JPH11217404A - Manufacture of vinyl chloride polymer - Google Patents
Manufacture of vinyl chloride polymerInfo
- Publication number
- JPH11217404A JPH11217404A JP2204898A JP2204898A JPH11217404A JP H11217404 A JPH11217404 A JP H11217404A JP 2204898 A JP2204898 A JP 2204898A JP 2204898 A JP2204898 A JP 2204898A JP H11217404 A JPH11217404 A JP H11217404A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- charged
- monomer
- polymerization
- chloride monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化ビニル単量
体、又は、塩化ビニル単量体及び塩化ビニル単量体と共
重合可能な単量体との混合物（以下、塩化ビニル系単量
体という。）の懸濁重合法において、水性媒体および塩
化ビニル系単量体の仕込み時間、昇温時間を短縮するこ
とにより、塩化ビニル系重合体製造時の重合工程の生産
性を向上させ、スケール付着防止をはかり、併せて得ら
れる塩化ビニル系重合体のフィッシュアイの改善、粒度
分布をシャープとする塩化ビニル系重合体の製造法に関
するものである。The present invention relates to a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer (hereinafter referred to as a vinyl chloride monomer). In the suspension polymerization method, the productivity of the polymerization step in the production of the vinyl chloride-based polymer is improved by shortening the charging time of the aqueous medium and the vinyl chloride-based monomer and the time required for raising the temperature. The present invention relates to a method for producing a vinyl chloride polymer in which the fish eye of a vinyl chloride polymer obtained in addition to the adhesion prevention is improved and the particle size distribution is sharpened.
【０００２】[0002]
【従来の技術】通常、塩化ビニル系単量体の懸濁重合は
バッチ式で行われ、塩化ビニル系重合体の製造の際に
は、重合反応器に水性媒体、懸濁剤、重合開始剤および
添加剤を仕込んだ後、重合系内を脱気して塩化ビニル系
単量体等を仕込み、攪拌しながら重合反応器のジャケッ
トに温水循環または水蒸気を通し、重合温度まで昇温し
て重合反応を開始させる。その後、重合反応熱が出てき
た時点から重合反応器のジャケットに冷却水を通して重
合温度を一定に保つべく冷却を行い、所定の重合率に到
達するまで重合反応を継続する。そして、重合反応終了
後、塩化ビニル系単量体等の未反応単量体を回収し、塩
化ビニル系重合体を反応器から排出する一連の重合操作
を行っている。2. Description of the Related Art Generally, a suspension polymerization of a vinyl chloride monomer is carried out in a batch system. When a vinyl chloride polymer is produced, an aqueous medium, a suspending agent, and a polymerization initiator are supplied to a polymerization reactor. After adding the additives and additives, the inside of the polymerization system is degassed and the vinyl chloride monomer and the like are charged.While stirring, warm water circulation or steam is passed through the jacket of the polymerization reactor, and the temperature is raised to the polymerization temperature to perform polymerization. Initiate the reaction. Thereafter, from the point when the polymerization reaction heat is generated, cooling is carried out by passing cooling water through the jacket of the polymerization reactor to keep the polymerization temperature constant, and the polymerization reaction is continued until a predetermined polymerization rate is reached. After the completion of the polymerization reaction, a series of polymerization operations for recovering an unreacted monomer such as a vinyl chloride monomer and discharging the vinyl chloride polymer from the reactor are performed.
【０００３】しかし、このような従来法においては、内
容積に対して伝熱面積の小さい大型の重合反応器では昇
温に長時間を要し、このことが塩化ビニル系重合体の生
産性低下の一因となっている。However, in such a conventional method, it takes a long time to raise the temperature in a large polymerization reactor having a small heat transfer area with respect to the internal volume, which lowers the productivity of the vinyl chloride polymer. Is one of the causes.
【０００４】このような問題を解決するため、種々の方
法が提案されている。[0004] In order to solve such a problem, various methods have been proposed.
【０００５】例えば加温水を用いた昇温時間短縮の方法
として、特公昭５８−５０６０３号公報には、３０℃以
下の水、懸濁剤と重合開始剤をオートクレーブに仕込
み、その後塩化ビニル系単量体を仕込み、攪拌混合した
後加温水を仕込んで重合を開始する方法、特開平４−２
４８８０４号公報には、常温の水性媒体、懸濁剤を仕込
み、攪拌を開始した後塩化ビニル系単量体、重合開始剤
及び加温水を仕込んで重合を開始する方法、特開昭６０
−４７００７号公報には、塩化ビニル系単量体、重合開
始剤、分散安定剤等を４０℃以下の温度で均一混合した
後、加温水を仕込む方法などが提案されている。For example, as a method of shortening the heating time using heated water, Japanese Patent Publication No. 58-50603 discloses that an autoclave is charged with water at 30 ° C. or lower, a suspending agent and a polymerization initiator, and then a vinyl chloride-based monomer is added. A method of charging a polymer, stirring and mixing, and then adding warm water to initiate polymerization.
JP-A-48804 discloses a method in which an aqueous medium at normal temperature and a suspending agent are charged, stirring is started, and then a vinyl chloride monomer, a polymerization initiator and heated water are charged to start polymerization.
Japanese Patent No. 47007 proposes a method in which a vinyl chloride monomer, a polymerization initiator, a dispersion stabilizer and the like are uniformly mixed at a temperature of 40 ° C. or lower, and then heated water is charged.
【０００６】さらに、加温水を用いた昇温時間の短縮
と、加温水及び塩化ビニル系単量体を同時に仕込む仕込
時間の短縮を組み合わせた方法としては、特公昭６０−
２６４８８号公報には、重合開始剤が全量溶解した塩化
ビニル系単量体及び分散安定剤が全量溶解した加温水を
５０％以上同時に仕込む方法、特公平７−１１９２４７
号公報には、塩化ビニル系単量体及び加温水を７０％以
上を同時に仕込み、少なくとも２０％の分散安定剤を塩
化ビニル系単量体仕込み中に仕込み、重合開始剤を塩化
ビニル系単量体全量の３０〜１００％仕込む間、かつ重
合反応器内の塩化ビニル系単量体の水に対する重量比が
１．５以下の時点で全量仕込む方法などが提案されてい
る。Further, as a method combining the shortening of the heating time using heated water and the shortening of the charging time for simultaneously charging the heated water and the vinyl chloride monomer, Japanese Patent Publication No.
Japanese Patent Publication No. 26488 discloses a method in which 50% or more of a vinyl chloride monomer in which a polymerization initiator is completely dissolved and heated water in which a dispersion stabilizer is entirely dissolved are simultaneously charged by 50% or more.
In the publication, a vinyl chloride monomer and warming water are simultaneously charged at 70% or more, at least 20% of a dispersion stabilizer is charged during the vinyl chloride monomer charging, and a polymerization initiator is used as a vinyl chloride monomer. A method has been proposed in which the total amount is charged while 30 to 100% of the total amount of the body is charged and when the weight ratio of the vinyl chloride monomer to water in the polymerization reactor is 1.5 or less.
【０００７】[0007]
【発明が解決しようとする課題】しかし、３０℃以下の
水、懸濁剤及び重合開始剤をオートクレーブに仕込み、
その後塩化ビニル系単量体を仕込み、攪拌混合した後加
熱した水を仕込んで重合を開始する特公昭５８−５０６
０３号公報に記載の方法や、常温の水性媒体、懸濁剤を
仕込み、攪拌を開始した後塩化ビニル系単量体、重合開
始剤及び加温水を仕込んで重合を開始する特開平４−２
４８８０４号公報に記載の方法では、加熱した水を使用
することにより、重合温度への昇温時間の短縮は図れる
が、低温水と高温水といった２種類の温度の異なる水を
使用するため操作が煩雑であると共に、昇温時間短縮の
ためには１種類の温水を使用する場合に比べて予め低温
水が仕込まれている分、必然的に高温の水を使用する必
要があり、温水の温度が高いと重合反応が急激に開始さ
れるため重合反応器内壁へのスケールの発生や粗粒の生
成といった問題を有している。However, water at 30 ° C. or lower, a suspending agent and a polymerization initiator are charged into an autoclave,
Thereafter, a vinyl chloride monomer is charged, the mixture is stirred and mixed, and then heated water is charged to initiate polymerization.
JP-A-4-2, in which an aqueous medium and a suspending agent at room temperature are charged, stirring is started, and then a vinyl chloride monomer, a polymerization initiator and heated water are charged to start polymerization.
In the method described in JP-A-48804, the time for raising the temperature to the polymerization temperature can be shortened by using heated water, but the operation is performed because two types of water having different temperatures, such as low-temperature water and high-temperature water, are used. In addition to the complexity, it is necessary to use high-temperature water because the low-temperature water is preliminarily used in order to shorten the heating time. When the content is high, the polymerization reaction is rapidly started, which causes problems such as generation of scale on the inner wall of the polymerization reactor and generation of coarse particles.
【０００８】一方、１種類の温水を使用する方法とし
て、塩化ビニル系単量体、重合開始剤、分散安定剤等を
４０℃以下の温度で均一混合した後、加温水を仕込む特
開昭６０−４７００７号公報に記載の方法では、重合開
始剤を含んだ塩化ビニル系単量体を加温水より先に仕込
むことから塩化ビニル系単量体が直接重合反応器壁面と
接触した状態となり、ここに加温水を仕込むことにより
重合が開始されるので、塩化ビニル系重合体が重合反応
器壁面に付着しスケールとなり、得られる塩化ビニル重
合体のフィッシュアイの悪化をもたらす。また、塩化ビ
ニル系単量体の仕込後に加温水を仕込むため、塩化ビニ
ル系単量体中に加温水が分散した状態（塩化ビニル系単
量体が連続相）から、加温水中に塩化ビニル系単量体が
分散する状態（塩化ビニル単量体が分散相）への相転移
が起こるため、粗粒の生成や粒度分布が広くなるといっ
た品質上の問題を有する。さらに、相転移が起こらなけ
れば重合反応器内で塩化ビニル系重合体が塊状となり重
合器から排出できないという生産上の大きな問題を引き
起こす。On the other hand, as a method of using one kind of warm water, a method of uniformly mixing a vinyl chloride monomer, a polymerization initiator, a dispersion stabilizer and the like at a temperature of 40 ° C. or less and then adding warm water is disclosed in In the method described in JP-A-47007, a vinyl chloride-based monomer containing a polymerization initiator is charged before heating water, so that the vinyl chloride-based monomer comes into direct contact with the polymerization reactor wall surface. The polymerization is started by charging warm water into the reactor, so that the vinyl chloride polymer adheres to the wall of the polymerization reactor to form a scale, resulting in deterioration of fish eyes of the obtained vinyl chloride polymer. In addition, since heated water is charged after the vinyl chloride monomer is charged, the state in which the heated water is dispersed in the vinyl chloride monomer (the continuous phase of the vinyl chloride monomer) is changed into the heated water. Since a phase transition to a state in which the system monomer is dispersed (a vinyl chloride monomer is in a dispersed phase) occurs, there is a quality problem that coarse particles are formed and a particle size distribution is widened. Furthermore, if the phase transition does not occur, the vinyl chloride-based polymer becomes a lump in the polymerization reactor and cannot be discharged from the polymerization reactor, which causes a serious problem in production.
【０００９】また、加温水を用いた昇温時間の短縮と、
加温水と塩化ビニル系単量体を同時に仕込む仕込時間の
短縮を組み合わせた方法のうち、重合開始剤が全量溶解
した塩化ビニル系単量体と、分散安定剤が全量溶解した
加温水を５０％以上同時に仕込む特公昭６０−２６４８
８号公報に記載の方法は、重合開始剤を塩化ビニル系単
量体に溶解して仕込むため、塩化ビニル系単量体の温度
を低温に保持するか、あるいは重合活性の低い重合開始
剤を用いる必要があり、塩化ビニル系単量体の温度を低
温に保持する場合は昇温時間の短縮が図れず、また重合
活性の低い重合開始剤を使用する場合は重合時間の短縮
が図れないため、生産性向上の効果が小さい。さらに昇
温時間を短縮するためには、塩化ビニル系単量体の温度
が低い分、より高温の水を使用する必要があり、重合反
応器内壁へのスケールの付着や粗粒の生成が問題とな
る。また、分散安定剤を加温水に溶解し仕込む場合、加
温水の温度が分散安定剤の曇点を超えると分散安定剤が
析出するため仕込配管等へ付着し仕込みが困難となるた
め、曇点の高い分散安定剤を使用するか、あるいは配管
内への付着を防止する措置を高じなければならないとい
った問題を有する。[0009] Further, shortening of the heating time using heated water,
Among the methods combining the shortening of the charging time in which the warming water and the vinyl chloride monomer are simultaneously charged, 50% of the vinyl chloride monomer in which the polymerization initiator is completely dissolved and the warm water in which the dispersion stabilizer is completely dissolved are 50%. Tokubo Sho-2648 to be charged simultaneously
In the method described in JP-A No. 8 (1996) -1989, a polymerization initiator is dissolved in a vinyl chloride-based monomer and charged, so that the temperature of the vinyl chloride-based monomer is kept low or a polymerization initiator having a low polymerization activity is used. It is necessary to use, because when the temperature of the vinyl chloride monomer is kept at a low temperature, the time required for raising the temperature cannot be shortened, and when a polymerization initiator having low polymerization activity is used, the polymerization time cannot be shortened. The effect of improving productivity is small. In order to further reduce the temperature rise time, it is necessary to use higher-temperature water because of the lower temperature of the vinyl chloride monomer, which causes problems such as adhesion of scale to the inner wall of the polymerization reactor and formation of coarse particles. Becomes In addition, when the dispersion stabilizer is dissolved in warm water and charged, if the temperature of the heated water exceeds the cloud point of the dispersion stabilizer, the dispersion stabilizer precipitates and adheres to the charging pipe or the like, making the charging difficult. It is necessary to use a dispersion stabilizer having a high water content or to take measures to prevent adhesion to the piping.
【００１０】塩化ビニル系単量体と加温水を７０％以上
同時に仕込み、少なくとも２０％の分散安定剤を塩化ビ
ニル系単量体仕込み中に仕込み、重合開始剤を塩化ビニ
ル系単量体全量の３０〜１００％仕込む間、かつ重合器
内の単量体の水に対する重量比が１．５以下の時点で全
量仕込む特公平７−１１９２４７号公報に記載の方法
は、塩化ビニル系単量体仕込中に分散安定剤を少なくと
も２０％仕込むため分散安定剤の濃度にむらができるた
め、粒度分布が広くなるという問題があった。さらに、
塩化ビニル系単量体と加温水の同時仕込みでは、塩化ビ
ニル系単量体と加温水の仕込比率の制御を行わない場
合、塩化ビニル系単量体と水性媒体の相転移が起こる恐
れがあり、特に生産性向上のために１バッチ当たりの塩
化ビニル系単量体の仕込量を多くした場合、塩化ビニル
系単量体に対する加温水の比率が小さくなるため、塩化
ビニル系単量体や加温水の仕込タイミングや仕込速度の
微妙なコントロールが必要となる。At least 70% of a vinyl chloride monomer and warming water are simultaneously charged, at least 20% of a dispersion stabilizer is charged during the charging of the vinyl chloride monomer, and a polymerization initiator is added to the total amount of the vinyl chloride monomer. The method described in Japanese Patent Publication No. 7-119247, in which the entire amount is charged during the charging of 30 to 100% and at the time when the weight ratio of the monomer in the polymerization vessel to water is 1.5 or less, is based on the method of charging the vinyl chloride monomer. Since at least 20% of the dispersion stabilizer is charged therein, the concentration of the dispersion stabilizer can be uneven, so that there is a problem that the particle size distribution is widened. further,
In the simultaneous charging of the vinyl chloride monomer and the warming water, if the ratio of the vinyl chloride monomer and the warming water is not controlled, phase transition between the vinyl chloride monomer and the aqueous medium may occur. In particular, if the amount of the vinyl chloride monomer charged per batch is increased to improve productivity, the ratio of the heated water to the vinyl chloride monomer becomes small. Fine control of hot water charging timing and charging speed is required.
【００１１】そこで、本発明の目的は、上記課題を解決
した塩化ビニル系重合体の製造時の生産性に優れ、得ら
れる塩化ビニル系重合体の粒度分布がシャープであり、
フィッシュアイが改善される塩化ビニル系重合体の製造
法を提供することにある。Therefore, an object of the present invention is to provide a vinyl chloride polymer which is excellent in productivity in solving the above-mentioned problems, has a sharp particle size distribution of the obtained vinyl chloride polymer,
It is an object of the present invention to provide a method for producing a vinyl chloride polymer having improved fish eyes.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、前記課題
を解決し重合工程のサイクル時間を短縮すべく鋭意検討
を進めた結果、特定の条件にて塩化ビニル系重合体の製
造を行うことにより、重合時間の短縮による重合工程の
サイクル時間の短縮を達成できるとともに、得られる塩
化ビニル系重合体のフィッシュアイ、粒度分布を損なう
ことなく、また、スケールの付着のないことを見出し本
発明を完成させるに至った。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems and to shorten the cycle time of the polymerization step. As a result, the present inventors have produced a vinyl chloride polymer under specific conditions. By this, it was possible to achieve a reduction in the cycle time of the polymerization step by shortening the polymerization time, and it was found that the resulting vinyl chloride polymer did not impair the fisheye and particle size distribution and that there was no scale adhesion. Was completed.
【００１３】即ち、本発明は、塩化ビニル系単量体を重
合開始剤及び分散安定剤の存在下、水性媒体中で懸濁重
合を行い塩化ビニル系重合体を製造する方法において、
攪拌下にて、分散安定剤の全量及び用いるべき塩化ビニ
ル系単量体に対して３０〜５０重量％に相当する４０℃
以上の水性媒体を重合反応器に仕込み、その後、引き続
き重合反応器内の塩化ビニル系単量体に対する水性媒体
の重量比を０．８以上に維持しながら塩化ビニル系単量
体及び４０℃以上の水性媒体を仕込み、かつ重合開始剤
を塩化ビニル系単量体の仕込量が用いるべき塩化ビニル
系単量体の５０重量％以上１００重量％未満の範囲とな
った時点で仕込むことを特徴とする塩化ビニル系重合体
の製造法に関するものである。That is, the present invention relates to a method for producing a vinyl chloride polymer by subjecting a vinyl chloride monomer to suspension polymerization in an aqueous medium in the presence of a polymerization initiator and a dispersion stabilizer.
Under stirring, 40 ° C. corresponding to 30 to 50% by weight based on the total amount of the dispersion stabilizer and the vinyl chloride monomer to be used.
The above aqueous medium was charged into a polymerization reactor, and thereafter, while maintaining the weight ratio of the aqueous medium to the vinyl chloride monomer in the polymerization reactor at 0.8 or more, the vinyl chloride monomer and 40 ° C. or more And the polymerization initiator is charged when the charged amount of the vinyl chloride-based monomer is in the range of 50% by weight or more and less than 100% by weight of the vinyl chloride-based monomer to be used. And a method for producing a vinyl chloride polymer.
【００１４】以下、本発明について更に詳細に説明す
る。Hereinafter, the present invention will be described in more detail.
【００１５】本発明において用いられる塩化ビニル系単
量体とは、塩化ビニル単量体、又は、塩化ビニル単量体
及び塩化ビニル単量体との共重合可能な単量体との混合
物であり、塩化ビニル単量体との共重合可能な単量体と
しては、塩化ビニル単量体との共重合が可能な単量体で
あればいかなるものも使用することができ、例えばエチ
レン，プロピレン等のオレフィン類、酢酸ビニル，ステ
アリン酸ビニル等のビニルエステル類、エチルビニルエ
ーテル，セチルビニルエーテル等のビニルエーテル類、
アクリル酸メチル，アクリル酸エチル，アクリル酸ブチ
ル，アクリル酸プロピル等のアクリル酸エステル類、マ
レイン酸，フマル酸のエステル類または無水物、スチレ
ン等の芳香族ビニル化合物、アクリロニトリル等の従来
から塩化ビニルと共重合可能な単量体として知られてい
る単量体が挙げられる。そして、該共重合可能な単量体
は、塩化ビニル単量体に対し通常２０重量％以下の割合
で使用することが好ましい。The vinyl chloride monomer used in the present invention is a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer. As the monomer copolymerizable with the vinyl chloride monomer, any monomer that can be copolymerized with the vinyl chloride monomer can be used, for example, ethylene, propylene, etc. Olefins, vinyl esters such as vinyl acetate and vinyl stearate, vinyl ethers such as ethyl vinyl ether and cetyl vinyl ether,
Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate and propyl acrylate; esters or anhydrides of maleic acid and fumaric acid; aromatic vinyl compounds such as styrene; and vinyl chloride such as acrylonitrile. Examples include monomers known as copolymerizable monomers. The copolymerizable monomer is preferably used at a ratio of usually 20% by weight or less based on the vinyl chloride monomer.
【００１６】本発明において用いられる４０℃以上の水
性媒体とは、重合反応器内への仕込み時に４０℃以上の
温度を保持している水性媒体であり、予め４０℃以上に
加温しておいても、仕込中に加温しても差し支えない。
そして、該水性媒体は、重合反応器内の温度制御が容易
に行え、特に粒度分布、ロールフィッシュアイに優れた
塩化ビニル系重合体が得られることから４０℃以上９０
℃以下の水性媒体であることが好ましい。The aqueous medium having a temperature of 40 ° C. or higher used in the present invention is an aqueous medium which maintains a temperature of 40 ° C. or higher when charged into a polymerization reactor. Or warming during the preparation.
The aqueous medium can easily control the temperature in the polymerization reactor, and can obtain a vinyl chloride polymer having excellent particle size distribution and roll fish eye.
It is preferably an aqueous medium at a temperature of not more than ° C.
【００１７】本発明において用いられる４０℃以上の水
性媒体とは、水又は水を主成分とする媒体であり、本発
明の目的を逸脱しない限りにおいていかなるものを含ん
でも問題ない。The aqueous medium having a temperature of 40 ° C. or higher used in the present invention is water or a medium containing water as a main component, and may include any medium without departing from the object of the present invention.
【００１８】本発明において用いられる重合開始剤とし
ては、一般に重合開始剤として知られているものを用い
ることができ、例えばジイソプロピルパーオキシジカー
ボネート、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等
のパーオキシカーボネート化合物；ｔ−ブチルパーオキ
シネオデカノエート、α−クミルパーオキシネオデカノ
エート、ｔ−ヘキシルパーオキシビバレート、ｔ−アミ
ルパーオキシネオデカノエート、１，１−ジメチル−３
−ヒドロキシブチルパーオキシネオデカノエート、ｔ−
ヘキシルパーオキシジグリコレート、α−クミルパーオ
キシネオデカネート等のパーオキシエステル化合物；ア
セチルシクロヘキシルスルホニルパーオキシド等の過酸
化物；アゾビス（２，４−ジメチルバレロニトリル），
アゾビス（４−メトキシ−２，４−ジメチルバレロニト
リル）等のアゾ化合物；過酸化水素等を挙げることがで
き、これらは一種単独または二種以上の組合わせで使用
することも可能である。As the polymerization initiator used in the present invention, those generally known as polymerization initiators can be used. For example, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl Peroxy carbonate compounds such as peroxy dicarbonate; t-butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, t-hexyl peroxy vivalate, t-amyl peroxy neodecanoate, 1 , 1-dimethyl-3
-Hydroxybutyl peroxy neodecanoate, t-
Peroxyester compounds such as hexylperoxydiglycolate and α-cumylperoxyneodecanate; peroxides such as acetylcyclohexylsulfonyl peroxide; azobis (2,4-dimethylvaleronitrile);
An azo compound such as azobis (4-methoxy-2,4-dimethylvaleronitrile); hydrogen peroxide; and the like, and these can be used alone or in combination of two or more.
【００１９】そして、本発明において重合開始剤は、塩
化ビニル系単量体１００重量部に対して０．００１〜１
重量部の範囲で使用することが好ましい。In the present invention, the polymerization initiator is used in an amount of 0.001 to 1 based on 100 parts by weight of the vinyl chloride monomer.
It is preferred to use in the range of parts by weight.
【００２０】本発明の方法において用いられる分散安定
剤としては特に限定はなく、一般的に懸濁重合の分散安
定剤として使用されているもので良く、例えばメチルセ
ルロース，ヒドロキシエチルセルロース，ヒドロキシプ
ロピルセルロース，ヒドロキシプロピルメチルセルロー
ス等のセルロース誘導体；部分けん化ポリビニルアルコ
ール、アクリル酸重合体、ゼラチン等の水溶性ポリマ
ー；ノニオン界面活性剤；アニオン界面活性剤等が挙げ
られ、これらは一種単独でまたは二種以上組合わせ使用
することも可能である。The dispersion stabilizer used in the method of the present invention is not particularly limited, and those generally used as suspension stabilizers in suspension polymerization may be used. For example, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl cellulose, and the like may be used. Cellulose derivatives such as propylmethylcellulose; water-soluble polymers such as partially saponified polyvinyl alcohol, acrylic acid polymer, and gelatin; nonionic surfactants; anionic surfactants; and the like, used alone or in combination of two or more. It is also possible.
【００２１】該分散安定剤は、塩化ビニル系単量体１０
０重量部に対して０．０１〜１重量部の範囲で用いるこ
とが好ましい。The dispersion stabilizer is a vinyl chloride monomer 10
It is preferable to use 0.01 to 1 part by weight based on 0 part by weight.
【００２２】本発明の製造法は、まず、撹拌下にて、分
散安定剤の全量及び用いるべき塩化ビニル系単量体に対
して３０〜５０重量％に相当する４０℃以上の水性媒体
を重合反応器に仕込むことを特徴とするものである。こ
こで、撹拌していない状態で分散安定剤及び４０℃以上
の水性媒体を仕込んだ場合、該分散安定剤が水性媒体中
に均一に溶解又は分散しないため、得られる塩化ビニル
系重合体が粗大粒子となったり、ロールフィッシュアイ
が悪化したりする。また、最悪の場合には、重合反応器
内で塩化ビニル系重合体が塊状となり重合反応器から排
出できないという生産上の大きな問題を引き起こす。In the production method of the present invention, first, an aqueous medium at 40 ° C. or higher corresponding to 30 to 50% by weight of the total amount of the dispersion stabilizer and the vinyl chloride monomer to be used is polymerized under stirring. It is characterized by being charged into a reactor. Here, when the dispersion stabilizer and the aqueous medium having a temperature of 40 ° C. or more are charged without stirring, the obtained vinyl chloride polymer is coarse because the dispersion stabilizer does not uniformly dissolve or disperse in the aqueous medium. It becomes particles or roll fish eyes deteriorate. In the worst case, the production of the vinyl chloride-based polymer becomes bulky in the polymerization reactor and cannot be discharged from the polymerization reactor.
【００２３】本発明における分散安定剤全量の仕込方法
は、特に制限はなく、例えば用いるべき塩化ビニル系単
量体に対して３０〜５０重量％に相当する４０℃以上の
水性媒体と分散安定剤全量を同時に重合反応器内に仕込
んでも、分散安定剤全量を仕込んだ後用いるべき塩化ビ
ニル系単量体に対して３０〜５０重量％に相当する４０
℃以上の水性媒体を仕込んでも、また用いるべき塩化ビ
ニル系単量体に対して３０〜５０重量％に相当する４０
℃以上の水性媒体を仕込んだ後分散安定剤全量を仕込ん
でも良い。ここで、分散安定剤の全量を重合反応器に仕
込む前に塩化ビニル系単量体の仕込みを開始した場合、
残りの一部の分散安定剤は塩化ビニル系単量体に局部的
に吸収され、分散安定剤の濃度むら又は分散むらが発生
するために得られる塩化ビニル系重合体は粒度分布が広
く、微粉が多いものとなってしまう。The method of charging the entire amount of the dispersion stabilizer in the present invention is not particularly limited. For example, an aqueous medium at 40 ° C. or higher corresponding to 30 to 50% by weight based on the vinyl chloride monomer to be used and the dispersion stabilizer Even when the entire amount is charged into the polymerization reactor at the same time, the amount equivalent to 30 to 50% by weight based on the vinyl chloride monomer to be used after charging the entire amount of the dispersion stabilizer is 40.
Even if an aqueous medium at a temperature of not less than 0 ° C. is charged, the amount of the aqueous medium corresponding to 30 to 50% by weight relative to the vinyl chloride monomer to be used is 40%.
After the aqueous medium having a temperature of not lower than 0 ° C. is charged, the whole amount of the dispersion stabilizer may be charged. Here, when charging of the vinyl chloride monomer is started before charging the entire amount of the dispersion stabilizer to the polymerization reactor,
The remaining part of the dispersion stabilizer is locally absorbed by the vinyl chloride-based monomer, and the concentration of the dispersion stabilizer or dispersion unevenness occurs. Will be many.
【００２４】また、用いるべき塩化ビニル系単量体に対
して３０重量％より少ない４０℃以上の水性媒体を仕込
んだ段階で塩化ビニル系単量体の仕込みを開始した場
合、重合反応器内で塩化ビニル系単量体と水性媒体の相
転移が発生し、この相転移によりスケールが付着した
り、得られる塩化ビニル系重合体のロールフィッシュア
イが悪化するという問題を有する。さらに、最悪の場
合、重合反応器内で塩化ビニル系重合体が塊状となり重
合器から排出できないという生産上の大きな問題を引き
起こす恐れがある。一方、塩化ビニル系単量体に対して
５０重量％より多い４０℃以上の水性媒体を仕込んだ段
階で塩化ビニル系単量体の仕込みを開始した場合、水性
媒体の仕込時間が長くなるため、塩化ビニル系重合体の
生産性が低下する。また、高温の水性媒体を使用した場
合、全重合資材を仕込んだ後の重合反応器内温度は所定
重合温度となるにしても、塩化ビニル系単量体仕込開始
時には、重合反応器内圧力が重合温度到達時の圧力より
高くなってしまい危険であるため、水性媒体の温度を高
めることができす、全資材仕込後所定重合温度までの昇
温に時間を要し、生産性が低下してしまう。When the charging of the vinyl chloride monomer is started at the stage when the aqueous medium having a temperature of 40 ° C. or less, which is less than 30% by weight based on the vinyl chloride monomer to be used, is charged in the polymerization reactor. A phase transition occurs between the vinyl chloride-based monomer and the aqueous medium, and this phase transition causes a problem that a scale is attached and a roll fish eye of the obtained vinyl chloride-based polymer is deteriorated. Further, in the worst case, there is a possibility that the vinyl chloride-based polymer becomes a lump in the polymerization reactor and cannot be discharged from the polymerization reactor, causing a serious problem in production. On the other hand, when the charging of the vinyl chloride-based monomer is started at the stage where more than 50% by weight of the vinyl chloride-based monomer is added to the aqueous medium at 40 ° C. or more, the charging time of the aqueous medium becomes longer. The productivity of the vinyl chloride polymer decreases. When a high-temperature aqueous medium is used, even if the temperature in the polymerization reactor after charging all the polymerization materials reaches a predetermined polymerization temperature, the pressure in the polymerization reactor is reduced when the vinyl chloride monomer is charged. Because it is dangerous because it becomes higher than the pressure at the time of reaching the polymerization temperature, it is possible to raise the temperature of the aqueous medium, it takes time to raise the temperature to the predetermined polymerization temperature after charging all the materials, and the productivity is reduced. I will.
【００２５】本発明の製造法は、撹拌下にて分散安定剤
全量及び用いるべき塩化ビニル系単量体に対して３０〜
５０重量％に相当する４０℃以上の水性媒体を仕込み、
その後、重合反応器内の塩化ビニル系単量体に対する水
性媒体の重量比を０．８以上に維持しながら塩化ビニル
系単量体及び４０℃以上の水性媒体を仕込み、かつ重合
開始剤を塩化ビニル系単量体の仕込量が用いるべき塩化
ビニル系単量体の５０重量％以上１００重量％未満の範
囲となった時点で仕込むものである。ここで、重合反応
器内の塩化ビニル系単量体と水性媒体の重量比が０．８
より小さい場合、塩化ビニル系単量体と水性媒体の相転
移が発生し、この相転移によりスケールが付着したり、
得られる塩化ビニル系重合体のロールフィッシュアイが
悪化するという問題を有する。また、重合開始剤を塩化
ビニル系単量体の仕込量が用いるべき塩化ビニル系単量
体の５０重量％未満の時点で仕込んだ場合、重合開始剤
が塩化ビニル系単量体に均一に溶解しないため、得られ
る塩化ビニル系重合体のロールフィッシュアイが悪くな
る。一方、重合開始剤を塩化ビニル系単量体の仕込量が
用いるべき塩化ビニル系単量体の１００重量％に達した
時点、つまり、塩化ビニル系単量体の仕込みが終了した
後、重合開始剤を仕込んだ場合、重合工程中のスケール
付着が甚だしくなる。The production method of the present invention is characterized in that the total amount of the dispersion stabilizer and the amount of the
An aqueous medium at 40 ° C. or higher corresponding to 50% by weight is charged,
Thereafter, while maintaining the weight ratio of the aqueous medium to the vinyl chloride monomer in the polymerization reactor at 0.8 or more, the vinyl chloride monomer and the aqueous medium at 40 ° C. or more were charged, and the polymerization initiator was chlorinated. The vinyl monomer is charged when the amount of the vinyl monomer reaches a range of 50% by weight or more and less than 100% by weight of the vinyl chloride monomer to be used. Here, the weight ratio between the vinyl chloride monomer and the aqueous medium in the polymerization reactor is 0.8.
If it is smaller, a phase transition occurs between the vinyl chloride monomer and the aqueous medium, and this phase transition causes scale to adhere,
There is a problem that the roll fish eye of the obtained vinyl chloride polymer deteriorates. Also, when the polymerization initiator is charged at a time when the amount of the vinyl chloride monomer charged is less than 50% by weight of the vinyl chloride monomer to be used, the polymerization initiator is uniformly dissolved in the vinyl chloride monomer. Therefore, the roll fish eye of the obtained vinyl chloride polymer deteriorates. On the other hand, when the charged amount of the vinyl chloride monomer reaches 100% by weight of the vinyl chloride monomer to be used, that is, after the vinyl chloride monomer has been charged, the polymerization is started. When the agent is charged, scale adhesion during the polymerization process becomes severe.
【００２６】[0026]
【実施例】以下、実施例および比較例にもとづき本発明
を説明するが、本発明はこれらに限定されるものではな
い。The present invention will be described below based on examples and comparative examples, but the present invention is not limited to these examples.
【００２７】実施例及び比較例により得られた塩化ビニ
ル系重合体の評価は、下記方法により測定した。The evaluation of the vinyl chloride polymers obtained in Examples and Comparative Examples was measured by the following method.
【００２８】〜粒度分布〜 得られた塩化ビニル系重合体をＪＩＳ Ｚ ８８０１に
準じた４５メッシュの篩にかけ、該篩を通過したサンプ
ルをさらにＪＩＳ Ｚ ８８０１に準じた６０メッシ
ュ、８０メッシュ、１００メッシュ、１４０メッシュ、
２００メッシュの篩いで篩い、該サンプルの８５重量％
の塩化ビニル系重合体粒子が通過した篩目の大きさ（Ａ
（μｍ））、１５重量％の塩化ビニル系重合体粒子が通
過した篩目の大きさ（Ｂ（μｍ））及び５０重量％の塩
化ビニル系重合体粒子が通過した篩目の大きさ（Ｃ（μ
ｍ））を測定し、その結果を下記式に挿入することによ
り粒度分布を算出した。Particle Size Distribution The obtained vinyl chloride polymer is sieved through a 45-mesh sieve according to JIS Z 8801, and the sample passing through the sieve is further subjected to 60-mesh, 80-mesh, and 100-mesh according to JIS Z 8801. , 140 mesh,
Sieve with a 200 mesh sieve, 85% by weight of the sample
Size of the sieve through which the vinyl chloride polymer particles of (A)
(Μm)), the sieve size (B (μm)) through which 15% by weight of the vinyl chloride polymer particles passed, and the sieve size (C (C) through which 50% by weight of the vinyl chloride polymer particles passed) (Μ
m)) was measured, and the particle size distribution was calculated by inserting the result into the following equation.
【００２９】粒度分布＝（Ａ−Ｂ）／Ｃ 〜平均粒径〜 得られた塩化ビニル系重合体をＪＩＳ Ｚ ８８０１に
準じた４５メッシュの篩にかけ、該篩を通過したサンプ
ルを用い、該サンプルの５０重量％の塩化ビニル系重合
体粒子が通過するふるいの目の大きさ（μｍ）を平均粒
径として表す。Particle size distribution = (A−B) / C (average particle size) The obtained vinyl chloride polymer is passed through a 45-mesh sieve according to JIS Z 8801, and a sample passed through the sieve is used. The size (μm) of the sieve through which 50% by weight of the vinyl chloride polymer particles pass is expressed as the average particle size.
【００３０】〜４５メッシュオン〜 得られた塩化ビニル系重合体をＪＩＳ Ｚ ８８０１に
準じた４５メッシュの篩にかけ、該篩にかけるサンプル
全量に対する該篩上に残ったサンプルの重量比率（百分
率）を４５メッシュオンとして表す。４５45 mesh on〜 The obtained vinyl chloride polymer is sieved through a 45 mesh sieve according to JIS Z 8801, and the weight ratio (percentage) of the sample remaining on the sieve to the total amount of the sample sieved is determined. Expressed as 45 mesh on.
【００３１】〜かさ比重〜 ＪＩＳ Ｋ ６７２１に準じた。Bulk specific gravity According to JIS K6721.
【００３２】〜フィッシュアイ〜 得られた塩化ビニル系重合体１００重量部、Ｃａ−Ｚｎ
系粉末複合安定剤１．５重量部、有機燐系安定化助剤
０．５重量部、群青３重量部およびＤＯＰ（ジオクチル
フタレート）５０重量部を混合し、１５０℃のロールで
厚さ０．３５ｍｍとして５分間混練し、０．３５ｍｍの
シートを分取し、シート５０ｃｍ2中の透明粒子の数を
もって示す。~ Fisheye ~ 100 parts by weight of the obtained vinyl chloride polymer, Ca-Zn
1.5 parts by weight of a composite powder composite stabilizer, 0.5 parts by weight of an organic phosphorus-based stabilizing aid, 3 parts by weight of ultramarine blue and 50 parts by weight of DOP (dioctyl phthalate) were mixed and rolled at 150 ° C. to a thickness of 0.1 part. The mixture was kneaded at 35 mm for 5 minutes, and a 0.35 mm sheet was taken out and indicated by the number of transparent particles in 50 cm 2 of the sheet.
【００３３】〜スケール付着状況〜 重合反応器壁についたスケール量を目視で評価した。-Scale adhesion state-The amount of scale attached to the polymerization reactor wall was visually evaluated.
【００３４】 ○良好 ×悪い（付着が激しい） 実施例１ １．６ｍ3の逆流コンデンサーを設置した重合反応器を
使用し、該重合反応器のジャケットに４０℃の温水を循
環し、重合反応器内を脱気した後、撹拌下にて４０℃に
加温した脱イオン水５７６ｋｇ及び分散安定剤としてけ
ん化度８０モル％、平均重合度２６００の部分ケン化ポ
リビニルアルコール３．５％溶液７８００ｇの仕込みを
同時に開始した。脱イオン水は１０分間、分散安定剤は
２分間で重合反応器内に仕込んだ。そして、脱イオン水
及び分散安定剤の仕込み開始３分後（脱イオン水１７
２．８ｋｇ（用いるべき塩化ビニル系単量体に対して３
１．６重量％に相当）を仕込んだ段階）に、塩化ビニル
単量体５４６ｋｇの仕込みを開始し、塩化ビニル単量体
は６分間で仕込んだ。なお、塩化ビニル単量体３８０ｋ
ｇ（用いるべき塩化ビニル単量体の約７０重量％）を仕
込んだ段階で、予めポットに仕込んでおいた純度７０重
量％のクミルパーオキシネオデカノエート３６８ｇ及び
純度７０％のｔ−ブチルパーオキシネオデカノエート３
６８ｇを重合反応器内に仕込んだ。ここで、塩化ビニル
単量体に対する脱イオン水の重量比（以下、水モノマー
比と略す。）が最も低くなる塩化ビニル単量体仕込み終
了時の水モノマー比は０．９７であった。脱イオン水仕
込み終了後、２５分間かけて５７．５℃まで昇温し、仕
込み開始から重合温度到達までの昇温時間は３５分間で
あった。○ good × bad (heavy adhesion) Example 1 A polymerization reactor equipped with a 1.6 m 3 backflow condenser was used, and warm water at 40 ° C. was circulated through the jacket of the polymerization reactor. After degassing the inside, 576 kg of deionized water heated to 40 ° C. with stirring and 7,800 g of a 3.5% solution of a partially saponified polyvinyl alcohol having a saponification degree of 80 mol% and an average polymerization degree of 2600 as a dispersion stabilizer were prepared. Started at the same time. Deionized water was charged into the polymerization reactor in 10 minutes and dispersion stabilizer in 2 minutes. Then, three minutes after the start of charging the deionized water and the dispersion stabilizer (deionized water 17
2.8 kg (3 to vinyl chloride monomer to be used
(Equivalent to 1.6% by weight)), 546 kg of vinyl chloride monomer was started, and the vinyl chloride monomer was charged in 6 minutes. In addition, the vinyl chloride monomer 380k
g (about 70% by weight of the vinyl chloride monomer to be used), 368 g of 70% by weight of cumyl peroxy neodecanoate previously charged in a pot and 70% by weight of t-butyl par Oxyneo decanoate 3
68 g were charged into the polymerization reactor. Here, the water monomer ratio at the end of the preparation of the vinyl chloride monomer at which the weight ratio of deionized water to the vinyl chloride monomer (hereinafter abbreviated as water monomer ratio) was the lowest was 0.97. After the deionized water charging was completed, the temperature was raised to 57.5 ° C. over 25 minutes, and the temperature rising time from the start of charging to the polymerization temperature was 35 minutes.
【００３５】そして、重合反応器内圧力が５７．５℃に
おける飽和蒸気圧より０．２ＭＰａ低下した段階で重合
を終了し、未反応塩化ビニル単量体を回収し、得られた
スラリーを脱水乾燥し、塩化ビニル重合体を得た。The polymerization is terminated when the pressure in the polymerization reactor drops by 0.2 MPa from the saturated vapor pressure at 57.5 ° C., the unreacted vinyl chloride monomer is recovered, and the obtained slurry is dehydrated and dried. Thus, a vinyl chloride polymer was obtained.
【００３６】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表１に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 1 shows the results.
【００３７】得られた塩化ビニル重合体の粉体特性及び
フィッシュアイは良好なものであり、塩化ビニル重合体
の製造時のスケールの付着も認められなかった。The powder characteristics and fisheye of the obtained vinyl chloride polymer were good, and no adhesion of scale during production of the vinyl chloride polymer was observed.
【００３８】実施例２ 重合反応器のジャケットに５０℃の温水を循環し、撹拌
下にて５０℃の脱イオン水と分散安定剤の仕込みを同時
に開始した。脱イオン水は１０分間、分散安定剤は２分
間で重合反応器内に仕込んだ。そして、脱イオン水及び
分散安定剤の仕込み開始３分後（脱イオン水１７２．８
ｋｇ（用いるべき塩化ビニル系単量体に対して３１．６
重量％に相当）を仕込んだ段階）に、塩化ビニル単量体
の仕込みを開始し、塩化ビニル単量体を５分間で仕込
み、脱イオン水仕込終了後に１０分間で重合温度に昇温
した。仕込み開始から重合温度に到達するまでの昇温時
間は２０分間を要し、水モノマー比が最も低くなる塩化
ビニル単量体仕込み終了時の水モノマー比は０．８５で
あった。EXAMPLE 2 Warm water at 50 ° C. was circulated through the jacket of the polymerization reactor, and the addition of deionized water at 50 ° C. and the dispersion stabilizer were simultaneously started under stirring. Deionized water was charged into the polymerization reactor in 10 minutes and dispersion stabilizer in 2 minutes. Then, 3 minutes after the start of charging the deionized water and the dispersion stabilizer (172.8 deionized water)
kg (31.6 for the vinyl chloride monomer to be used)
(Equivalent to% by weight)), the vinyl chloride monomer was started to be charged, the vinyl chloride monomer was charged in 5 minutes, and the temperature was raised to the polymerization temperature in 10 minutes after the completion of the deionized water charging. The temperature raising time from the start of charging to reaching the polymerization temperature required 20 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 0.85.
【００３９】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Other than the above, a vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００４０】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表１に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 1 shows the results.
【００４１】得られた塩化ビニル重合体の粉体特性及び
フィッシュアイは良好なものであり、塩化ビニル重合体
の製造時のスケールの付着も認められなかった。The powder characteristics and fisheye of the obtained vinyl chloride polymer were good, and no adhesion of scale during the production of the vinyl chloride polymer was observed.
【００４２】実施例３ 重合反応器のジャケットに６０℃の温水を循環し、撹拌
下にて６０℃の脱イオン水と分散安定剤の仕込みを同時
に開始した。脱イオン水は１０分間、分散安定剤は２分
間で重合反応器内に仕込んだ。そして、脱イオン水及び
分散安定剤の仕込み開始３分後（脱イオン水１７２．８
ｋｇ（用いるべき塩化ビニル系単量体に対して３１．６
重量％に相当）を仕込んだ段階）に、塩化ビニル単量体
の仕込みを開始し、塩化ビニル単量体を６分間で仕込
み、脱イオン水仕込終了後に５分間で重合温度に昇温し
た。仕込み開始から重合温度に到達するまでの昇温時間
は１５分間を要し、水モノマー比が最も低くなる塩化ビ
ニル単量体仕込み終了時の水モノマー比は０．９７であ
った。Example 3 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor, and the addition of deionized water at 60 ° C. and the dispersion stabilizer were simultaneously started under stirring. Deionized water was charged into the polymerization reactor in 10 minutes and dispersion stabilizer in 2 minutes. Then, 3 minutes after the start of charging the deionized water and the dispersion stabilizer (172.8 deionized water)
kg (31.6 for the vinyl chloride monomer to be used)
(Corresponding to% by weight)), the vinyl chloride monomer was started to be charged, the vinyl chloride monomer was charged in 6 minutes, and the polymerization temperature was raised to 5 minutes after the completion of the deionized water charging. The temperature raising time from the start of charging to reaching the polymerization temperature required 15 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 0.97.
【００４３】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Other than the above, a vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００４４】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表１に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 1 shows the results.
【００４５】得られた塩化ビニル重合体の粉体特性及び
フィッシュアイは良好なものであり、塩化ビニル重合体
の製造時のスケールの付着も認められなかった。The powder characteristics and fisheye of the obtained vinyl chloride polymer were good, and no adhesion of scale during the production of the vinyl chloride polymer was observed.
【００４６】実施例４ 重合反応器のジャケットに６０℃の温水を循環し、撹拌
下にて６０℃の脱イオン水と分散安定剤の仕込みを同時
に開始した。脱イオン水は１０分間、分散安定剤は２分
間で重合反応器内に仕込んだ。そして、脱イオン水及び
分散安定剤の仕込み開始５分後（脱イオン水２７０ｋｇ
（用いるべき塩化ビニル系単量体に対して４９重量％に
相当）を仕込んだ段階）に、塩化ビニル単量体の仕込み
を開始し、塩化ビニル単量体を４分間で仕込み、脱イオ
ン水仕込終了後に５分間で重合温度に昇温した。仕込み
開始から重合温度に到達するまでの昇温時間は１５分間
を要し、水モノマー比が最も低くなる塩化ビニル単量体
仕込み終了時の水モノマー比は０．９７であった。Example 4 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor, and the addition of deionized water at 60 ° C. and the dispersion stabilizer were simultaneously started under stirring. Deionized water was charged into the polymerization reactor in 10 minutes and dispersion stabilizer in 2 minutes. Then, 5 minutes after the start of charging the deionized water and the dispersion stabilizer (270 kg of deionized water)
(Equivalent to 49% by weight based on the vinyl chloride-based monomer to be used)), start charging the vinyl chloride monomer, charge the vinyl chloride monomer in 4 minutes, and add deionized water. After completion of the charging, the temperature was raised to the polymerization temperature in 5 minutes. The temperature raising time from the start of charging to reaching the polymerization temperature required 15 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 0.97.
【００４７】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Except for these, the vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００４８】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表１に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 1 shows the results.
【００４９】得られた塩化ビニル重合体の粉体特性及び
フィッシュアイは良好なものであり、塩化ビニル重合体
の製造時のスケールの付着も認められなかった。The powder characteristics and fish eye of the obtained vinyl chloride polymer were good, and no scale adhesion was observed during the production of the vinyl chloride polymer.
【００５０】比較例１ 重合反応器のジャケットに４０℃の温水を循環し、撹拌
下にて４０℃の脱イオン水、分散安定剤および塩化ビニ
ル単量体の仕込みを同時に開始した。脱イオン水は１０
分間、分散安定剤は２分間、塩化ビニル単量体は６分間
で重合反応器内に仕込んだ。そして、脱イオン水仕込終
了後に２５分間で重合温度に昇温した。仕込み開始から
重合温度に到達するまでの昇温時間は３５分間を要し、
水モノマー比が最も低くなる塩化ビニル単量体仕込み終
了時の水モノマー比は０．６４であった。COMPARATIVE EXAMPLE 1 Warm water at 40 ° C. was circulated through the jacket of the polymerization reactor, and charging of 40 ° C. deionized water, a dispersion stabilizer and a vinyl chloride monomer was simultaneously started under stirring. 10 for deionized water
Minutes, the dispersion stabilizer was charged into the polymerization reactor in 2 minutes, and the vinyl chloride monomer was charged in the polymerization reactor in 6 minutes. After the completion of the deionized water charging, the temperature was raised to the polymerization temperature in 25 minutes. The time required for the temperature to rise from the start of the charging to the polymerization temperature is 35 minutes,
The water monomer ratio at the end of the vinyl chloride monomer charge at which the water monomer ratio became the lowest was 0.64.
【００５１】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Other than the above, a vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００５２】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表２に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 2 shows the results.
【００５３】得られた塩化ビニル重合体は、粗粒化し、
ロールフィッシュアイが大きく悪化し、スケールの付着
も激しいものであった。The obtained vinyl chloride polymer is coarsened,
The roll fish eye was greatly deteriorated, and the scale adhered severely.
【００５４】比較例２ 重合反応器のジャケットに６０℃の温水を循環し、撹拌
下にて６０℃の脱イオン水と分散安定剤の仕込みを同時
に開始し、脱イオン水は１０分間、分散安定剤は２分間
で重合反応器内に仕込んだ。そして、脱イオン水及び分
散安定剤の仕込み開始３分後（脱イオン水１７２．８ｋ
ｇ（用いるべき塩化ビニル系単量体に対して３１．６重
量％に相当）を仕込んだ段階）に、塩化ビニル単量体の
仕込みを開始し、塩化ビニル単量体を４分間で仕込み、
脱イオン水仕込終了後に５分間で重合温度に昇温した。
仕込み開始から重合温度に到達するまでの昇温時間は１
５分間を要し、水モノマー比が最も低くなる塩化ビニル
単量体仕込み終了時の水モノマー比は０．７５であっ
た。COMPARATIVE EXAMPLE 2 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor, and charging of deionized water at 60 ° C. and a dispersion stabilizer were simultaneously started under stirring. The agent was charged into the polymerization reactor in 2 minutes. Then, three minutes after the start of charging the deionized water and the dispersion stabilizer (172.8 k of deionized water)
g (corresponding to 31.6% by weight with respect to the vinyl chloride-based monomer to be used)), charging of the vinyl chloride monomer was started, and the vinyl chloride monomer was charged in 4 minutes.
After the deionized water was charged, the temperature was raised to the polymerization temperature in 5 minutes.
The heating time from the start of charging until the polymerization temperature is reached is 1
It took 5 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 0.75.
【００５５】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Other than the above, a vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００５６】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表２に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 2 shows the results.
【００５７】得られた塩化ビニル重合体は、粗粒化し、
ロールフィッシュアイが大きく悪化し、スケールの付着
も激しいものであった。The obtained vinyl chloride polymer is coarsened,
The roll fish eye was greatly deteriorated, and the scale adhered severely.
【００５８】比較例３ 重合反応器のジャケットに６０℃の温水を循環し、撹拌
下にて６０℃の脱イオン水、分散安定剤および塩化ビニ
ル単量体の仕込みを同時に開始し、脱イオン水は１０分
間、分散安定剤は２分間、塩化ビニル単量体は１０分間
で重合反応器内に仕込んだ。そして、脱イオン水仕込終
了後に５分間で重合温度に昇温した。仕込み開始から重
合温度に到達するまでの昇温時間は１５分間を要し、水
モノマー比が最も低くなる塩化ビニル単量体仕込み終了
時の水モノマー比は１．０７であった。COMPARATIVE EXAMPLE 3 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor, and simultaneously charged with 60 ° C. deionized water, a dispersion stabilizer and a vinyl chloride monomer under stirring, Was charged into the polymerization reactor in 10 minutes, the dispersion stabilizer in 2 minutes, and the vinyl chloride monomer in 10 minutes. Then, the temperature was raised to the polymerization temperature in 5 minutes after the completion of the charged deionized water. The temperature raising time from the start of charging to reaching the polymerization temperature required 15 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 1.07.
【００５９】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Except for these, the vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００６０】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表２に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 2 shows the results.
【００６１】得られた塩化ビニル重合体は、粗粒化し、
ロールフィッシュアイが大きく悪化し、スケールの付着
も激しいものであった。The obtained vinyl chloride polymer is coarsened,
The roll fish eye was greatly deteriorated, and the scale adhered severely.
【００６２】比較例４ 重合反応器のジャケットに６０℃の温水を循環し、撹拌
下６０℃の脱イオン水の仕込を開始し、脱イオン水は１
０分間で重合反応器内に仕込んだ。そして、脱イオン水
の仕込み開始３分後（脱イオン水１７２．８ｋｇ（用い
るべき塩化ビニル系単量体に対して３１．６重量％に相
当）を仕込んだ段階）に、塩化ビニル単量体及び分散安
定剤の仕込みを開始し、塩化ビニル単量体は６分間、分
散安定剤は２分間で仕込み、脱イオン水仕込終了後に５
分間で重合温度に昇温した。仕込み開始から重合温度に
到達するまでの昇温時間は１５分間を要し、水モノマー
比が最も低くなる塩化ビニル単量体仕込み終了時の水モ
ノマー比は０．９７であった。Comparative Example 4 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor, and charging of 60 ° C. deionized water was started with stirring.
It was charged in the polymerization reactor in 0 minutes. Then, 3 minutes after the start of the charging of the deionized water (at a stage where 172.8 kg of deionized water (corresponding to 31.6% by weight based on the vinyl chloride monomer to be used)), the vinyl chloride monomer was added. And the dispersion stabilizer were started, the vinyl chloride monomer was charged in 6 minutes, the dispersion stabilizer was charged in 2 minutes, and 5 minutes after the deionized water was charged.
The temperature was raised to the polymerization temperature in minutes. The temperature raising time from the start of charging to reaching the polymerization temperature required 15 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 0.97.
【００６３】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Except for these, the vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００６４】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表２に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 2 shows the results.
【００６５】得られた塩化ビニル重合体は、粗粒化し、
ロールフィッシュアイが大きく悪化し、スケールの付着
も激しいものであった。The obtained vinyl chloride polymer is coarsened,
The roll fish eye was greatly deteriorated, and the scale adhered severely.
【００６６】比較例５ 重合反応器のジャケットに６０℃の温水を循環し、６０
℃の脱イオン水及び分散安定剤の仕込みを開始し、脱イ
オン水は１０分間、分散安定剤は２分間で重合反応器内
に仕込んだ。そして、脱イオン水の仕込み開始３分後
（脱イオン水１７２．８ｋｇ（用いるべき塩化ビニル系
単量体に対して３１．６重量％に相当）を仕込んだ段
階）に、攪拌を開始するとともに塩化ビニル単量体の仕
込みを開始し、塩化ビニル単量体は６分間で仕込み、脱
イオン水仕込終了後に５分間で重合温度に昇温した。仕
込み開始から重合温度に到達するまでの昇温時間は１５
分間を要し、水モノマー比が最も低くなる塩化ビニル単
量体仕込み終了時の水モノマー比は０．９７であった。Comparative Example 5 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor.
The charging of the deionized water and the dispersion stabilizer at 0 ° C. was started. The deionized water was charged into the polymerization reactor in 10 minutes, and the dispersion stabilizer was charged in the polymerization reactor in 2 minutes. After 3 minutes from the start of the charging of the deionized water (at the stage of charging 172.8 kg of deionized water (corresponding to 31.6% by weight based on the vinyl chloride monomer to be used)), stirring is started and The charging of the vinyl chloride monomer was started, the vinyl chloride monomer was charged in 6 minutes, and the temperature was raised to the polymerization temperature in 5 minutes after the completion of the deionized water charging. The heating time from the start of the charging until the polymerization temperature is reached is 15
It took 0.9 minute, and the water monomer ratio at the end of the preparation of the vinyl chloride monomer at which the water monomer ratio became the lowest was 0.97.
【００６７】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Except for these, the vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００６８】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表３に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 3 shows the results.
【００６９】得られた塩化ビニル重合体は、粗粒化し、
ロールフィッシュアイが大きく悪化し、スケールの付着
も激しいものであった。The vinyl chloride polymer obtained is coarsened,
The roll fish eye was greatly deteriorated, and the scale adhered severely.
【００７０】比較例６ 重合反応器のジャケットに６０℃の温水を循環し、撹拌
下にて６０℃の脱イオン水及び分散安定剤の仕込を同時
に開始し、分散安定剤は２分間、脱イオン水は１０分間
で重合反応器内に仕込んだ。そして、脱イオン水の仕込
み開始３分後（脱イオン水１７２．８ｋｇ（用いるべき
塩化ビニル系単量体に対して３１．６重量％に相当）を
仕込んだ段階）に、塩化ビニル単量体の仕込みを開始
し、塩化ビニル単量体は６分間で仕込み、その後、続い
て重合開始剤を仕込んだ。脱イオン水仕込終了後に５分
間で重合温度に昇温した。仕込み開始から重合温度に到
達するまでの昇温時間は１５分間を要し、水モノマー比
が最も低くなる塩化ビニル単量体仕込み終了時の水モノ
マー比は０．９７であった。COMPARATIVE EXAMPLE 6 Warm water at 60 ° C. was circulated through the jacket of the polymerization reactor, and charging of deionized water at 60 ° C. and a dispersion stabilizer were simultaneously started under stirring. The dispersion stabilizer was deionized for 2 minutes. Water was charged into the polymerization reactor in 10 minutes. Then, 3 minutes after the start of the charging of the deionized water (at a stage where 172.8 kg of deionized water (corresponding to 31.6% by weight based on the vinyl chloride monomer to be used)), the vinyl chloride monomer was added. Was started, the vinyl chloride monomer was charged in 6 minutes, and then the polymerization initiator was charged. After the deionized water was charged, the temperature was raised to the polymerization temperature in 5 minutes. The temperature raising time from the start of charging to reaching the polymerization temperature required 15 minutes, and the water monomer ratio at the end of the vinyl chloride monomer charging at which the water monomer ratio became the lowest was 0.97.
【００７１】これら以外のことは、実施例１と同様の方
法により、塩化ビニル重合体の重合を行った。Other than these, a vinyl chloride polymer was polymerized in the same manner as in Example 1.
【００７２】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表３に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 3 shows the results.
【００７３】得られた塩化ビニル重合体は、粗粒化し、
ロールフィッシュアイが大きく悪化し、スケールの付着
も激しいものであった。The obtained vinyl chloride polymer is coarsened,
The roll fish eye was greatly deteriorated, and the scale adhered severely.
【００７４】比較例７ 重合反応器のジャケットに３０℃の温水を循環し、３０
℃の脱イオン及び分散安定剤の仕込を同時に開始し、脱
イオン水は１０分間、分散安定剤は２分間で重合反応器
内に仕込み脱気した。脱気後、塩化ビニル単量体を６分
間で仕込み、塩化ビニル単量体仕込開始と共に撹拌を開
始した。また、塩化ビニル単量体を４００ｋｇ仕込んだ
段階で重合開始剤を仕込み、塩化ビニル単量体仕込み終
了後に４０分間で重合温度に昇温した。仕込み開始から
重合温度に到達するまでの昇温時間は５６分間を要し、
水モノマー比が最も低くなる塩化ビニル単量体仕込み終
了時の水モノマー比は１．０７であった。Comparative Example 7 Warm water of 30 ° C. was circulated through the jacket of the polymerization reactor.
The deionized water and the dispersion stabilizer were started at the same time, and deionized water was charged into the polymerization reactor for 10 minutes and the dispersion stabilizer was charged and degassed for 2 minutes. After deaeration, the vinyl chloride monomer was charged for 6 minutes, and stirring was started when the vinyl chloride monomer was charged. Further, at the stage when 400 kg of the vinyl chloride monomer was charged, a polymerization initiator was charged, and after the vinyl chloride monomer was charged, the temperature was raised to the polymerization temperature in 40 minutes. The heating time from the start of charging to reaching the polymerization temperature required 56 minutes,
The water monomer ratio at the end of the preparation of the vinyl chloride monomer at which the water monomer ratio became the lowest was 1.07.
【００７５】得られた塩化ビニル重合体を上記の評価方
法により評価測定した。その結果を表３に示す。The obtained vinyl chloride polymer was evaluated and measured by the above evaluation method. Table 3 shows the results.
【００７６】仕込み昇温に時間を要するため、生産性の
低いものであった。Since it took a long time to raise the temperature, the productivity was low.
【００７７】[0077]
【表１】 [Table 1]
【００７８】[0078]
【表２】 [Table 2]
【００７９】[0079]
【表３】 [Table 3]
【００８０】[0080]
【発明の効果】本発明の製造法によると、粗粒化やロー
ルフィッシュアイの悪化、嵩比重の低下、スケール付着
を伴うことなく、仕込み昇温時間が大幅に短縮でき、塩
化ビニル系重合体の生産性を大幅に高めることができ、
その工業的価値は極めて高いものである。According to the production method of the present invention, the temperature rise time for charging can be greatly reduced without coarsening, deterioration of roll fish eyes, reduction of bulk specific gravity, and scale adhesion. Can greatly increase the productivity of
Its industrial value is extremely high.
Claims (1)
安定剤の存在下、水性媒体中で懸濁重合を行い塩化ビニ
ル系重合体を製造する方法において、攪拌下にて、分散
安定剤の全量及び用いるべき塩化ビニル系単量体に対し
て３０〜５０重量％に相当する４０℃以上の水性媒体を
重合反応器に仕込み、その後、引き続き重合反応器内の
塩化ビニル系単量体に対する水性媒体の重量比を０．８
以上に維持しながら、塩化ビニル系単量体及び４０℃以
上の水性媒体を仕込み、かつ重合開始剤を塩化ビニル系
単量体の仕込量が用いるべき塩化ビニル系単量体の５０
重量％以上１００重量％未満の範囲となった時点で仕込
むことを特徴とする塩化ビニル系重合体の製造法。1. A method for producing a vinyl chloride polymer by subjecting a vinyl chloride monomer to suspension polymerization in an aqueous medium in the presence of a polymerization initiator and a dispersion stabilizer. An aqueous medium having a temperature of 40 ° C. or higher corresponding to 30 to 50% by weight based on the total amount of the agent and the vinyl chloride monomer to be used is charged into the polymerization reactor, and then the vinyl chloride monomer in the polymerization reactor is continuously charged. 0.8 weight ratio of aqueous medium to
While maintaining the above conditions, the vinyl chloride monomer and the aqueous medium at 40 ° C. or higher were charged, and the polymerization initiator was charged with the amount of the vinyl chloride monomer to be used.
A method for producing a vinyl chloride-based polymer, comprising charging at a time when the amount falls within a range of not less than 100% by weight and not more than 100% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02204898A JP3915225B2 (en) | 1998-02-03 | 1998-02-03 | Production method of vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02204898A JP3915225B2 (en) | 1998-02-03 | 1998-02-03 | Production method of vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11217404A true JPH11217404A (en) | 1999-08-10 |
| JP3915225B2 JP3915225B2 (en) | 2007-05-16 |
Family
ID=12072052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02204898A Expired - Fee Related JP3915225B2 (en) | 1998-02-03 | 1998-02-03 | Production method of vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3915225B2 (en) |
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1998
- 1998-02-03 JP JP02204898A patent/JP3915225B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3915225B2 (en) | 2007-05-16 |
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