JPH0776602A - Production of vinyl chloride-based polymer - Google Patents
Production of vinyl chloride-based polymerInfo
- Publication number
- JPH0776602A JPH0776602A JP5246395A JP24639593A JPH0776602A JP H0776602 A JPH0776602 A JP H0776602A JP 5246395 A JP5246395 A JP 5246395A JP 24639593 A JP24639593 A JP 24639593A JP H0776602 A JPH0776602 A JP H0776602A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- oil
- polymerization
- suspension
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塩化ビニル系重合体の
製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a vinyl chloride polymer.
【０００２】[0002]
【従来の技術】塩化ビニル又は塩化ビニルを含有する単
量体の混合物を水性媒体中で懸濁重合する方法において
は、通常、触媒として油溶性開始剤が用いられ、これは
例えばトルエン、イソパラフィン等の有機溶剤に溶解し
た状態で重合器に仕込まれる。原材料の重合器への仕込
みは、通常、水性媒体及び懸濁剤を仕込んだ後に単量体
を仕込むという順序で行われ、油溶性開始剤の仕込みは
単量体の仕込みの前後に行われる。In the method of suspension polymerization of vinyl chloride or a mixture of monomers containing vinyl chloride in an aqueous medium, an oil-soluble initiator is usually used as a catalyst, such as toluene or isoparaffin. It is charged into the polymerization vessel in a state of being dissolved in the organic solvent of. The raw materials are usually charged into the polymerization vessel in the order of charging the aqueous medium and the suspending agent and then the monomer, and the oil-soluble initiator is charged before and after the charging of the monomers.
【０００３】しかし、上記の仕込み方法によると油溶性
開始剤の溶剤として使用された有機溶剤が生成した重合
体中に残留するために、製品の品質低下や加工時におけ
る悪臭の原因となる。また、重合中に油溶性開始剤が高
温にさらされることがあると油溶性開始剤の分解が連鎖
的に進行し易く、重合の安定性、安全性が低いという難
点がある。However, according to the above-mentioned charging method, the organic solvent used as the solvent for the oil-soluble initiator remains in the produced polymer, which causes deterioration of product quality and a bad odor during processing. Further, if the oil-soluble initiator is exposed to a high temperature during the polymerization, the decomposition of the oil-soluble initiator is likely to proceed in a chain, and the stability and safety of the polymerization are low.
【０００４】これらの難点を解決するために、油溶性開
始剤を水性エマルジョンとして仕込む方法が提案されて
いる（特開昭６１−１３０３１５、特開昭６２−８６０
０５）。この方法によれば、有機溶剤をほとんど使用せ
ずに済む他、油溶性開始剤の微粒子が個々に水中に分散
しているため高温にさらされた場合でも開始剤の分解が
起こりにくく、安定にかつ安全に重合を行うことができ
る。しかし、油溶性開始剤の水性エマルジョンを使用し
て懸濁重合を行った場合には、油溶性開始剤が微粒であ
るものの溶解していないために、単量体との混合に時間
がかかり油溶性開始剤が単量体中に均一に分散しにくい
という難点がある。In order to solve these problems, a method of charging an oil-soluble initiator as an aqueous emulsion has been proposed (JP-A-61-130315 and JP-A-62-860).
05). According to this method, in addition to using almost no organic solvent, since the fine particles of the oil-soluble initiator are individually dispersed in water, decomposition of the initiator does not easily occur even when exposed to high temperature, and stable. And, the polymerization can be performed safely. However, when suspension polymerization is carried out using an aqueous emulsion of an oil-soluble initiator, the oil-soluble initiator is in the form of fine particles but is not dissolved. There is a drawback that the soluble initiator is difficult to be uniformly dispersed in the monomer.
【０００５】この難点は、特に生産性の高い製造方法、
例えば、仕込み水として加熱水を使用する方法等の原材
料の仕込み工程から重合反応の開始に至る時間を大幅に
短縮する方法や、大型の重合器を使用する方法を行った
場合に不利をもたらす。この開始剤の水性エマルジョン
を使用して、該製造方法を行った場合、単量体との混合
が十分行われないまま重合が開始するので、重合系にお
いて不均一な反応が生じることとなり、得られる重合体
の品質が安定しない、フィッシュアイが増加する等の問
題が起こる。This problem is caused by a particularly high productivity manufacturing method,
For example, there are disadvantages when a method of significantly reducing the time from the step of charging raw materials to the start of the polymerization reaction, such as a method of using heated water as charging water, or a method of using a large-sized polymerization vessel. When the production method is carried out using an aqueous emulsion of this initiator, the polymerization starts without sufficient mixing with the monomer, resulting in a non-uniform reaction in the polymerization system. Problems such as unstable quality of the obtained polymer and increase of fish eyes occur.
【０００６】[0006]
【発明が解決しようとする課題】そこで、本発明の課題
は、油溶性開始剤の水性エマルジョンを使用して、塩化
ビニル又は塩化ビニルを含有する単量体混合物を水性媒
体中で懸濁重合する方法において、仕込み水として加熱
水を使用する方法等の原材料の仕込み工程から重合反応
の開始に至る時間を大幅に短縮する方法、大型の重合器
を使用する方法等を行った場合でも、安定した品質の、
特にフィッシュアイの少ない重合体が得られる塩化ビニ
ル系重合体の製造方法を提供することである。The object of the present invention is therefore to suspension polymerize vinyl chloride or a monomer mixture containing vinyl chloride in an aqueous medium using an aqueous emulsion of an oil-soluble initiator. In the method, even when the method of significantly reducing the time from the raw material charging step to the start of the polymerization reaction, such as the method of using heated water as the charging water, the method of using a large-sized polymerization vessel, etc. were stable. Of quality,
It is an object of the present invention to provide a method for producing a vinyl chloride polymer, which can obtain a polymer having less fish eyes.
【０００７】[0007]
【課題を解決するための手段】本発明は、塩化ビニル又
は塩化ビニルを含有する単量体の混合物と油溶性開始剤
の水性エマルジョンとを含有する水性懸濁液を重合器中
で懸濁重合することにより塩化ビニル系重合体を製造す
る方法において、前記油溶性開始剤の水性エマルジョン
を調製し、前記水性懸濁液の調製に使用する懸濁剤の少
なくとも一部であって且つ前記油溶性開始剤の水性エマ
ルジョン中の油溶性開始剤当り５０重量％以上の量の前
記懸濁剤を該水性エマルジョンと混合し、得られた混合
液を重合器中に供給し前記水性懸濁液を調製して懸濁重
合を開始することを特徴とする塩化ビニル系重合体の製
造方法を提供するものである。The present invention is a suspension polymerization of an aqueous suspension containing vinyl chloride or a mixture of monomers containing vinyl chloride and an aqueous emulsion of an oil-soluble initiator in a polymerization vessel. In the method for producing a vinyl chloride-based polymer by preparing an aqueous emulsion of the oil-soluble initiator, which is at least a part of the suspending agent used in the preparation of the aqueous suspension, and the oil-soluble An amount of 50% by weight or more of the suspending agent based on the oil-soluble initiator in the aqueous emulsion of the initiator is mixed with the aqueous emulsion, and the resulting mixed solution is fed into a polymerization vessel to prepare the aqueous suspension. The present invention provides a method for producing a vinyl chloride-based polymer, which comprises initiating suspension polymerization.
【０００８】[0008]
【作用】本発明は、油溶性開始剤の水性エマルジョンに
予め懸濁剤を混合して重合器中に供給することを重要な
特徴とする。即ち本発明においては、懸濁剤と水性エマ
ルジョンとの混合により油溶性開始剤の個々のエマルジ
ョン粒子表面に懸濁剤粒子が分布するため、この混合液
を重合器中に供給して単量体の水性懸濁液と混合する
と、油溶性開始剤のエマルジョン粒子が直ちに該水性懸
濁剤中に均一に分散するものと信じられる。従って、懸
濁剤と水性エマルジョンとの混合液を重合器中に供給し
た後に直ちに重合を開始した場合にも、重合反応が均一
に進行し、安定な品質の重合体を得ることができ、しか
もフィッシュアイの発生も有効に抑制できるのである。The present invention has an important feature that an aqueous emulsion of an oil-soluble initiator is mixed with a suspending agent in advance and fed into a polymerization vessel. That is, in the present invention, since the suspension agent particles are distributed on the surface of each emulsion particle of the oil-soluble initiator by mixing the suspension agent and the aqueous emulsion, this mixture liquid is supplied into the polymerization vessel to supply the monomer. It is believed that the emulsion particles of the oil-soluble initiator will immediately disperse uniformly in the aqueous suspension when mixed with the aqueous suspension. Therefore, even when the polymerization is started immediately after supplying the mixed solution of the suspending agent and the aqueous emulsion into the polymerization vessel, the polymerization reaction proceeds uniformly and a polymer of stable quality can be obtained. The generation of fish eyes can also be effectively suppressed.
【０００９】[0009]
【発明の好適態様の説明】油溶性開始剤 本発明の製造方法で使用される油溶性開始剤としては、
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−ブチルパーオキシピパレー
ト、ｔ−ヘキシルパーオキシピパレート、α−クミルパ
ーオキシネオデカネート、２，４，４−トリメチルペン
チル−２−パーオキシ−２−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、２，４，４−トリメチルペンチル−２
−パーオキシフェノキシアセテート、３，３，５−トリ
メチルヘキサノイルパーオキシド、ラウロイルパーオキ
シド、クメンハイドロパーオキシド等のパーオキシド化
合物；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）等のアゾ化合物等が挙げられる。これらの油溶性開
始剤は、一種又は二種以上組み合わせて用いられる。BEST MODE FOR CARRYING OUT THE INVENTION Oil-soluble initiator The oil-soluble initiator used in the production method of the present invention includes:
For example, peroxycarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate; t-butyl peroxypiparate, t-hexylperoxypiparate, α- Peroxy ester compounds such as cumyl peroxy neodecanoate and 2,4,4-trimethylpentyl-2-peroxy-2-neodecanate; acetylcyclohexylsulfonyl peroxide and 2,4,4-trimethylpentyl-2
-Peroxyphenoxyacetate, 3,3,5-trimethylhexanoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and other peroxide compounds; azobis-2,4-dimethylvaleronitrile, azobis (4-methoxy-2,4) -Dimethylvaleronitrile) and other azo compounds and the like. These oil-soluble initiators are used alone or in combination of two or more.
【００１０】上記の油溶性開始剤は、通常、単量体１０
０重量部に対して０．００１〜１重量部添加される。油溶性開始剤の水性エマルジョン 油溶性開始剤の水性エマルジョンの調製は、例えば、粉
末状あるいは液状の油溶性開始剤と水とを混合し、乳化
剤等の分散助剤を添加して調製する。また、ホモジナイ
ザー、コロイドミル等の高速剪断混合機を用いれば、よ
り均一な水性エマルジョンを得ることができる。The above-mentioned oil-soluble initiator is usually a monomer 10
0.001 to 1 part by weight is added to 0 part by weight. Aqueous Emulsion of Oil-Soluble Initiator An aqueous emulsion of an oil-soluble initiator is prepared, for example, by mixing a powdery or liquid oil-soluble initiator with water and adding a dispersion aid such as an emulsifier. If a high speed shear mixer such as a homogenizer or a colloid mill is used, a more uniform aqueous emulsion can be obtained.
【００１１】上記水性エマルジョンの調製に使用される
乳化剤等の分散助剤は従来使用されているものでよく、
例えば、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重合体；ソルビタンモノラ
ウレート、ソルビタントリオレート、ソルビタンモノス
テアレート、グリセリントリステアレート、エチレンオ
キシド−プロピレンオキシドブロック共重合体等の油溶
性乳化剤、ポリオキシエチレンソルビタンモノラウレー
ト、ポリオキシエチレングリセリンオレート、ラウリン
酸等の水溶性乳化剤；炭酸カルシウム、リン酸カルシウ
ム等の無機塩化合物；ドデシルベンゼンスルホン酸ナト
リウム、ラウリル硫酸ナトリウム等の有機酸塩等が挙げ
られる。これらの分散助剤は、一種又は二種以上組み合
わせて使用してもよい。The dispersion aid such as an emulsifier used for preparing the above-mentioned aqueous emulsion may be a conventionally used one,
For example, water-soluble polymers such as partially saponified polyvinyl alcohol, acrylic acid polymers and gelatin; oils such as sorbitan monolaurate, sorbitan trioleate, sorbitan monostearate, glycerin tristearate and ethylene oxide-propylene oxide block copolymers. Water-soluble emulsifiers, water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate and lauric acid; inorganic salt compounds such as calcium carbonate and calcium phosphate; organic acid salts such as sodium dodecylbenzene sulfonate and sodium lauryl sulfate Is mentioned. These dispersion aids may be used alone or in combination of two or more.
【００１２】上記の水性エマルジョン中の油溶性開始剤
の平均粒径は特に限定されないが、５μｍ以下であるこ
とが好ましい。また、上記の水性エマルジョン中の油溶
性開始剤の濃度は特に限定されないが、一般には、１０
〜３０重量％の範囲内であることが好ましい。油溶性開
始剤の濃度が低過ぎると、必要量の開始剤当りの該水溶
性エマルジョンの仕込み量が多くなるので仕込み時間が
長くなり、また、高過ぎると該エマルジョンが高粘度と
なるためにポンプアップが難しくなる傾向がある。The average particle size of the oil-soluble initiator in the above aqueous emulsion is not particularly limited, but is preferably 5 μm or less. The concentration of the oil-soluble initiator in the above aqueous emulsion is not particularly limited, but is generally 10
It is preferably in the range of ˜30% by weight. If the concentration of the oil-soluble initiator is too low, the amount of the water-soluble emulsion charged per required amount of the initiator will be large, and the charging time will be long.If it is too high, the emulsion will have a high viscosity, and the pump Up tends to be difficult.
【００１３】懸濁剤 単量体を含む水性懸濁液の調製に使用する懸濁剤として
は、例えば、水溶性の部分けん化ポリビニルアルコー
ル；メチルセルロース、エチルセルロース、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水溶性のセルロ
ースエーテル等が挙げられる。これらの懸濁剤の中で
も、特に好適なものは、水溶性の部分けん化ポリビニル
アルコールであり、より好適なものはけん化度で６０〜
９０モル％のものである。懸濁剤の使用量は、通常、油
溶性開始剤の使用量によっても異なるが、一般的には、
単量体１００重量部に対して０．０１〜１重量部であ
る。 Suspending agents Examples of suspending agents used for preparing an aqueous suspension containing a monomer include water-soluble partially saponified polyvinyl alcohol; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose. And water-soluble cellulose ethers. Among these suspending agents, a particularly preferable one is a water-soluble partially saponified polyvinyl alcohol, and a more preferable one has a saponification degree of 60 to 60.
90 mol%. The amount of the suspension agent usually varies depending on the amount of the oil-soluble initiator used, but in general,
It is 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer.
【００１４】懸濁剤の供給 本発明において、懸濁剤は油溶性開始剤の水性エマルジ
ョンと混合して重合器中に供給される。懸濁剤と油溶性
開始剤の水性エマルジョンとの混合液は、開始剤の濃度
で少なくとも２重量％以上、特に３〜６重量％となるよ
う調製することが好ましい。開始剤の濃度が低過ぎる
と、上記混合液の仕込み量が多くなるために開始剤の実
質的仕込み時間が長くなり、生産効率が低下する恐れが
ある。上記懸濁剤は直接に水性エマルジョンと混合して
もよいし、水溶液として混合してもよいが、通常、水溶
液として混合することが好適である。水溶液として使用
する場合には、通常、該水溶液中の懸濁剤の濃度は１〜
１０重量％程度である。 Supply of Suspending Agent In the present invention, the suspending agent is mixed with the aqueous emulsion of the oil-soluble initiator and supplied into the polymerization vessel. The mixed solution of the suspension agent and the aqueous emulsion of the oil-soluble initiator is preferably prepared so that the concentration of the initiator is at least 2% by weight or more, and particularly 3 to 6% by weight. If the concentration of the initiator is too low, the charging amount of the above-mentioned mixed solution becomes large, so that the charging time of the initiator is substantially lengthened and the production efficiency may decrease. The above-mentioned suspending agent may be directly mixed with the aqueous emulsion or may be mixed as an aqueous solution, but it is usually preferable to be mixed as an aqueous solution. When used as an aqueous solution, the concentration of the suspending agent in the aqueous solution is usually 1 to
It is about 10% by weight.
【００１５】懸濁剤全量のうち、油溶性開始剤当り少な
くとも５０重量％、特に６０重量％以上の量は、水性エ
マルジョンとの混合に使用するべきである。この量が５
０重量％未満であると、油溶性開始剤の単量体中への分
散状態が十分に改善されず、得られる重合体のフィッシ
ュアイが増加することとなる。また、一部の懸濁剤を水
性エマルジョンと混合し、残量の懸濁剤を直接あるいは
水性媒体とともに重合器中に供給してもよい。特に、懸
濁剤の仕込み量が、開始剤の使用量に比してかなり多量
となる場合には、開始剤の供給効率等の観点から、この
供給方法は有効である。Of the total amount of suspension, at least 50% by weight, in particular 60% by weight or more, based on the oil-soluble initiator, should be used for mixing with the aqueous emulsion. This amount is 5
When it is less than 0% by weight, the dispersion state of the oil-soluble initiator in the monomer is not sufficiently improved, and the fish eye of the obtained polymer increases. Alternatively, a part of the suspending agent may be mixed with the aqueous emulsion, and the remaining amount of the suspending agent may be supplied directly or together with the aqueous medium into the polymerization vessel. In particular, when the amount of the suspension agent charged is considerably larger than the amount of the initiator used, this supply method is effective from the viewpoint of the supply efficiency of the initiator and the like.
【００１６】油溶性開始剤の水性エマルジョンと懸濁剤
とを混合する工程は、得られる混合液を重合器に仕込む
直前に行うことが好ましい。混合した状態で長時間放置
しておくと開始剤の分解が始まり、開始剤の活性がなく
なる恐れがあるからである。また、混合操作は混合液が
肉眼で判断して見かけ上均一な状態になれば十分であ
り、それを超えて長く混合操作を行うと開始剤の活性低
下を招く恐れが大きい。油溶性開始剤の水性エマルジョ
ンと懸濁剤とを混合する方法は、特に限定されない。例
えば、懸濁剤の溶解槽に直接に油溶性開始剤の水性エマ
ルジョンを投入し攪拌してもよいし、懸濁剤溶液の仕込
み用の配管にインラインミキサーを取り付けて、懸濁剤
と油溶性開始剤の水性エマルジョンとを混合してから重
合器に仕込んでもよい。これらの方法以外に、ホモジナ
イザー、コロイドミル等を用いた高速剪断による混合方
法も挙げられる。The step of mixing the aqueous emulsion of the oil-soluble initiator and the suspending agent is preferably carried out immediately before charging the resulting mixed solution into the polymerization vessel. This is because if left in a mixed state for a long time, decomposition of the initiator may start and the activity of the initiator may be lost. Further, it is sufficient for the mixing operation that the mixed solution is visually uniform when judged by the naked eye, and if the mixing operation is performed longer than that, the activity of the initiator may be lowered. The method of mixing the aqueous emulsion of the oil-soluble initiator and the suspension agent is not particularly limited. For example, an aqueous emulsion of an oil-soluble initiator may be directly added to a suspension tank for a suspension agent and stirred, or an in-line mixer may be attached to a pipe for preparing a suspension agent solution to disperse the suspension agent and the oil-soluble agent. It is also possible to mix with the aqueous emulsion of the initiator and then charge it in the polymerization vessel. In addition to these methods, a mixing method by high-speed shearing using a homogenizer, a colloid mill or the like can also be mentioned.
【００１７】単量体 重合に供される単量体としては、塩化ビニル又は塩化ビ
ニルを含有する単量体の混合物が用いられる。塩化ビニ
ルを含有する単量体の混合物は、塩化ビニル単量体と、
塩化ビニルと共重合可能な他のビニル系単量体との混合
物である。該混合物中、塩化ビニルの含有率は、好まし
くは５０重量％以上である。塩化ビニルと共重合可能な
他のビニル系単量体としては、例えば、酢酸ビニル、プ
ロピオン酸ビニル等のビニルエステル；アクリル酸メチ
ル、アクリル酸エチル等のアクリル酸エステル；メタク
リル酸メチル、メタクリル酸エチル等のメタクリル酸エ
ステル；エチレン、プロピレン等のオレフィン；ラウリ
ルビニルエーテル、イソブチルビニルエーテル等のビニ
ルエーテル；無水マレイン酸；アクリロニトリル；スチ
レン；塩化ビニリデン等が挙げられる。これらは、一種
又は二種以上組み合わせて用いられる。As the monomer used for the monomer polymerization, vinyl chloride or a mixture of monomers containing vinyl chloride is used. The mixture of monomers containing vinyl chloride, vinyl chloride monomer,
It is a mixture with another vinyl-based monomer copolymerizable with vinyl chloride. The content of vinyl chloride in the mixture is preferably 50% by weight or more. Other vinyl monomers copolymerizable with vinyl chloride include, for example, vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid esters such as methyl acrylate and ethyl acrylate; methyl methacrylate and ethyl methacrylate. And the like; olefins such as ethylene and propylene; vinyl ethers such as lauryl vinyl ether and isobutyl vinyl ether; maleic anhydride; acrylonitrile; styrene; and vinylidene chloride. These are used alone or in combination of two or more.
【００１８】その他の添加剤 本発明のその他の条件は、通常の塩化ビニル又は塩化ビ
ニルを含む単量体混合物の水性媒体中における懸濁重合
と同様である。本発明の製造方法では、必要に応じて、
塩化ビニル系重合体の製造に使用される重合調整剤、連
鎖移動剤、ｐＨ調整剤、ゲル化改良剤、帯電防止剤、架
橋剤、安定剤、充填剤、緩衝剤、スケール防止剤、抗酸
化剤等を添加することができる。 Other Additives The other conditions of the present invention are the same as the suspension polymerization of a conventional vinyl chloride or a monomer mixture containing vinyl chloride in an aqueous medium. In the production method of the present invention, if necessary,
Polymerization regulators, chain transfer agents, pH regulators, gelation improvers, antistatic agents, crosslinking agents, stabilizers, fillers, buffers, scale inhibitors, antioxidants used in the production of vinyl chloride polymers Agents and the like can be added.
【００１９】重合 重合は、次のように行う。設定した重合温度付近に加熱
した脱イオン水〔通常、（重合温度−５）〜（重合温度
＋１０）℃の温度で使用する〕を重合器に仕込む。この
脱イオン水の温度が低過ぎると、反応混合物の昇温時間
を十分に短縮することができない。また、高過ぎると、
ガラス玉状の重合体が生成し易くなりフィッシュアイの
原因となったり、重合開始時の反応混合物の温度が設定
した重合温度よりも高くなるために温度コントロールす
るための操作が複雑になる等の不都合が生じる。上記脱
イオン水の仕込み量は、通常、単量体１００重量部に対
して８０〜３００重量部である。 Polymerization Polymerization is carried out as follows. Deionized water heated to around the set polymerization temperature [usually used at a temperature of (polymerization temperature −5) to (polymerization temperature +10) ° C.] is charged into a polymerization vessel. If the temperature of this deionized water is too low, the temperature rising time of the reaction mixture cannot be shortened sufficiently. Also, if it is too high,
A glass bead-shaped polymer is likely to be generated, which causes fish eyes, and the temperature of the reaction mixture at the start of polymerization becomes higher than the set polymerization temperature, which complicates the operation for controlling the temperature. Inconvenience occurs. The charged amount of the deionized water is usually 80 to 300 parts by weight based on 100 parts by weight of the monomer.
【００２０】次いで、重合器内を脱気して０．１〜３０
０ｍｍＨｇに減圧した後、攪拌しながら単量体、及び油
溶性開始剤の水性エマルジョンと懸濁剤との混合液を別
々の配管で同時に仕込む（原材料の仕込みは、加える順
番を決めて段階的に行ってもよい）。攪拌しながら昇温
を開始し、３０〜８０℃の反応温度で重合する。この
時、重合器の内圧は、３〜１２ｋｇｆ／ｃｍ2 ・Ｇ程度
である。重合中には、必要に応じて、重合中の懸濁系を
安定に維持するために、水、重合開始剤、及び分散助
剤、懸濁剤等の分散剤の一種又は二種以上を添加するこ
とができる。また、重合時の反応温度は、重合される単
量体の種類によって異なり、例えば、塩化ビニルを重合
する場合には３０〜８０℃で重合を行い、塩化ビニルと
スチレンとの混合物を重合する場合には５０〜１５０℃
で重合を行う。Then, the inside of the polymerization vessel is deaerated to 0.1 to 30.
After reducing the pressure to 0 mmHg, a mixture of the monomer and the aqueous emulsion of the oil-soluble initiator and the suspension agent is simultaneously charged in separate pipes with stirring (the raw materials are added stepwise by determining the order of addition). You may go). The temperature rise is started with stirring, and polymerization is carried out at a reaction temperature of 30 to 80 ° C. At this time, the internal pressure of the polymerization vessel is about 3 to 12 kgf / cm 2 · G. During the polymerization, if necessary, in order to maintain a stable suspension system during the polymerization, one or more kinds of water, a polymerization initiator, and a dispersant such as a dispersion aid and a suspending agent are added. can do. Further, the reaction temperature at the time of polymerization varies depending on the kind of the monomer to be polymerized. For example, in the case of polymerizing vinyl chloride, the polymerization is carried out at 30 to 80 ° C., and the mixture of vinyl chloride and styrene is polymerized. 50 to 150 ℃
Polymerize with.
【００２１】重合は、重合器の内圧が重合中の圧力から
０．１〜４．０ｋｇｆ／ｃｍ2 ・Ｇ降圧した時に、ある
いは重合器外周に装備されたジャケット内に流入、流出
させる冷却水の入口温度と出口温度との差がほぼなくな
った時（すなわち重合反応による発熱がなくなった時）
に、完了したと判断される。そして、未反応の単量体を
回収し脱水し乾燥して目的の重合体を得る。The polymerization is carried out when the internal pressure of the polymerization vessel is lowered by 0.1 to 4.0 kgf / cm 2 · G from the pressure during the polymerization, or when the cooling water is made to flow into and out of the jacket mounted on the outer circumference of the polymerization vessel. When there is almost no difference between the inlet temperature and the outlet temperature (that is, when the heat generated by the polymerization reaction disappears)
It is judged that it is completed. Then, the unreacted monomer is recovered, dehydrated and dried to obtain the target polymer.
【００２２】[0022]
【実施例】以下の実施例及び比較例において、次に列挙
する懸濁剤溶液及び開始剤の水性エマルジョンを使用し
た。懸濁剤溶液 懸濁剤溶液Ａ： 平均重合度２６００、けん化度８０．
２モル％の水溶性部分けん化ポリビニルアルコール２５
２ｇを５０００ｇの脱イオン水に溶解したもの（濃度
４．８％）。 懸濁剤溶液Ｂ： メトキシ置換度２９．２重量％、ヒド
ロキシプロポキシ置換度８．９重量％のヒドロキシプロ
ピルメチルセルロース（２重量％水溶液の２０℃におけ
る粘度が４９．５ｃＰのもの）１６８ｇを４５００ｇの
脱イオン水に溶解したもの（濃度３．６重量％）。 懸濁剤溶液Ｃ： 懸濁剤溶液Ａ５２５２ｇと懸濁剤溶液
Ｂ４６６８ｇとを混合したもの。EXAMPLES In the following examples and comparative examples, the following suspension solutions and aqueous emulsions of initiators were used. Suspending agent solution Suspending agent solution A: average degree of polymerization 2600, degree of saponification 80.
2 mol% water-soluble partially saponified polyvinyl alcohol 25
2 g dissolved in 5000 g deionized water (concentration 4.8%). Suspending agent solution B: Dehydration of 4500 g of 168 g of hydroxypropylmethylcellulose having a methoxy substitution degree of 29.2% by weight and a hydroxypropoxy substitution degree of 8.9% by weight (the viscosity of a 2% by weight aqueous solution at 20 ° C. is 49.5 cP). What was dissolved in deionized water (concentration 3.6% by weight). Suspending agent solution C: A mixture of 5252 g of suspending agent solution A and 4668 g of suspending agent solution B.
【００２３】開始剤の水性エマルジョン エマルジョンａ： ジ−２−エチルヘキシルパーオキシ
ジカーボネートの水性エマルジョンである（固形分の濃
度２０ｗｔ％、エマルジョンの平均粒径３．８μｍ）。 エマルジョンｂ： エマルジョンａに、乳化剤としてポ
リオキシエチレンソルビタンモノラウレートを対開始剤
量で１．５ｗｔ％添加したものである（エマルジョンの
平均粒径１．１μｍ）。 Initiator Aqueous Emulsion Emulsion a: An aqueous emulsion of di-2-ethylhexyl peroxydicarbonate (concentration of solid content: 20 wt%, average particle size of emulsion: 3.8 μm). Emulsion b: Polyoxyethylene sorbitan monolaurate as an emulsifier was added to the emulsion a in an amount of 1.5 wt% based on the amount of the initiator (average particle size of the emulsion: 1.1 μm).
【００２４】実施例１ 懸濁剤溶液Ａ５２５２ｇにエマルジョンａ１４００ｇ
（開始剤含有量２８０ｇ）を加え、約１５分間攪拌し混
合液を調製した（該混合液中の懸濁剤量と開始剤量との
比は２５２ｇ／２８０ｇ＝０．９０であった）。次い
で、冷却ジャケットが付設された内容積２０００リット
ルのステンレス製重合器の器内を脱気して重合器内圧を
１００ｍｍＨｇとした後、攪拌しながら６０℃に加熱し
た脱イオン水９８０ｋｇ、上記混合液、懸濁剤溶液Ｂ
４６６８ｇ、及び塩化ビニル単量体７００ｋｇを別々の
配管で同時に仕込んだ（この時重合器内の温度は５６．
５℃であった）。攪拌しながらジャケットに熱水を通し
て昇温を開始し、重合器内が、５７．５℃まで昇温した
ところで、その温度を保ち重合を続けた。重合器内の内
圧が６．０ｋｇ／ｃｍ2 ・Ｇ に達した時点で反応を停
止し、未反応の単量体を回収した後、重合体スラリーを
脱水し乾燥して塩化ビニル重合体を得た。得られた重合
体について、後記の要領で、嵩比重、粒度分布、可塑剤
吸収量、フィッシュアイ、熱安定性の測定を行った。そ
の結果を表１に示す。 Example 1 1400 g of emulsion a in 5252 g of suspension solution A
(Initiator content: 280 g) was added and stirred for about 15 minutes to prepare a mixed solution (the ratio of the amount of the suspending agent to the amount of the initiator in the mixed solution was 252 g / 280 g = 0.90). Then, after degassing the inside of the polymerization vessel made of stainless steel with an internal volume of 2000 liters equipped with a cooling jacket so that the internal pressure of the polymerization vessel was 100 mmHg, 980 kg of deionized water heated to 60 ° C. with stirring, the above mixed solution , Suspension agent B
4668 g and 700 kg of vinyl chloride monomer were simultaneously charged in separate pipes (at this time, the temperature in the polymerization vessel was 56.
It was 5 ° C). While stirring, hot water was passed through the jacket to start heating, and when the temperature in the polymerization vessel was raised to 57.5 ° C., the temperature was maintained and polymerization was continued. When the internal pressure in the polymerization vessel reached 6.0 kg / cm 2 · G, the reaction was stopped, unreacted monomers were collected, and then the polymer slurry was dehydrated and dried to obtain a vinyl chloride polymer. It was The obtained polymer was measured for bulk specific gravity, particle size distribution, plasticizer absorption, fish eye, and thermal stability as described below. The results are shown in Table 1.
【００２５】実施例２ 懸濁剤溶液Ｂ４６６８ｇにエマルジョンａ１４００ｇ
（開始剤含有量２８０ｇ）を加え、約１５分間攪拌し混
合液を調製した（該混合液中の懸濁剤量と開始剤量との
比は１６８ｇ／２８０ｇ＝０．６０であった）。次い
で、冷却ジャケットが付設された内容積２０００リット
ルのステンレス製重合器の器内を脱気して重合器内圧を
１００ｍｍＨｇとした後、攪拌しながら６０℃に加熱し
た脱イオン水９８０ｋｇ、上記混合液、懸濁剤溶液Ａ
５２５２ｇ、及び塩化ビニル単量体７００ｋｇを別々の
配管で同時に仕込んだ。攪拌しながらジャケットに熱水
を通して昇温を開始し、重合器内が、５７．５℃まで昇
温したところで、その温度を保ち重合を続けた。重合器
内の内圧が６．０ｋｇ／ｃｍ2 ・Ｇ に達した時点で反
応を停止し、未反応の単量体を回収した後、重合体スラ
リーを脱水し乾燥して塩化ビニル重合体を得た。得られ
た重合体について、実施例１と同様にして各種の特性を
測定した。その結果を表１に示す。 Example 2 1468 g of emulsion a in 4668 g of suspension solution B
(Initiator content: 280 g) was added and stirred for about 15 minutes to prepare a mixed solution (the ratio of the amount of the suspending agent to the amount of the initiator in the mixed solution was 168 g / 280 g = 0.60). Then, after degassing the inside of the polymerization vessel made of stainless steel with an internal volume of 2000 liters equipped with a cooling jacket so that the internal pressure of the polymerization vessel was 100 mmHg, 980 kg of deionized water heated to 60 ° C. with stirring, the above mixed solution , Suspension agent A
5252 g and 700 kg of vinyl chloride monomer were simultaneously charged through separate pipes. While stirring, hot water was passed through the jacket to start heating, and when the temperature in the polymerization vessel was raised to 57.5 ° C., the temperature was maintained and polymerization was continued. When the internal pressure in the polymerization vessel reached 6.0 kg / cm 2 · G, the reaction was stopped, unreacted monomers were collected, and then the polymer slurry was dehydrated and dried to obtain a vinyl chloride polymer. It was Various properties of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.
【００２６】実施例３ 懸濁剤溶液Ｃ９９２０ｇにエマルジョンａ１４００ｇ
（開始剤含有量２８０ｇ）を加え、約１５分間攪拌し混
合液を調製した（該混合液中の懸濁剤量と開始剤量との
比は４２０ｇ／２８０ｇ＝１．５であった）。次いで、
冷却ジャケットが付設された内容積２０００リットルの
ステンレス製重合器の器内を脱気して重合器内圧を１８
０ｍｍＨｇとした後、攪拌しながら６０℃に加熱した脱
イオン水９８０ｋｇ、上記混合液及び塩化ビニル単量体
７００ｋｇを別々の配管で同時に仕込んだ。攪拌しなが
らジャケットに熱水を通して昇温を開始し、重合器内
が、５７．５℃まで昇温したところで、その温度を保ち
重合を続けた。重合器内の内圧が６．０ｋｇ／ｃｍ2 ・
Ｇ に達した時点で反応を停止し、未反応の単量体を回
収した後、重合体スラリーを脱水し乾燥して塩化ビニル
重合体を得た。得られた重合体について、実施例１と同
様にして各種の特性を測定した。その結果を表１に示
す。 Example 3 1940 g of emulsion a in 9920 g of suspension solution C
(Initiator content: 280 g) was added and stirred for about 15 minutes to prepare a mixed solution (the ratio of the amount of the suspending agent to the amount of the initiator in the mixed solution was 420 g / 280 g = 1.5). Then
The inside pressure of the polymerization vessel was increased to 18 by degassing the inside of the polymerization vessel made of stainless steel with an internal volume of 2000 liters equipped with a cooling jacket.
After adjusting the pressure to 0 mmHg, 980 kg of deionized water heated to 60 ° C. with stirring, the mixed solution and 700 kg of vinyl chloride monomer were simultaneously charged in separate pipes. While stirring, hot water was passed through the jacket to start heating, and when the temperature in the polymerization vessel was raised to 57.5 ° C., the temperature was maintained and polymerization was continued. The internal pressure in the polymerization vessel is 6.0 kg / cm 2 ·
The reaction was stopped when it reached G 2, and the unreacted monomer was recovered, and then the polymer slurry was dehydrated and dried to obtain a vinyl chloride polymer. Various properties of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.
【００２７】実施例４ 懸濁剤溶液Ｃとエマルジョンａとの混合液を別途調製し
て重合器に仕込むことに代えて、懸濁剤の仕込配管に取
り付けられたインラインミキサー内で懸濁剤溶液Ｃ９９
２０ｇとエマルジョンａ１４００ｇとを混合し、得られ
た混合液を直接該インラインミキサー内から重合器に仕
込んだ以外は、実施例３と同様にして重合体を製造し
た。得られた重合体について、実施例１と同様にして各
種の特性を測定した。その結果を表１に示す。 Example 4 Instead of separately preparing a mixed solution of the suspension agent solution C and the emulsion a and charging it in the polymerization vessel, the suspension agent solution was put in an in-line mixer attached to a suspension agent charging pipe. C99
A polymer was produced in the same manner as in Example 3 except that 20 g of the emulsion a and 1400 g of the emulsion a were mixed and the resulting mixed solution was directly charged into the polymerization vessel from the in-line mixer. Various properties of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.
【００２８】比較例１ 冷却ジャケットが付設された内容積２０００リットルの
ステンレス製重合器の器内を脱気して重合器内圧を１０
０ｍｍＨｇとした後、攪拌しながら６０℃に加熱した脱
イオン水 ９８０ｋｇ、懸濁剤溶液Ａ ５２５２ｇ、エ
マルジョンａ１４００ｇ、懸濁剤溶液Ｂ ４６６８ｇ及
び塩化ビニル単量体 ７００ｋｇを別々の配管で同時に
仕込んだ。攪拌しながらジャケットに熱水を通して昇温
を開始し、重合器内が、５７．５℃まで昇温したところ
で、その温度を保ち重合を続けた。重合器内の内圧が
６．０ｋｇ／ｃｍ2 ・Ｇ に達した時点で反応を停止
し、未反応の単量体を回収した後、重合体スラリーを脱
水し乾燥して塩化ビニル重合体を得た。得られた重合体
について、実施例１と同様にして各種の特性を測定し
た。その結果を表１に示す。 Comparative Example 1 The inside pressure of the polymerization vessel was adjusted to 10 by degassing the inside of the polymerization vessel made of stainless steel having an internal volume of 2000 liters and equipped with a cooling jacket.
After adjusting the pressure to 0 mmHg, 980 kg of deionized water heated to 60 ° C. with stirring, 5252 g of suspending agent solution A, 1400 g of emulsion a, 4668 g of suspending agent solution B, and 700 kg of vinyl chloride monomer were simultaneously charged in separate pipes. While stirring, hot water was passed through the jacket to start heating, and when the temperature in the polymerization vessel was raised to 57.5 ° C., the temperature was maintained and polymerization was continued. When the internal pressure in the polymerization vessel reached 6.0 kg / cm 2 · G, the reaction was stopped, unreacted monomers were collected, and then the polymer slurry was dehydrated and dried to obtain a vinyl chloride polymer. It was Various properties of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.
【００２９】比較例２ エマルジョンａに代えてエマルジョンｂを使用した以外
は比較例１と同様にして重合体を製造し、実施例１と同
様にして各種の特性を測定した。その結果を表１に示
す。 Comparative Example 2 A polymer was produced in the same manner as in Comparative Example 1 except that Emulsion b was used in place of Emulsion a, and various characteristics were measured in the same manner as in Example 1. The results are shown in Table 1.
【００３０】比較例３ 冷却ジャケットが付設された内容積２０００リットルの
ステンレス製重合器に６０℃に加熱した脱イオン水９８
０ｋｇ及び懸濁剤溶液Ｃ９９２０ｇを仕込み、重合器内
を脱気して重合器内圧を１８０ｍｍＨｇとした後、攪拌
しながら塩化ビニル単量体７００ｋｇ及びエマルジョン
ａ４６７ｇを別々の配管で同時に仕込んだ。攪拌しなが
らジャケットに熱水を通して昇温を開始し、重合器内
が、５７．５℃まで昇温したところで、その温度を保ち
重合を続けた。重合器内の内圧が６．０ｋｇ／ｃｍ2 ・
Ｇ に達した時点で反応を停止し、未反応の単量体を回
収した後、重合体スラリーを脱水し乾燥して塩化ビニル
重合体を得た。得られた重合体について、実施例１と同
様にして各種の特性を測定した。その結果を表１に示
す。 Comparative Example 3 98 deionized water heated to 60 ° C. was placed in a stainless steel polymerization vessel having an internal volume of 2000 liter and equipped with a cooling jacket.
0 kg and a suspension agent solution C9920 g were charged, the inside of the polymerization vessel was degassed to a polymerization vessel internal pressure of 180 mmHg, and then 700 kg of vinyl chloride monomer and 467 g of emulsion a were simultaneously charged with separate pipes while stirring. While stirring, hot water was passed through the jacket to start heating, and when the temperature in the polymerization vessel was raised to 57.5 ° C., the temperature was maintained and polymerization was continued. The internal pressure in the polymerization vessel is 6.0 kg / cm 2 ·
The reaction was stopped when it reached G 2, and the unreacted monomer was recovered, and then the polymer slurry was dehydrated and dried to obtain a vinyl chloride polymer. Various properties of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.
【００３１】比較例４ 懸濁剤溶液Ｃ９９２０ｇのうち２６４５ｇにエマルジョ
ンａ１４００ｇを加え、約１５分間攪拌して混合液を調
製した（該混合液中の懸濁剤量と開始剤量との比は１１
２ｇ／２８０ｇ＝０．４０である）。冷却ジャケットが
付設された内容積２０００リットルのステンレス製重合
器に６０℃に加熱した脱イオン水９８０ｋｇ、上記混合
液、懸濁剤溶液Ｃの残り分７２７５ｇ及び塩化ビニル単
量体７００ｋｇを別々の配管で同時に仕込んだ。攪拌し
ながらジャケットに熱水を通して昇温を開始し、重合器
内が、５７．５℃まで昇温したところで、その温度を保
ち重合を続けた。COMPARATIVE EXAMPLE 4 1400 g of emulsion a was added to 2645 g of 9920 g of the suspension solution C and stirred for about 15 minutes to prepare a mixed solution (the ratio of the amount of the suspending agent to the amount of the initiator in the mixed solution was 11).
2g / 280g = 0.40). Separately piped 980 kg of deionized water heated to 60 ° C., the above mixed solution, the remaining amount of suspension agent solution C, 7275 g, and 700 kg of vinyl chloride monomer in a 2000-liter stainless steel polymerization vessel equipped with a cooling jacket. I prepared it at the same time. While stirring, hot water was passed through the jacket to start heating, and when the temperature in the polymerization vessel was raised to 57.5 ° C., the temperature was maintained and polymerization was continued.
【００３２】重合器内の内圧が６．０ｋｇ／ｃｍ2 ・Ｇ
に達した時点で反応を停止し、未反応の単量体を回収
した後、重合体スラリーを脱水し乾燥して塩化ビニル重
合体を得た。得られた重合体について、実施例１と同様
にして各種の特性を測定した。その結果を表１に示す。The internal pressure in the polymerization vessel is 6.0 kg / cm 2 · G
The reaction was stopped when the temperature reached, and the unreacted monomer was recovered, and then the polymer slurry was dehydrated and dried to obtain a vinyl chloride polymer. Various properties of the obtained polymer were measured in the same manner as in Example 1. The results are shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】各例において得られた塩化ビニル系重合体
の各種の特性（嵩比重、粒度分布、可塑剤吸収量、フィ
ッシュアイ及び熱安定性）は、以下の方法により測定し
た。The various properties (bulk specific gravity, particle size distribution, plasticizer absorption, fish eye and thermal stability) of the vinyl chloride polymer obtained in each example were measured by the following methods.
【００３５】嵩比重 ＪＩＳ Ｋ−６７２１に従って測定した。粒度分布 ＪＩＳ Ｚ−８８０１に準じた＃６０、＃８０、＃１０
０、＃１２０、＃１５０及び＃２００の各篩を用いて篩
分けし、篩を通過した重合体の重量％を求めた。 Bulk specific gravity was measured according to JIS K-6721. Particle size distribution # 60, # 80, # 10 according to JIS Z-8801
It screened using each sieve of 0, # 120, # 150, and # 200, and weight% of the polymer which passed the sieve was calculated | required.
【００３６】可塑剤吸収量 塩化ビニル重合体１０ｇに対して、ジオクチルフタレー
ト（ＤＯＰ）１５ｃｃを加え十分練り合わせた後、３０
００回転／分で６０分間遠心分離し、１ｇあたりの塩化
ビニル重合体に吸収されたＤＯＰの重量％を測定した。フィッシュアイ 試料の塩化ビニル重合体１００重量部、三塩基性硫酸鉛
１重量部、ステアリン酸鉛１．５重量部、酸化チタン
０．２重量部、カーボンブラック０．１重量部、及びＤ
ＯＰ５０重量部からなる混合物を調製し、該混合物をロ
ールを用いて、厚さ０．２ｍｍのシートに成形した。得
られたシートの１００ｃｍ2 あたりに含まれるフィシュ
アイの個数を計数した。 Plasticizer absorption amount To 10 g of vinyl chloride polymer, 15 cc of dioctyl phthalate (DOP) was added and kneaded sufficiently, then 30
Centrifugation was carried out at 00 rpm for 60 minutes, and the weight% of DOP absorbed by the vinyl chloride polymer was measured per 1 g. 100 parts by weight of vinyl chloride polymer of fish eye sample, 1 part by weight of tribasic lead sulfate, 1.5 parts by weight of lead stearate, 0.2 part by weight of titanium oxide, 0.1 part by weight of carbon black, and D
A mixture containing 50 parts by weight of OP was prepared, and the mixture was formed into a sheet having a thickness of 0.2 mm by using a roll. The number of fish eyes contained in 100 cm 2 of the obtained sheet was counted.
【００３７】熱安定性 試料の塩化ビニル系重合体１００重量部に、ステアリン
酸亜鉛１．０重量部、ステアリン酸バリウム１．０重量
部、エポキシ化大豆油５．０重量部及びＤＯＰ４５．０
重量部を加え、１５０℃のロールで５分間混練した後、
厚さ０．８ｍｍのシートを成形した。このシートを１９
０℃のオーブン中に入れて黒化するまでの時間を測定
し、熱安定性を評価した。To 100 parts by weight of a vinyl chloride polymer as a heat stability sample, 1.0 part by weight of zinc stearate, 1.0 part by weight of barium stearate, 5.0 parts by weight of epoxidized soybean oil and DOP45.0.
After adding parts by weight and kneading with a roll at 150 ° C. for 5 minutes,
A sheet having a thickness of 0.8 mm was formed. This sheet 19
The heat stability was evaluated by measuring the time required for blackening by placing in an oven at 0 ° C.
【００３８】[0038]
【発明の効果】本発明の製造方法により、高品質の、特
には、フィッシュアイが少なく、熱安定性に優れた塩化
ビニル系重合体が得られる。また、本発明の製造方法
は、開始剤が重合系に速やかに分散するので、特に、単
量体と上記混合液が混合されると同時に重合反応が開始
される方法、例えば、予め設定された重合温度付近に加
熱した水を重合器に仕込み、脱気後、単量体の仕込みと
同時あるいは仕込み後に上記混合液を同時に仕込む方
法；予め脱気した重合器に、単量体、上記混合液及び重
合温度付近に加熱した水を同時に仕込む方法等に有効で
ある。EFFECTS OF THE INVENTION According to the production method of the present invention, a high-quality vinyl chloride polymer having a small number of fish eyes and excellent thermal stability can be obtained. Further, in the production method of the present invention, since the initiator is rapidly dispersed in the polymerization system, a method in which the polymerization reaction is started at the same time when the monomer and the mixed solution are mixed, for example, is set in advance. A method in which water heated to around the polymerization temperature is charged into a polymerization vessel, and after degassing, the above mixed solution is charged at the same time as or after charging the monomer; It is also effective for a method of charging water heated near the polymerization temperature at the same time.
Claims (4)
量体の混合物と油溶性開始剤の水性エマルジョンとを含
有する水性懸濁液を重合器中で懸濁重合することにより
塩化ビニル系重合体を製造する方法において、 前記油溶性開始剤の水性エマルジョンを調製し、 前記水性懸濁液の調製に使用する懸濁剤の少なくとも一
部であって且つ前記油溶性開始剤の水性エマルジョン中
の油溶性開始剤当り５０重量％以上の量の前記懸濁剤を
該水性エマルジョンと混合し、 得られた混合液を重合器中に供給し前記水性懸濁液を調
製して懸濁重合を開始することを特徴とする塩化ビニル
系重合体の製造方法。1. A vinyl chloride polymer by suspension-polymerizing an aqueous suspension containing vinyl chloride or a mixture of monomers containing vinyl chloride and an aqueous emulsion of an oil-soluble initiator in a polymerization vessel. A method of producing an aqueous emulsion of the oil-soluble initiator, wherein the oil is at least part of the suspending agent used in the preparation of the aqueous suspension and in the aqueous emulsion of the oil-soluble initiator. The suspension agent is mixed with the aqueous emulsion in an amount of 50% by weight or more per the soluble initiator, and the resulting mixed solution is fed into a polymerization vessel to prepare the aqueous suspension to initiate suspension polymerization. A method for producing a vinyl chloride-based polymer, comprising:
混合される懸濁剤が、水溶液の形で使用される請求項１
に記載の製造方法。2. The suspending agent mixed with the aqueous emulsion of the oil-soluble initiator is used in the form of an aqueous solution.
The manufacturing method described in.
が、単量体１００重量部当り０．０１〜１重量部の量で
使用される請求項１に記載の製造方法。3. The method according to claim 1, wherein the suspending agent used for preparing the aqueous suspension is used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the monomer.
の一部が前記油溶性開始剤の水性エマルジョンと混合さ
れ、残量の懸濁剤が該水性エマルジョンとは別個に重合
器中に供給される請求項３に記載の製造方法。4. A portion of the suspending agent used to prepare the aqueous suspension is mixed with the aqueous emulsion of the oil-soluble initiator, and the remaining amount of suspending agent is separate from the aqueous emulsion. The manufacturing method according to claim 3, which is supplied inside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5246395A JPH0776602A (en) | 1993-09-07 | 1993-09-07 | Production of vinyl chloride-based polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5246395A JPH0776602A (en) | 1993-09-07 | 1993-09-07 | Production of vinyl chloride-based polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0776602A true JPH0776602A (en) | 1995-03-20 |
Family
ID=17147883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5246395A Pending JPH0776602A (en) | 1993-09-07 | 1993-09-07 | Production of vinyl chloride-based polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776602A (en) |
-
1993
- 1993-09-07 JP JP5246395A patent/JPH0776602A/en active Pending
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