring tank by discharging so that the linear speed of the nozzle outlet is the rate of 50 to 200 mm / s coagulant And a coagulation step of coagulating the graft polymer to obtain a slurry solution, followed by a solidification step of keeping the obtained slurry solution at 70 to 100 ° C. to solidify the coagulated graft polymer. A method for producing a polymer.
体の含有量が３０〜８０重量％であることを特徴とする
請求項１に記載の重合体の製造方法。2. The method for producing a polymer according to claim 1, wherein the content of the diene rubber-like polymer in the graft polymer is 30 to 80% by weight.
グラフト重合体固形分濃度が１５〜３０重量％であるこ
とを特徴とする請求項１に記載の重合体の製造方法。3. The method according to claim 1, wherein the solid content of the graft polymer in the slurry in the stirring tank in the coagulation step is 15 to 30% by weight.
８０℃であることを特徴とする請求項１に記載の重合体
の製造方法。4. The liquid temperature of the stirring tank in the coagulation step is 50 to 50.
The method for producing a polymer according to claim 1, wherein the temperature is 80 ° C.
拌翼の先端を４００〜４０００ｍｍ／ｓの周速で回転さ
せて行うことを特徴とする請求項１に記載の重合体の製
造方法。5. The method according to claim 1, wherein the stirring in the stirring tank in the coagulation step is performed by rotating the tip of the stirring blade at a peripheral speed of 400 to 4000 mm / s. .
特徴とする請求項１に記載の重合体の製造方法。6. The method for producing a polymer according to claim 1, wherein the stirring tank is a closed continuous stirring tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11037868A JP2000239315A (en) | 1999-02-16 | 1999-02-16 | Production of polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11037868A JP2000239315A (en) | 1999-02-16 | 1999-02-16 | Production of polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000239315A true JP2000239315A (en) | 2000-09-05 |
Family
ID=12509526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11037868A Pending JP2000239315A (en) | 1999-02-16 | 1999-02-16 | Production of polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000239315A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017061646A (en) * | 2015-09-25 | 2017-03-30 | 株式会社カネカ | Method for producing coagulated latex particles |
| JP2021501065A (en) * | 2017-11-08 | 2021-01-14 | エルジー・ケム・リミテッド | High molecular weight latex resin powder manufacturing equipment and manufacturing method |
| JP2021036010A (en) * | 2019-08-30 | 2021-03-04 | 日本ゼオン株式会社 | Production method of acrylic rubber containing reactive group |
| CN114805640A (en) * | 2022-04-20 | 2022-07-29 | 青岛科技大学 | Non-acid flocculation method of styrene-butadiene latex |
-
1999
- 1999-02-16 JP JP11037868A patent/JP2000239315A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017061646A (en) * | 2015-09-25 | 2017-03-30 | 株式会社カネカ | Method for producing coagulated latex particles |
| JP2021501065A (en) * | 2017-11-08 | 2021-01-14 | エルジー・ケム・リミテッド | High molecular weight latex resin powder manufacturing equipment and manufacturing method |
| JP2021036010A (en) * | 2019-08-30 | 2021-03-04 | 日本ゼオン株式会社 | Production method of acrylic rubber containing reactive group |
| CN114805640A (en) * | 2022-04-20 | 2022-07-29 | 青岛科技大学 | Non-acid flocculation method of styrene-butadiene latex |
| CN114805640B (en) * | 2022-04-20 | 2023-06-20 | 青岛科技大学 | Non-acid flocculation method for styrene-butadiene latex |
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