JPH05295008A - Suspension polymerization of vinyl chloride-based monomer - Google Patents
Suspension polymerization of vinyl chloride-based monomerInfo
- Publication number
- JPH05295008A JPH05295008A JP15024391A JP15024391A JPH05295008A JP H05295008 A JPH05295008 A JP H05295008A JP 15024391 A JP15024391 A JP 15024391A JP 15024391 A JP15024391 A JP 15024391A JP H05295008 A JPH05295008 A JP H05295008A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- suspension
- monomer
- polyvinyl acetate
- 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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は塩化ビニル系単量体の懸
濁重合方法に関し、さらに詳しくは、かさ比重が大き
く、適度な粒度を有し、かつゲル化性、粉体流動性に優
れた、成形加工性の改良された高品質の塩化ビニル系樹
脂を高生産性にて製造するための製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a suspension polymerization method for vinyl chloride-based monomers, and more specifically, it has a large bulk specific gravity, has an appropriate particle size, and is excellent in gelation property and powder fluidity. In addition, the present invention relates to a production method for producing a high-quality vinyl chloride resin with improved molding processability with high productivity.
【０００２】[0002]
【従来の技術】一般に、塩化ビニル系単量体の懸濁重合
は、懸濁剤の界面化学的作用と攪拌による機械的せん断
作用により単量体を水性媒体中に油滴として分散させ、
この油滴内に溶解した重合開始剤によって重合が開始し
進行するが、同時に液状の単量体油滴は重合の進行に伴
ってその粘度が増大し、ついには樹脂状の重合体粒子に
転化する。そして重合初期の転化率がおよそ５％に達す
るまでの過程において油滴単位の合体、分散が繰返し行
われ、この段階で粒子構造の基本骨格が形成される。塩
化ビニル系樹脂として最終的に得られる重合体粒子は、
複数の油滴単位から構成された凝集体であり、その内部
は空隙を有する微粒子の集合体である。2. Description of the Related Art Generally, in the suspension polymerization of vinyl chloride-based monomers, the monomers are dispersed as oil droplets in an aqueous medium by the interfacial chemical action of a suspending agent and the mechanical shearing action by stirring.
Polymerization is initiated and proceeds by the polymerization initiator dissolved in the oil droplets, but at the same time, the viscosity of the liquid monomer oil droplets increases with the progress of the polymerization, and finally the resin monomer-like polymer particles are converted. To do. Then, in the process of reaching a conversion rate of about 5% at the initial stage of polymerization, uniting and dispersion of the oil droplet units are repeated, and at this stage, the basic skeleton of the particle structure is formed. Polymer particles finally obtained as a vinyl chloride resin,
It is an aggregate composed of a plurality of oil droplet units, and the inside thereof is an aggregate of fine particles having voids.
【０００３】それ故に、塩化ビニル系単量体の懸濁重合
では、懸濁剤系の種類・量などの懸濁剤処方、攪拌速度
・動力などの攪拌条件、および液状単量体から樹脂状重
合体への転化速度、すなわち重合反応速度などの重合諸
条件が粒子構造を決定する上で非常に重要な因子となる
ものであり、これらの条件が樹脂の粒子構造に起因する
品質特性、例えば粒度、かさ比重、ゲル化性、粉体流動
性などを支配することが知られている。Therefore, in the suspension polymerization of vinyl chloride type monomers, the type and amount of the suspending agent system, the suspending agent formulation, the stirring conditions such as stirring speed and power, and the liquid monomer to resin state. The rate of conversion into a polymer, that is, various polymerization conditions such as the polymerization reaction rate are very important factors in determining the particle structure, and these conditions are quality characteristics due to the particle structure of the resin, for example, It is known to control particle size, bulk specific gravity, gelling property, powder fluidity and the like.
【０００４】従来、塩化ビニル系樹脂の押出成形時の加
工生産性を高めたり、バッチ混合器での処理量を増やす
ために、かさ比重が高く、ゲル化性に優れ、しかも適度
な粒度を有した粉体流動性、成形加工性に優れた樹脂が
要求されていた。このような要求に合致する樹脂を製造
するための懸濁重合方法として、例えば還流凝縮器を付
設した重合器を用い、初期仕込み時の水／単量体比を
０．８〜１．０とし、重合中に水を追加する方法（特公
平３−４５６１号）、重合中に単量体を追加する方法
（特開昭５０−９７６７９号）、重合中に重合温度を高
める方法（特開昭６１−２０７４１０号）などが開示さ
れているが、これらの方法は、かさ比重を高めるという
効果が不十分であるほか、重合系の懸濁安定性が不十分
であるために粗粒化したり、重合操作が煩雑になるなど
の問題点があった。Conventionally, in order to improve the processing productivity during extrusion molding of vinyl chloride resin and to increase the processing amount in a batch mixer, the bulk specific gravity is high, the gelation property is excellent, and the particle size is appropriate. There has been a demand for a resin having excellent powder fluidity and molding processability. As a suspension polymerization method for producing a resin that meets such requirements, for example, a polymerization vessel equipped with a reflux condenser is used, and the water / monomer ratio at the time of initial charging is set to 0.8 to 1.0. , A method of adding water during the polymerization (Japanese Patent Publication No. 3-4561), a method of adding a monomer during the polymerization (Japanese Patent Application Laid-Open No. 50-97679), and a method of increasing the polymerization temperature during the polymerization (Japanese Patent Application Laid-Open No. Sho-SHO). 61-207410) and the like are disclosed, but these methods are insufficient in the effect of increasing the bulk specific gravity, and coarsening due to insufficient suspension stability of the polymerization system, There was a problem that the polymerization operation became complicated.
【０００５】また懸濁剤処方に関する懸濁重合方法とし
て、複数種の部分ケン化ポリ酢酸ビニルおよびセルロー
ス誘導体を組み合わせて使用する方法が多数提案されて
いる。例えば、特公昭６３−３９６０６号、特公平１−
２７０８８号、特公平２−２２０８１号、特公平２−６
２１２１号、特開昭６１−１４１７０３号、特開昭６２
−２６０８０３号、特開昭６２−２６３２０６号、特開
昭６３−１５６８０９号、特開昭６３−２６４６１１
号、特開昭６３−２７５６０６号などである。As a suspension polymerization method relating to the formulation of a suspension agent, many methods have been proposed in which a plurality of kinds of partially saponified polyvinyl acetate and a cellulose derivative are used in combination. For example, Japanese Patent Publication No. 63-39606, Japanese Patent Publication No. 1-
No. 27088, Japanese Patent Publication No. 2-22081, Japanese Patent Publication No. 2-6
2121, JP-A-61-141703, JP-A-62.
-260803, JP-A-62-263206, JP-A-63-156809, JP-A-63-264611.
And JP-A-63-275606.
【０００６】しかしこれら従来技術に開示された処方に
は、確かにかさ比重を高める効果は認められるものの、
その効果が不十分であったり、あるいは粒度、ゲル化
性、粉体流動性など、その他の品質特性が劣るなどの欠
点があり、成形加工性の優れた樹脂を高生産性にて安定
的に得るための方法としては、未だ満足できるものでは
ない。However, although the formulas disclosed in these prior arts certainly have the effect of increasing the bulk specific gravity,
There are drawbacks such as insufficient effect or poor quality characteristics such as particle size, gelling property, powder flowability, etc., and resin with excellent moldability can be stably produced with high productivity. The way to get it is not yet satisfactory.
【０００７】[0007]
【発明が解決しようとする課題】本発明者らは前記欠点
を解決すべく鋭意研究を重ねた結果、特定の懸濁剤およ
び懸濁助剤を特定重量比で併用し、重合初期の攪拌動力
を特定範囲に制御して６時間以内に重合完結することに
より、かさ比重が高く、ゲル化性に優れ、しかも適度な
粒度を有した粉体流動性および成形加工性の改良された
塩化ビニル系重合体を高生産性にて製造できることを見
出し、本発明を完成するに至った。すなわち本発明の目
的は、高品質の塩化ビニル系重合体を高生産性で製造す
る改良された方法を提供することにある。DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors in order to solve the above-mentioned drawbacks, as a result, a specific suspending agent and a suspension aid were used in combination at a specific weight ratio, and stirring power at the initial stage of polymerization was used. By controlling the temperature within a specific range and completing the polymerization within 6 hours, a vinyl chloride-based resin having a high bulk specific gravity, excellent gelation properties, and an appropriate particle size and improved powder flowability and molding processability. They have found that a polymer can be produced with high productivity, and have completed the present invention. That is, the object of the present invention is to provide an improved method for producing a high-quality vinyl chloride polymer with high productivity.
【０００８】[0008]
【課題を解決するための手段】本発明のかかる目的は、
塩化ビニル系単量体を油溶性重合開始剤の存在下に水性
媒体中で懸濁重合するに際し、（Ａ）平均ケン化度６５
〜９５モル％の部分ケン化ポリ酢酸ビニルおよびヒドロ
キシプロピルメチルセルロースから成る群より選ばれた
少なくとも１種の懸濁剤、および（Ｂ）平均ケン化度１
５〜５５モル％の部分ケン化ポリ酢酸ビニルおよびＨＬ
Ｂ値が２〜１０の非イオン性界面活性剤から成る群より
選ばれた少なくとも１種の懸濁助剤の両者を、（Ａ）／
（Ｂ）の重量比が０．５〜２０となるよう併用し、かつ
重合開始から転化率が少なくとも５％に達するまでの期
間の重合器の内容液１m3あたりの正味攪拌動力を１．０
〜２．０kW／m3に制御して重合を行い、６時間以内に重
合完結させることによって達成される。The object of the present invention is to:
Upon suspension polymerization of a vinyl chloride-based monomer in an aqueous medium in the presence of an oil-soluble polymerization initiator, (A) average saponification degree of 65
To 95 mol% of partially saponified polyvinyl acetate and at least one suspending agent selected from the group consisting of hydroxypropyl methylcellulose, and (B) an average saponification degree of 1.
5-55 mol% partially saponified polyvinyl acetate and HL
(A) / both of at least one suspension aid selected from the group consisting of nonionic surfactants having a B value of 2 to 10
(B) is used in combination so that the weight ratio is 0.5 to 20, and the net stirring power per 1 m 3 of the content liquid in the polymerization vessel is 1.0 during the period from the initiation of polymerization until the conversion reaches at least 5%.
It is achieved by controlling the polymerization to ˜2.0 kW / m 3 and completing the polymerization within 6 hours.
【０００９】以下、本発明を詳細に説明する。本発明に
おいて、塩化ビニルと共重合し得る単量体としては、例
えば酢酸ビニルに代表されるアルキルビニルエステル
類、セチルビニルエーテルに代表されるアルキルビニル
エーテル類、エチレン、プロピレン等のα−モノオレフ
ィン類、アクリル酸メチル、メタクリル酸メチル等の
（メタ）アクリル酸アルキルエステル類、その他塩化ビ
ニリデン、スチレン等が例示されるが、共重合するもの
であればこれらに限定されない。The present invention will be described in detail below. In the present invention, as the monomer copolymerizable with vinyl chloride, for example, alkyl vinyl esters typified by vinyl acetate, alkyl vinyl ethers typified by cetyl vinyl ether, ethylene, α-monoolefins such as propylene, Examples thereof include (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate, and vinylidene chloride, styrene, and the like, but are not limited thereto as long as they can be copolymerized.
【００１０】本発明で使用する懸濁剤（Ａ）は、平均ケ
ン化度６５〜９５モル％の部分ケン化ポリ酢酸ビニルお
よびヒドロキシプロピルメチルセルロースから成る群よ
り選ばれた少なくとも１種である。これが部分ケン化ポ
リ酢酸ビニルから選択される場合は、ケン化度７０〜９
０モル％で、平均重合度が７００〜３０００のものが好
ましい。また、ヒドロキシプロピルメチルセルロースか
ら選択される場合には、メトキシ基含量２５〜３０重量
％、ヒドロキシプロポキシ基含量４〜１２重量％、およ
び２重量％水溶液の２０℃における粘度４０〜６０セン
チポイズのものが好ましい。The suspending agent (A) used in the present invention is at least one selected from the group consisting of partially saponified polyvinyl acetate having an average saponification degree of 65 to 95 mol% and hydroxypropylmethyl cellulose. If it is selected from partially saponified polyvinyl acetate, the degree of saponification is 70-9.
It is preferably 0 mol% and has an average degree of polymerization of 700 to 3000. Further, when selected from hydroxypropylmethyl cellulose, those having a methoxy group content of 25 to 30% by weight, a hydroxypropoxy group content of 4 to 12% by weight, and a 2% by weight aqueous solution having a viscosity of 40 to 60 centipoise at 20 ° C. are preferable. ..
【００１１】懸濁剤（Ａ）は水溶性成分であり、その分
散効果、懸濁保護効果により、粘度や粒子の凝集状態を
調節する作用を有することから、主懸濁剤、１次懸濁剤
などと呼ばれているのに対し、本発明で使用する成分
（Ｂ）は水に不溶ないしは難溶性であり、水性媒体中で
の懸濁重合に用いても界面活性能が小さいことから、一
般には懸濁助剤、補助懸濁剤、または２次懸濁剤などと
呼ばれている。本発明においては、これを懸濁助剤と称
する。The suspending agent (A) is a water-soluble component, and has a function of controlling the viscosity and the agglomeration state of particles due to its dispersing effect and suspension protecting effect. The component (B) used in the present invention is insoluble or sparingly soluble in water and has a low surface activity even when used in suspension polymerization in an aqueous medium, Generally, it is called a suspension auxiliary agent, an auxiliary suspension agent, a secondary suspension agent, or the like. In the present invention, this is called a suspension aid.
【００１２】本発明で用いる懸濁助剤（Ｂ）は、平均ケ
ン化度１５〜５５モル％の部分ケン化ポリ酢酸ビニルお
よびＨＬＢ値が２〜１０の非イオン性界面活性剤から成
る群より選ばれた少なくとも１種の化合物である。これ
が部分ケン化ポリ酢酸ビニルから選択される場合は、ケ
ン化度が３０〜５０モル％で重合度が２００〜８００の
範囲のものが好ましい。一方、ＨＬＢ値が２〜１０の非
イオン性界面活性剤としては、ソルビタンモノラウレー
ト、ソルビタンモノパルミテート、ソルビタン（モノ、
ジ、トリ）ステアレート、ソルビタンモノオレート等の
ソルビタン脂肪酸エステル類、ステアリン酸モノグリセ
ライド、オレイン酸モノグリセライド等のグリセリン脂
肪酸エステル類などが例示されるが、これらに限定され
ない。しかしながら、懸濁助剤（Ｂ）が前記の界面活性
剤から選択される場合には、ソルビタン脂肪酸エステル
類が好ましく、ソルビタンモノステアレートが特に好ま
しい。The suspension aid (B) used in the present invention is selected from the group consisting of partially saponified polyvinyl acetate having an average saponification degree of 15 to 55 mol% and a nonionic surfactant having an HLB value of 2 to 10. At least one compound selected. When this is selected from partially saponified polyvinyl acetate, those having a saponification degree of 30 to 50 mol% and a polymerization degree of 200 to 800 are preferable. On the other hand, as the nonionic surfactant having an HLB value of 2 to 10, sorbitan monolaurate, sorbitan monopalmitate, sorbitan (mono,
Examples thereof include, but are not limited to, sorbitan fatty acid esters such as di, tri) stearate and sorbitan monooleate, and glycerin fatty acid esters such as stearic acid monoglyceride and oleic acid monoglyceride. However, when the suspension aid (B) is selected from the abovementioned surfactants, sorbitan fatty acid esters are preferred and sorbitan monostearate is particularly preferred.
【００１３】懸濁助剤（Ｂ）は油溶性成分であり、単量
体油滴に溶解して油滴内部および表面に析出する微細重
合粒子の凝集を防止する作用を有するためと推察される
が、内部空隙に富み、スキン層の少ない重合体が得られ
るので、フィッシュアイや成形加工時のゲル化性、可塑
剤吸収性を改良する効果がある。The suspension aid (B) is an oil-soluble component, and it is presumed that it has the action of preventing the aggregation of fine polymer particles that dissolve in the monomer oil droplets and precipitate inside and on the surface of the oil droplets. However, since a polymer rich in internal voids and having a small skin layer is obtained, it has an effect of improving fish eye, gelling property at the time of molding and plasticizer absorbability.
【００１４】本発明においては、懸濁剤系として前記し
た懸濁剤（Ａ）および懸濁助剤（Ｂ）の両者の群からそ
れぞれ選択される各少なくとも１種を併用し、その重量
比（Ａ）／（Ｂ）を０．５〜２０、好ましくは１〜１０
とする。これが０．５に満たない場合には、樹脂のかさ
比重が低下するほか、製品樹脂中の微粉が増加して粉体
流動性が阻害される。また、この値が２０を越えると樹
脂のゲル化性が悪化するので、本発明の目的が達成でき
ない。懸濁剤（Ａ）の使用量は、通常、単量体１００重
量部あたり０．０３〜０．０８重量部の範囲である。In the present invention, at least one selected from the group consisting of both the above-mentioned suspending agent (A) and suspension aid (B) is used in combination as a suspending agent system, and the weight ratio ( A) / (B) is 0.5 to 20, preferably 1 to 10
And If this is less than 0.5, the bulk specific gravity of the resin decreases, and the fine powder in the product resin increases to impair the powder fluidity. On the other hand, if this value exceeds 20, the gelling property of the resin will deteriorate, so that the object of the present invention cannot be achieved. The amount of the suspending agent (A) used is usually in the range of 0.03 to 0.08 part by weight per 100 parts by weight of the monomer.
【００１５】本発明を実施するにあたり、まず予め脱気
した重合器に単量体、水、重合開始剤、および前記した
懸濁剤系を慣用の仕込み方法に従って仕込み、重合器の
ジャケットに熱媒体を循環させるなどの手段により、重
合器の内容物を攪拌下に所定の重合温度に昇温して重合
を開始させるのであるが、本発明においては、重合開始
から転化率が少なくとも５％、好ましくは１０〜３０％
に達するまでの期間、すなわち重合体粒子構造の基本骨
格が形成されるまでの間は、重合器の内容液１m3あたり
の正味攪拌動力を１．０〜２．０kW／m3、好ましくは
１．２〜１．６kW／m3に制御することが必須である。こ
の値が１．０kW／m3に満たない場合には、前記した懸濁
剤系を使用した場合でも、重合体粒子の粗粒化を招くほ
か、多孔性が損なわれてゲル化性が低下する。また、
２．０kW／m3を越えると、かさ比重が低下するばかりで
なく、粒度が細かくなるか、あるいはその他の重合条件
によっては粗粒が発生するという不利がある。転化率が
５％に達したのちの攪拌動力は特に限定されず、重合器
内が均一に攪拌されさえすればよい。In carrying out the present invention, first, a previously degassed polymerization vessel is charged with a monomer, water, a polymerization initiator, and the suspension agent system described above according to a conventional charging method, and a heating medium is placed in a jacket of the polymerization vessel. The content of the polymerization vessel is heated to a predetermined polymerization temperature with stirring to start the polymerization by a means such as circulating, but in the present invention, the conversion rate from the start of the polymerization is at least 5%, preferably Is 10 to 30%
Until the basic skeleton of the polymer particle structure is formed, the net stirring power per 1 m 3 of the content liquid in the polymerization vessel is 1.0 to 2.0 kW / m 3 , preferably 1 It is essential to control to 2 to 1.6 kW / m 3 . If this value is less than 1.0 kW / m 3 , even when the above-mentioned suspension agent system is used, polymer particles are coarsened and the porosity is impaired, resulting in a decrease in gelation property. To do. Also,
If it exceeds 2.0 kW / m 3 , not only the bulk specific gravity decreases, but also the particle size becomes fine, or coarse particles are generated depending on other polymerization conditions. The stirring power after the conversion reaches 5% is not particularly limited as long as the inside of the polymerization vessel is uniformly stirred.
【００１６】重合器の攪拌動力を制御する方法として
は、例えば「化学工学協会編：化学工学便覧、改訂三
版、１０６５〜１１１５頁、昭和４３年、丸善株式会
社」に詳細に記載されているように、各種形状の攪拌装
置についての攪拌系のレイノルズ数Ｒｅと動力数Ｎｐの
関係を表す実験式や線図を利用するか、またはある一定
の攪拌条件下での動力を実測することにより装置定数と
してのＮｐを実験的に求め、攪拌翼の回転数を変更する
ことによって動力を任意に調節することができる。A method for controlling the stirring power of the polymerization vessel is described in detail, for example, in "Chemical Engineering Association, edited by: Chemical Engineering Handbook, 3rd revised edition, pp. 1065-1115, 1968, Maruzen Co., Ltd." As described above, by using empirical formulas and diagrams showing the relationship between the Reynolds number Re and the power number Np of the stirring system for various types of stirring devices, or by measuring the power under a certain stirring condition The power can be arbitrarily adjusted by experimentally obtaining Np as a constant and changing the rotation speed of the stirring blade.
【００１７】すなわち、重合器の内容物の密度をρ（kg
／m3）、粘性係数をμ（kg／ｍ・sec)、攪拌翼の回転数
をｎ（１／sec)、翼スパンをｄ（ｍ）、動力換算係数を
ｇc（kg・ｍ／Kg・sec2）、減速機構部や軸封部での損
失を含まない正味の攪拌動力をＰ（Kg／ｍ・sec)とすれ
ば、ＲｅおよびＮｐはそれぞれ Ｒｅ＝ρｎｄ2 ／μ Ｎｐ＝Ｐ・ｇc ／ρｎ3 ｄ5 で定義されるものであり、公知文献または実験からＮｐ
を求めることができる。That is, the density of the contents of the polymerization vessel is ρ (kg
/ M 3 ), viscosity coefficient μ (kg / m · sec), stirring blade rotation speed n (1 / sec), blade span d (m), power conversion coefficient g c (kg · m / Kg)・ Sec 2 ), Re and Np are Re = ρnd 2 / μ Np = P ・, respectively, where P (Kg / m · sec) is the net stirring power that does not include loss in the speed reduction mechanism or shaft seal. It is defined by g c / ρn 3 d 5 , and Np is determined from known literature or experiments.
Can be asked.
【００１８】塩化ビニル系単量体の懸濁重合方法で一般
的に採用されている大型重合器の攪拌装置のＮｐの値は
およそ０．２〜２の範囲である。重合器内の液量をＶ
（m3）とすれば重合器の単位容積あたりの正味攪拌動力
Ｐｖ（kW／m3）は次式に従って算出することができる。 Ｐｖ＝Ｎｐ・ρｎ3 ｄ5 ・／１０２・Ｖ・ｇc したがって、特定の攪拌装置を用いて正味攪拌動力を調
整する場合には、動力は攪拌翼の回転数の３乗に比例す
るので、回転数を変更することにより動力を制御するこ
とができる。The Np value of the stirrer of a large-scale polymerization vessel which is generally employed in the suspension polymerization method of vinyl chloride type monomers is in the range of about 0.2 to 2. The amount of liquid in the polymerization vessel is V
If it is (m 3 ), the net stirring power Pv (kW / m 3 ) per unit volume of the polymerizer can be calculated according to the following equation. Pv = Npρn 3 d 5 102Vg c Therefore, when adjusting the net stirring power with a specific stirring device, since the power is proportional to the cube of the rotation speed of the stirring blade, The power can be controlled by changing the rotation speed.
【００１９】本発明において使用される攪拌翼や所望に
より使用されるバッフルなどの攪拌装置の形状は特に限
定されるものではなく、従来、塩化ビニル系単量体の懸
濁重量方法では一般的に採用されている公知の攪拌装置
を使用することができ、攪拌翼としてはタービン翼、フ
ァンタービン翼、ファウドラー翼およびブルーマージン
翼などが例示されるが、ファウドラー翼が好ましく、ま
たバッフルとしては板型、パイプ型、Ｄ型、ループ型お
よびＥ型（フィンガー型）などが例示されるが、パイプ
型、Ｄ型、Ｅ型のバッフルが好ましい。これらの攪拌翼
およびバッフルは塩化ビニルの重合で一般に使用されて
いるものでよく、例えば前記「化学工学便覧」または
「佐伯康治著：ポリマー製造プロセス、１５７〜１５９
ページ、１９７１年、工業調査会」などに説明されてい
る。The shape of a stirring device such as a stirring blade used in the present invention and a baffle used as desired is not particularly limited, and conventionally, in the suspension weight method of a vinyl chloride monomer, it has been generally used. A known stirring device that has been adopted can be used, and examples of stirring blades include turbine blades, fan turbine blades, Faudler blades, and Blue Margin blades, but Faudler blades are preferable, and baffles are plate-type. , Pipe type, D type, loop type and E type (finger type) are exemplified, but pipe type, D type and E type baffles are preferable. These stirring blades and baffles may be those commonly used in the polymerization of vinyl chloride. For example, the above "Handbook of Chemical Engineering" or "Koji Saeki: Polymer Manufacturing Process, 157-159".
Page, 1971, Industrial Research Board ".
【００２０】さらに本発明を実施するにあたっては、従
来工業的規模で採用されている内容積４０m3以上の大型
重合器では通常６時間を越えていた重合反応を、６時間
以内に完結させることが必須である。このような高速重
合を実施することにより液状単量体から樹脂状重合体へ
の転化速度が速まり、油滴どうしの離合集散の頻度、お
よびこの過程で油滴内部に生成する微小粒子の凝集状態
などが影響されるためと推定されるが、かさ比重の高い
重合体粒子を得ることが可能になる。しかも粉体の流動
性を阻害する微細な粒子の生成を抑制することができ、
成形加工時の樹脂の取扱性が改善されるという利点が伴
う。重合完結までの時間が６時間を越えると、かさ比重
や粉体流動性が低下するので本発明の目的が達成できな
い。Furthermore, in carrying out the present invention, it is possible to complete the polymerization reaction within 6 hours, which normally takes more than 6 hours in a large-scale polymerization vessel having an internal volume of 40 m 3 or more, which is conventionally used on an industrial scale. Required. By performing such high-speed polymerization, the conversion rate from liquid monomer to resinous polymer is increased, the frequency of separation and dispersion of oil droplets, and the aggregation of fine particles generated inside the oil droplets in this process. Although it is presumed that the state and the like are affected, it becomes possible to obtain polymer particles having a high bulk specific gravity. Moreover, it is possible to suppress the generation of fine particles that hinder the fluidity of the powder,
This is accompanied by the advantage that the handling of the resin during molding is improved. If the time until the completion of the polymerization exceeds 6 hours, the bulk specific gravity and the powder fluidity decrease, so that the object of the present invention cannot be achieved.
【００２１】なお本発明において重合完結までの時間、
すなわち重合時間とは、単量体などの各成分の仕込み終
了後昇温操作などにより重合器の内温が所定の重合温度
に達した時点から、重合器の圧力がその重合温度での自
然圧力で暫く推移した後未反応単量体の減少に伴って圧
力降下を始め、その降下巾が２kg／cm2 に達するまでの
時間と定義する。本発明における重合時間は、重合器の
温度制御や圧力管理などの安全面から３〜６時間とする
ことが好ましい。本発明において重合を完結させる方法
としては、重合禁止剤を添加したり、重合器から未反応
単量体を回収する方法が挙げられる。In the present invention, the time required to complete the polymerization,
That is, the polymerization time means the pressure of the polymerization vessel from the time when the internal temperature of the polymerization vessel reaches a predetermined polymerization temperature by the temperature rising operation after the completion of charging each component such as a monomer, and the natural pressure at the polymerization temperature. It is defined as the time until the pressure drop starts to decrease with the decrease of the unreacted monomer and reaches the drop width of 2 kg / cm 2 after a certain period of time. The polymerization time in the present invention is preferably 3 to 6 hours from the viewpoint of safety such as temperature control and pressure management of the polymerization vessel. Examples of the method of completing the polymerization in the present invention include a method of adding a polymerization inhibitor and a method of collecting unreacted monomers from the polymerization vessel.
【００２２】重合時間は公知のごとく、重合開始剤の使
用量で調節することができ、その使用量を増すことによ
って重合時間の短縮が可能である。本発明において６時
間以内に重合完結させるために使用する開始剤は、従来
から塩化ビニル系単量体の懸濁重合方法で一般的に使用
されていたものでよく、特に限定されないが、例えば
２，４，４−トリメチルペンチル−２−パーオキシネオ
デカノエート、ジ−２−エチルヘキシルパーオキシジカ
ーボネート、ジエトキシエチルパーオキシジカーボネー
ト、α−クミルパーオキシネオデカノエート、ｔ−ブチ
ルパーオキシネオデカノエート、ｔ−ブチルパーオキシ
ピバレート、３，５，５−トリメチルヘキサノイルパー
オキサイドおよびアセチルシクロヘキシルスルフォニル
パーオキサイドなどのような有機過酸化物、α，α′−
アゾビスイソブチロニトリルおよびα，α′−アゾビス
−２，４−ジメチルバレロニトリルなどのアゾ化合物が
挙げられ、これらの１種または２種以上の混合物が用い
られる。しかしながら１０時間半減期温度が３４〜５０
℃のパーエステル構造を有する開始剤を、重合に使用す
る全開始剤量の５０％以上使用することが好ましい。開
始剤の使用量は開始剤種類や重合温度によっても異なる
が、通常、単量体１００重量部あたり０．０２〜１重量
部の範囲である。As known in the art, the polymerization time can be adjusted by the amount of the polymerization initiator used, and the polymerization time can be shortened by increasing the amount used. In the present invention, the initiator used to complete the polymerization within 6 hours may be one that has been generally used in the conventional suspension polymerization method of vinyl chloride-based monomers and is not particularly limited, but for example, 2 , 4,4-Trimethylpentyl-2-peroxy neodecanoate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, α-cumylperoxy neodecanoate, t-butylperoxy Organic peroxides such as neodecanoate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide and acetylcyclohexylsulfonyl peroxide, α, α′-
Examples thereof include azo compounds such as azobisisobutyronitrile and α, α′-azobis-2,4-dimethylvaleronitrile, and one kind or a mixture of two or more kinds thereof is used. However, the 10-hour half-life temperature is 34 to 50
It is preferable to use the initiator having a perester structure at 0 ° C. in an amount of 50% or more of the total amount of the initiator used for the polymerization. The amount of the initiator used varies depending on the type of the initiator and the polymerization temperature, but is usually in the range of 0.02 to 1 part by weight per 100 parts by weight of the monomer.
【００２３】内容積４０m3以上の工業的規模の大型重合
器を用いて、本発明に従って６時間以内の高速重合を実
施するに際して多量の反応熱が発生するが、この反応熱
を除去するにあたって例えば特公平３−４２４９号に記
載された内部ジャケット式重合器、すなわち重合器本体
内面に冷熱媒体の通路を設けることにより伝熱性能を向
上させた重合器を用いれば、重合器の温度管理が容易に
なり、しかも熱除去に伴うスラリーの発泡や懸濁安定性
の低下などの悪影響もないので、本発明の目的を一層有
利に達成することができる。内部ジャケット式重合器と
しては重合時の総括伝熱係数が７００kcal／m2・hr・℃
以上の性能を有するものが好ましい。勿論、還流凝縮器
を用い、付加的に重合反応熱を除去する方法を採用する
ことも可能である。A large amount of heat of reaction is generated when high-speed polymerization is carried out within 6 hours according to the present invention using a large-scale industrial-scale polymerization vessel having an internal volume of 40 m 3 or more. For removing this reaction heat, for example, If the inner jacket type polymerizer described in Japanese Examined Patent Publication No. 3-4249, that is, the polymerizer having improved heat transfer performance by providing a passage for a cooling / heating medium on the inner surface of the main body of the polymerizer, temperature control of the polymerizer is easy. In addition, since there is no adverse effect such as foaming of the slurry and deterioration of suspension stability due to heat removal, the object of the present invention can be achieved more advantageously. As an inner jacket type polymerization vessel, the overall heat transfer coefficient during polymerization is 700 kcal / m 2 · hr · ° C.
Those having the above performance are preferable. Of course, it is also possible to employ a method in which a reflux condenser is used to additionally remove the heat of polymerization reaction.
【００２４】本発明を実施するにあたって還流凝縮器を
用いて熱除去を行う際には、重合中の還流凝縮器による
最大除熱割合を５０％未満として除熱を行う。ここで還
流凝縮器による除熱割合とは、重合反応に伴う発熱量に
対する還流凝縮器での除熱量の割合である。この割合が
５０％を越える場合には、スラリーの発泡により還流凝
縮器の伝熱面に重合体が付着堆積し、重合を繰り返し行
うと除熱が困難になるばかりでなく、単量体がスラリー
中から気化する際に重合系が激しく攪拌されるためと推
察されるが、懸濁安定性が損なわれて粗粒化したり、粒
子形状が不規則になり球状の樹脂を得ることができなく
なり、粉体流動性やかさ比重の低下を招くという不都合
が生じる。還流凝縮器の構造は特に限定されないが、一
般には多管式還流凝縮器が例示される。また、還流凝縮
器の使用方法は公知のいかなる方法をも採用することが
できるが、その最大除熱割合は５０％未満に制御する。When heat is removed by using a reflux condenser in carrying out the present invention, the heat is removed by setting the maximum rate of heat removal by the reflux condenser during polymerization to less than 50%. Here, the rate of heat removal by the reflux condenser is the rate of heat removal by the reflux condenser with respect to the amount of heat generated by the polymerization reaction. If this ratio exceeds 50%, the polymer adheres and deposits on the heat transfer surface of the reflux condenser due to the foaming of the slurry, which makes it difficult to remove heat when the polymerization is repeated, and the monomer is slurried. It is presumed that the polymerization system is vigorously stirred when vaporizing from the inside, but the suspension stability is impaired and coarse particles are generated, and it becomes impossible to obtain a spherical resin because the particle shape becomes irregular, There is an inconvenience that the powder fluidity and the bulk specific gravity are lowered. The structure of the reflux condenser is not particularly limited, but generally a multi-tube reflux condenser is exemplified. Any known method can be used as the reflux condenser, but the maximum heat removal rate is controlled to less than 50%.
【００２５】重合は通常、４０〜７０℃の温度で行わ
れ、所望に応じてメルカプトアルカノール、チオグリコ
ール酸アルキルエステルなどの連鎖移動剤、ｐＨ調整
剤、または重合禁止剤などを使用することもできる。水
は予め加温したものでもよく、また脱気したものでもよ
い。これらの各成分の仕込み量、部数、およびその他の
重合条件は、従来塩化ビニル系の重合で行われている慣
用の条件でよく、特に限定されるものではない。The polymerization is usually carried out at a temperature of 40 to 70 ° C., and if desired, a chain transfer agent such as mercaptoalkanol or thioglycolic acid alkyl ester, a pH adjusting agent, or a polymerization inhibitor may be used. .. The water may be preheated or degassed. The charged amount, the number of parts, and other polymerization conditions of each of these components may be conventional conditions conventionally used in vinyl chloride-based polymerization, and are not particularly limited.
【００２６】[0026]
【発明の効果】かくして本発明によれば、特定の懸濁剤
および懸濁助剤を特定重量比で併用し、さらに、重合粒
子の構造支配因子である攪拌動力、および重合反応速度
を特定範囲に制御することにより、粒度、かさ比重、ゲ
ル化性、粉体流動性など成形加工性に優れた塩化ビニル
系樹脂を得ることができ、しかも重合生産性を高めるこ
とができるという、従来技術では達成困難であった課題
を解決することができ、工業的見地から極めて有用であ
る。As described above, according to the present invention, a specific suspending agent and a suspending auxiliary agent are used together in a specific weight ratio, and further, the stirring power and the polymerization reaction rate, which are the structural controlling factors of the polymer particles, are within the specific ranges. It is possible to obtain a vinyl chloride resin excellent in molding processability such as particle size, bulk specific gravity, gelling property, powder fluidity, etc. It can solve problems that were difficult to achieve and is extremely useful from an industrial point of view.
【００２７】[0027]
【実施例】以下に実施例を挙げて本発明をさらに具体的
に説明する。なお、実施例、比較例の中の％および部
は、とくに断りのない限り重量基準である。また、塩化
ビニル系樹脂の物性値は次の方法により測定した。EXAMPLES The present invention will be described in more detail with reference to the following examples. In addition,% and parts in Examples and Comparative Examples are based on weight unless otherwise specified. The physical properties of the vinyl chloride resin were measured by the following methods.
【００２８】（１）平均粒径 ＪＩＳ基準の金網を使用した篩分析により、５０％通過
径として示した。(1) Average particle size The particle size was shown as 50% passing diameter by a sieve analysis using a JIS-standard wire mesh.
【００２９】（２）粗粒分 前記（１）の篩分析により、６０メッシュの金網に残留
する割合をもって示した。(2) Coarse Grain Content According to the sieve analysis of the above (1), it was shown as a ratio of remaining in the wire mesh of 60 mesh.
【００３０】（３）かさ比重 ＪＩＳ Ｋ６７２１に定める方法に準じて測定した値を
もって示した。(3) Bulk Specific Gravity It is shown as a value measured according to the method specified in JIS K6721.
【００３１】（４）粉体流動性 塩化ビニル系樹脂１２０mlが、ＪＩＳ Ｋ６７２１に定
めるかさ比重測定用ホッパーから、全量落下するのに要
する時間をもって示した。(4) Powder flowability The time required for all the vinyl chloride resin 120 ml to drop from the hopper for measuring the bulk specific gravity defined in JIS K6721 is shown.
【００３２】（５）ゲル化時間 東洋精機製作所製のラボプラストミルを使用し、ジャケ
ットの温度を１９０℃に保った容器内に塩化ビニル系樹
脂１００部（６５ｇ）、ステアリン酸鉛１部、三塩基性
硫酸鉛２．５部、二塩基性ステアリン酸鉛０．３部を投
入して３分間予熱した後、ローラーヘッドを３０rpm で
回転させながら混練を行い、混練トルクが安定し一定値
を示すまでの時間をもって示した。(5) Gelation time Using a Labo Plastomill manufactured by Toyo Seiki Seisakusho, 100 parts (65 g) of vinyl chloride resin, 1 part of lead stearate and 3 parts of vinyl chloride resin were placed in a container whose jacket temperature was maintained at 190 ° C. After adding 2.5 parts of basic lead sulfate and 0.3 part of dibasic lead stearate and preheating for 3 minutes, kneading is performed while rotating the roller head at 30 rpm, and the kneading torque is stable and shows a constant value. It was shown with the time until.
【００３３】実験番号１（実施例） 翼スパン１．７ｍのファウドラー型４枚後退攪拌翼およ
び外径０．２２ｍのパイプバッフル４本を装着した直径
３．２ｍ、内容積４５m3の内部ジャケット式ステンレス
製重合器を脱気した後、塩化ビニル単量体１００部（１
７．０トン）、水１１０部、懸濁剤としてケン化度が８
８モル％で平均重合度が２４００の部分ケン化ポリ酢酸
ビニル０．０５０部、懸濁助剤としてソルビタンモノス
テアレート０．０５０部、および重合開始剤として２，
４，４−トリメチルペンチル−２−パーオキシネオデカ
ノエート０．０５部を仕込み、攪拌翼の回転数を１１２
rpm に制御して攪拌下に重合器の内容物を温度５７℃に
昇温して、重合を開始させた。 Experiment No. 1 (Example) An inner jacket type with a diameter of 3.2 m and an internal volume of 45 m 3 equipped with four Faudler type backward stirring blades with a blade span of 1.7 m and four pipe baffles with an outer diameter of 0.22 m. After degassing the stainless steel polymerization vessel, 100 parts of vinyl chloride monomer (1
7.0 ton), 110 parts of water, saponification degree of 8 as suspending agent
0.050 part of partially saponified polyvinyl acetate having an average degree of polymerization of 2400 at 8 mol%, sorbitan monostearate 0.050 part as a suspension aid, and 2 as a polymerization initiator.
0.05 parts of 4,4-trimethylpentyl-2-peroxyneodecanoate was charged, and the stirring blade was rotated at 112 rpm.
The content of the polymerization vessel was heated to a temperature of 57 ° C. with stirring while controlling the rpm to start the polymerization.
【００３４】引続きこの回転数を維持し、重合器ジャケ
ットで反応熱を除去することにより内温を５７℃に保ち
ながら重合を継続させ、重合開始当初８．７kg／cm2 で
あった重合器の圧力が６．７kg／cm2 に降下した時点で
重合器から未反応単量体を回収し、重合完結させた。次
いで重合器の内容物を排出し、脱水乾燥することにより
塩化ビニル樹脂を得た。正味攪拌動力Ｐｖは重合開始時
１．５kW／m3であったが、その後重合の進行とともに徐
々に増加し、重合転化率が５％に達した時点では１．６
kW／m3を示した。重合時間は４．３時間であり、重合完
結時の転化率は８５％であった。By continuing to maintain this rotation speed and removing the reaction heat with the polymerization vessel jacket, the polymerization was continued while maintaining the internal temperature at 57 ° C., and the polymerization vessel was initially at 8.7 kg / cm 2 When the pressure dropped to 6.7 kg / cm 2 , the unreacted monomer was recovered from the polymerization vessel and the polymerization was completed. Then, the contents of the polymerization vessel were discharged and dehydrated and dried to obtain a vinyl chloride resin. The net stirring power Pv was 1.5 kW / m 3 at the start of the polymerization, but gradually increased with the progress of the polymerization thereafter, and was 1.6 at the time when the polymerization conversion rate reached 5%.
kW / m 3 is shown. The polymerization time was 4.3 hours, and the conversion rate at the completion of polymerization was 85%.
【００３５】実験番号２，３（実施例）および４，５（比較例） 表１に示した懸濁剤および懸濁助剤を用いた以外は、す
べて実験番号１と同一の条件で重合を行い、塩化ビニル
樹脂を得た。正味攪拌動力、重合時間、および重合完結
時の転化率はすべて実験番号１と同様であった。 Experiment Nos. 2 and 3 (Examples) and 4,5 (Comparative Examples) Polymerization was carried out under the same conditions as in Experiment No. 1 except that the suspending agents and suspension aids shown in Table 1 were used. Then, a vinyl chloride resin was obtained. The net stirring power, the polymerization time, and the conversion rate upon completion of the polymerization were all the same as in Experiment No. 1.
【００３６】実験番号１〜５の結果を対比して、表１に
示した。The results of Experiment Nos. 1 to 5 are shown in Table 1 in comparison.
【表１】 [Table 1]
【００３７】実験番号６，７（実施例）および８，９（比較例） 攪拌翼の回転数を表２に示した値となるよう制御するこ
とにより正味攪拌動力を調節した以外は、すべて実験番
号１と同一の条件で重合を行い、塩化ビニル樹脂を得
た。重合時間および重合完結時の転化率は、すべて実験
番号１と同様であった。 Experiment Nos. 6 and 7 (Examples) and 8 and 9 (Comparative Examples) All experiments were performed except that the net stirring power was adjusted by controlling the rotation speeds of the stirring blades to the values shown in Table 2. Polymerization was performed under the same conditions as No. 1 to obtain a vinyl chloride resin. The polymerization time and the conversion rate upon completion of the polymerization were all the same as in Experiment No. 1.
【００３８】実験番号１および６〜９の結果を対比し
て、表２に示した。The results of Experiment Nos. 1 and 6 to 9 are compared and shown in Table 2.
【表２】 [Table 2]
【００３９】実験番号１０，１１（実施例）および１２
〜１４（比較例） 表３に示した重合開始剤を用いることにより重合時間を
調節した以外は、すべて実験番号１と同一の条件で重合
を行い、塩化ビニル樹脂を得た。正味攪拌動力および重
合完結時の転化率は、すべて実験番号１と同様であっ
た。 Experiment Nos. 10, 11 (Example) and 12
-14 (Comparative example) Polymerization was performed under the same conditions as in Experiment No. 1 except that the polymerization time was adjusted by using the polymerization initiators shown in Table 3 to obtain a vinyl chloride resin. The net stirring power and the conversion rate upon completion of the polymerization were all the same as in Experiment No. 1.
【００４０】実験番号１および１０〜１４の結果を対比
して、表３に示した。The results of Experiment Nos. 1 and 10 to 14 are compared and shown in Table 3.
【表３】 [Table 3]
【００４１】実験番号１５〜１７（実施例）および１８（比較例） 実験番号１で用いた重合器の気相部に伝熱面積８０m2の
多管式還流凝縮器を連結し、重合器の内容物を昇温して
重合を開始させると同時に還流凝縮器に冷却水を通水し
て重合反応熱の除去を開始し、還流凝縮器による最大除
熱割合を表４に示した値に制御しながら重合を行い、重
合完結させた以外は、すべて実験番号１と同一の条件で
重合を行い、塩化ビニル樹脂を得た。正味攪拌動力、重
合時間および重合完結時の転化率は、すべて実験番号１
と同様であった。 Experiment Nos. 15 to 17 (Examples) and 18 (Comparative Examples) A multi-tube reflux condenser having a heat transfer area of 80 m 2 was connected to the gas phase part of the polymerization vessel used in Experiment No. At the same time as the contents are heated to start the polymerization, cooling water is passed through the reflux condenser to start the removal of the heat of the polymerization reaction, and the maximum heat removal rate by the reflux condenser is controlled to the value shown in Table 4. The polymerization was carried out under the same conditions as in Experiment No. 1 except that the polymerization was completed to obtain a vinyl chloride resin. The net stirring power, the polymerization time and the conversion rate at the completion of the polymerization were all in Experiment No. 1.
Was similar to.
【００４２】実験番号１５〜１８の結果を対比して、表
４に示した。The results of Experiment Nos. 15 to 18 are shown in Table 4 in comparison.
【表４】 [Table 4]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石井 靖道 岡山県倉敷市児島塩生字新浜2767の１ 日 本ゼオン株式会社内 (72)発明者 大川 正久 愛媛県新居浜市惣開町５番１号 住友化学 工業株式会社内 (72)発明者 大内 勲 福島県いわき市錦町落合16 呉羽化学工業 株式会社内 (72)発明者 若森 秀樹 福島県いわき市錦町落合16 呉羽化学工業 株式会社内 (72)発明者 大和 多実男 山口県徳山市晴海町１番２号 サン・アロ ー化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasumichi Ishii 1767, Niihama Shiojima, Kurashiki-shi, Okayama Zeon Corporation (72) Inventor Masahisa Okawa 5-5 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Industry Co., Ltd. (72) Inventor Isao Ouchi 16 Kuchiha Chemical Industry Co., Ltd. 16 Nishiki-cho, Iwaki-shi, Fukushima Prefecture (72) Inventor Hideki Wakamori 16 Ochiai Nishiki-cho, Iwaki-shi, Fukushima Prefecture (72) Inventor Yamato Tamio 1-2 Harumi-cho, Tokuyama City, Yamaguchi Prefecture Sun Arrow Chemical Co., Ltd.
Claims (3)
共重合し得る単量体と塩化ビニルとの混合物から選ばれ
た塩化ビニル系単量体を油溶性重合開始剤の存在下に水
性媒体中で懸濁重合するに際し、 （Ａ）平均ケン化度６５〜９５モル％の部分ケン化ポリ
酢酸ビニルおよびヒドロキシプロピルメチルセルロース
から成る群より選ばれた少なくとも１種の懸濁剤、およ
び （Ｂ）平均ケン化度１５〜５５モル％の部分ケン化ポリ
酢酸ビニルおよびＨＬＢ値が２〜１０の非イオン性界面
活性剤から成る群より選ばれた少なくとも１種の懸濁助
剤の両者を、（Ａ）／（Ｂ）の重量比が０．５〜２０と
なるよう併用し、かつ重合開始から転化率が少なくとも
５％に達するまでの期間の重合器の内容液１m3あたりの
正味攪拌動力を１．０〜２．０kW／m3に制御して重合を
行い、６時間以内に重合完結させることを特徴とする塩
化ビニル系単量体の懸濁重合方法。1. A vinyl chloride monomer selected from a vinyl chloride monomer or a mixture of a vinyl chloride and a monomer copolymerizable with vinyl chloride and vinyl chloride in an aqueous medium in the presence of an oil-soluble polymerization initiator. (A) at least one suspending agent selected from the group consisting of partially saponified polyvinyl acetate having an average saponification degree of 65 to 95 mol% and hydroxypropylmethylcellulose, and (B) Both a partially saponified polyvinyl acetate having an average degree of saponification of 15 to 55 mol% and at least one suspension aid selected from the group consisting of nonionic surfactants having an HLB value of 2 to 10, A) / (B) are used together in a weight ratio of 0.5 to 20, and the net stirring power per 1 m 3 of the content liquid in the polymerization vessel during the period from the initiation of polymerization until the conversion rate reaches at least 5%. 1.0~2.0kW / m 3 Control to perform polymerization, suspension polymerization vinyl chloride monomer, wherein the polymerization completed within 6 hours.
熱媒体の通路を設けた内容積４０m3以上の内部ジャケッ
ト式大型重合器を用いることを特徴とする請求項１記載
の塩化ビニル系単量体の懸濁重合方法。2. A vinyl chloride-based polymerizer according to claim 1, wherein a large-capacity inner jacket type polymerization reactor having an internal volume of 40 m 3 or more, equipped with a stirring device and provided with a passage for a cooling / heating medium on the inner surface of the polymerization reactor main body, is used. Method of suspension polymerization of monomers.
流凝縮器による最大除熱割合を５０％未満に制御して重
合を行うことを特徴とする請求項１または２記載の塩化
ビニル系単量体の懸濁重合方法。3. The vinyl chloride system according to claim 1, wherein the polymerization is carried out by using a polymerization vessel equipped with a reflux condenser and controlling the maximum heat removal rate by the reflux condenser to less than 50%. Method of suspension polymerization of monomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3150243A JP2574078B2 (en) | 1991-06-21 | 1991-06-21 | Suspension polymerization of vinyl chloride monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3150243A JP2574078B2 (en) | 1991-06-21 | 1991-06-21 | Suspension polymerization of vinyl chloride monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05295008A true JPH05295008A (en) | 1993-11-09 |
| JP2574078B2 JP2574078B2 (en) | 1997-01-22 |
Family
ID=15492696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3150243A Expired - Lifetime JP2574078B2 (en) | 1991-06-21 | 1991-06-21 | Suspension polymerization of vinyl chloride monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2574078B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006321946A (en) * | 2005-05-20 | 2006-11-30 | Shin Dai-Ichi Vinyl Corp | Method for producing vinyl chloride-based polymer |
| JP2006322013A (en) * | 2006-09-08 | 2006-11-30 | Sekisui Chem Co Ltd | Method for producing chlorinated vinyl chloride-based resin |
| CN100408604C (en) * | 2001-11-05 | 2008-08-06 | 株式会社吴羽 | Production process of vinylidene chloride resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578206A (en) * | 1980-06-17 | 1982-01-16 | Shin Etsu Chem Co Ltd | Suspension polymerization of vinyl chloride type monomer |
| JPS6118562U (en) * | 1984-07-06 | 1986-02-03 | 中央無線株式会社 | Yoke assembly for image pickup tube |
| JPS6339606A (en) * | 1986-08-06 | 1988-02-20 | Nippon Kokan Kk <Nkk> | Removing method for suspended matter, organic substance and dissolved inorganic substance contained in water |
| JPS63264611A (en) * | 1987-04-22 | 1988-11-01 | Shin Etsu Chem Co Ltd | Preparation of vinyl chloride polymer |
| JPS6418082A (en) * | 1987-06-19 | 1989-01-20 | Ampex | Method and apparatus for recording and reproducing radar signal information |
| JPS6438411A (en) * | 1987-08-05 | 1989-02-08 | Sun Arrow Kagaku Kk | Vinyl chloride resin and its preparation |
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1991
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578206A (en) * | 1980-06-17 | 1982-01-16 | Shin Etsu Chem Co Ltd | Suspension polymerization of vinyl chloride type monomer |
| JPS6118562U (en) * | 1984-07-06 | 1986-02-03 | 中央無線株式会社 | Yoke assembly for image pickup tube |
| JPS6339606A (en) * | 1986-08-06 | 1988-02-20 | Nippon Kokan Kk <Nkk> | Removing method for suspended matter, organic substance and dissolved inorganic substance contained in water |
| JPS63264611A (en) * | 1987-04-22 | 1988-11-01 | Shin Etsu Chem Co Ltd | Preparation of vinyl chloride polymer |
| JPS6418082A (en) * | 1987-06-19 | 1989-01-20 | Ampex | Method and apparatus for recording and reproducing radar signal information |
| JPS6438411A (en) * | 1987-08-05 | 1989-02-08 | Sun Arrow Kagaku Kk | Vinyl chloride resin and its preparation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408604C (en) * | 2001-11-05 | 2008-08-06 | 株式会社吴羽 | Production process of vinylidene chloride resin |
| JP2006321946A (en) * | 2005-05-20 | 2006-11-30 | Shin Dai-Ichi Vinyl Corp | Method for producing vinyl chloride-based polymer |
| JP4504251B2 (en) * | 2005-05-20 | 2010-07-14 | 新第一塩ビ株式会社 | Method for producing vinyl chloride polymer |
| JP2006322013A (en) * | 2006-09-08 | 2006-11-30 | Sekisui Chem Co Ltd | Method for producing chlorinated vinyl chloride-based resin |
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| Publication number | Publication date |
|---|---|
| JP2574078B2 (en) | 1997-01-22 |
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