JP2003002911A - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymerInfo
- Publication number
- JP2003002911A JP2003002911A JP2001183412A JP2001183412A JP2003002911A JP 2003002911 A JP2003002911 A JP 2003002911A JP 2001183412 A JP2001183412 A JP 2001183412A JP 2001183412 A JP2001183412 A JP 2001183412A JP 2003002911 A JP2003002911 A JP 2003002911A
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- Japan
- Prior art keywords
- polymerization
- weight
- vinyl chloride
- polyvinyl alcohol
- added
- 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.)
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- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化ビニル系重合
体の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a vinyl chloride polymer.
【０００２】[0002]
【従来の技術】通常、塩化ビニル単量体の重合は加熱・
冷却のためのジャケット、攪拌装置等を備えた重合器を
用い、バッチ式の水懸濁重合方法で行われている。即
ち、重合器に水性媒体、塩化ビニル系単量体、分散剤及
び重合開始剤を仕込み、昇温して所定の重合温度に上げ
懸濁重合反応を行い、反応熱が出てきた時点からジャケ
ットに冷却水を通して冷却し、重合温度を所定温度に維
持して懸濁重合を進行させ、重合終了後、未反応の塩化
ビニル単量体を回収すると共に塩化ビニル重合体を取り
出す一連の操作で重合されている。2. Description of the Related Art Usually, vinyl chloride monomer is polymerized by heating.
A batch type water suspension polymerization method is carried out using a polymerization vessel equipped with a jacket for cooling, a stirrer and the like. That is, an aqueous medium, a vinyl chloride-based monomer, a dispersant and a polymerization initiator are charged in a polymerization vessel, the temperature is raised to a predetermined polymerization temperature to carry out a suspension polymerization reaction, and the jacket is started from the time when heat of reaction comes out. Cooling water is passed through and the polymerization temperature is maintained at a predetermined temperature to allow suspension polymerization to proceed.After completion of the polymerization, unreacted vinyl chloride monomer is recovered and the vinyl chloride polymer is taken out by a series of operations. Has been done.
【０００３】又、近年における重合器の大型化に伴い、
重合物に対する伝熱面積が減少し、このため冷却能力が
不足するという問題が生じている。その対策として、大
型の還流凝縮器を設置し徐熱する方法が採用されてい
る。Further, with the recent enlargement of the polymerization vessel,
There is a problem that the heat transfer area for the polymer is reduced, and thus the cooling capacity is insufficient. As a countermeasure, a method of installing a large reflux condenser and gradually heating is adopted.
【０００４】しかし、仕込時の重合反応物の泡立ちがお
こりフィッシュアイが発生する、泡立ち又は重合反応物
の飛散により重合器内へスケールが付着し粗粒品が増大
する、スケールの付着により徐熱能力が低下する等の欠
点があった。However, foaming of the polymerization reaction product at the time of charging causes fish eyes, scales adhere to the inside of the polymerization vessel due to foaming or scattering of the polymerization reaction product, and coarse particles increase. There were drawbacks such as reduced ability.
【０００５】これらの問題点を解決せんとして種々の提
案がなされている。例えば、特開平３−２１２４０９号
公報には、懸濁重合する際にけん化度２０〜５０モル
％、平均重合度２００〜４００の部分けん化ポリビニル
アルコールと消泡剤を添加する塩化ビニル系重合体の製
造方法が提案され、特開平７−２８６００３号公報等に
は、懸濁重合する際に、消泡剤である特定の構造を有す
るアセチレングリコール誘導体を添加する塩化ビニル系
重合体の製造方法が提案されている。Various proposals have been made to solve these problems. For example, JP-A-3-212409 discloses a vinyl chloride polymer to which a partially saponified polyvinyl alcohol having a saponification degree of 20 to 50 mol% and an average degree of polymerization of 200 to 400 and an antifoaming agent are added during suspension polymerization. A production method has been proposed, and Japanese Patent Application Laid-Open No. 7-286003 proposes a method for producing a vinyl chloride polymer by adding an acetylene glycol derivative having a specific structure which is an antifoaming agent during suspension polymerization. Has been done.
【０００６】消泡剤の添加は反応系の泡立ちを抑える効
果はあるものの、消泡剤が重合体の粒度分布や空隙率に
悪影響を及ぼし、ひどい時には異常反応をおこすという
欠点があった。Although the addition of the defoaming agent has the effect of suppressing the foaming of the reaction system, it has the drawback that the defoaming agent adversely affects the particle size distribution and the porosity of the polymer and causes an abnormal reaction in severe cases.
【０００７】一方、特開平５−１２５１０５号公報に
は、懸濁重合する際に、分散剤としてケン化度が６８〜
７６モル％の部分ケン化ポリビニルアルコール、重量平
均分子量が２００〜８００万のポリエチレンオキサイド
及びヒドロキシプロピルメチルセルロースを併用する塩
化ビニル系重合体の製造方法が提案されている。On the other hand, in Japanese Unexamined Patent Publication (Kokai) No. 5-125105, a saponification degree as a dispersant is 68 to 68 during suspension polymerization.
A method for producing a vinyl chloride-based polymer has been proposed in which 76 mol% of partially saponified polyvinyl alcohol, polyethylene oxide having a weight average molecular weight of 2 to 8 million, and hydroxypropylmethyl cellulose are used in combination.
【０００８】上記重合方法では、フィッシュアイの発
生、重合の際にスケールの付着、粗粒品の発生等はある
程度改善されるが、依然として不充分であった。In the above polymerization method, generation of fish eyes, adhesion of scale during polymerization, generation of coarse particles, etc. were improved to some extent, but they were still insufficient.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、上記
欠点に鑑み、経済的に重合でき、且つ、フィッシュアイ
の発生が少なく、且つ重合の際にスケールの付着が少な
くて粗粒品の少ない塩化ビニル系重合体を得ることので
きる製造方法を提供することにある。In view of the above-mentioned drawbacks, the object of the present invention is to produce a coarse-grained product which can be polymerized economically, has less fish eyes, and has less scale attached during the polymerization. An object of the present invention is to provide a production method capable of obtaining a small amount of vinyl chloride polymer.
【００１０】[0010]
【課題を解決するための手段】本発明の塩化ビニル系重
合体の製造方法は、還流凝縮器を備えた重合器を用い
て、塩化ビニル単量体を主体とするビニル系単量体を、
分散剤を含有する水性媒体中で重合開始剤によって懸濁
重合するに際し、前記分散剤が粘度平均分子量が２００
万〜８００万のポリエチレンオキサイド（Ａ）、ケン化
度が６８〜７６モル％の部分ケン化ポリビニルアルコー
ル（Ｂ）及びヒドロキシプロピルメチルセルロース
（Ｃ）よりなり、重合開始剤の添加前にポリエチレンオ
キサイド（Ａ）、及び部分ケン化ポリビニルアルコール
（Ｂ）とヒドロキシプロピルメチルセルロース（Ｃ）の
いずれか一方を添加し、重合開始剤の添加後に部分ケン
化ポリビニルアルコール（Ｂ）とヒドロキシプロピルメ
チルセルロース（Ｃ）のうち他方を添加することを特徴
とする。The method for producing a vinyl chloride-based polymer of the present invention uses a polymerization vessel equipped with a reflux condenser to produce a vinyl-based monomer mainly containing vinyl chloride monomer,
Upon suspension polymerization with a polymerization initiator in an aqueous medium containing a dispersant, the dispersant has a viscosity average molecular weight of 200.
1 to 8 million polyethylene oxide (A), a saponification degree of 68 to 76 mol% partially saponified polyvinyl alcohol (B) and hydroxypropylmethyl cellulose (C), and polyethylene oxide (A) is added before the addition of the polymerization initiator. ) And partially saponified polyvinyl alcohol (B) and hydroxypropylmethyl cellulose (C) are added, and the other of the partially saponified polyvinyl alcohol (B) and hydroxypropyl methyl cellulose (C) is added after the addition of the polymerization initiator. Is added.
【００１１】本発明で使用されるビニル系単量体は、塩
化ビニル単量体を主体とする。即ち、塩化ビニル単量体
単独若しくは塩化ビニル単量体を主体（５０重量％以上
含む）とする、塩化ビニル単量体と重合可能なビニルモ
ノマーとの混合物である。The vinyl-based monomer used in the present invention is mainly composed of vinyl chloride monomer. That is, it is a mixture of a vinyl chloride monomer and a polymerizable vinyl monomer containing vinyl chloride monomer alone or a vinyl chloride monomer as a main component (containing 50% by weight or more).
【００１２】上記ビニルモノマーとしては、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；
（メタ）アクリル酸メチル、（メタ）アクリル酸エチル
等の（メタ）アクリル酸エステル；エチレン、プロピレ
ン等のオレフィン；（メタ）アクリル酸、無水マレイン
酸、アクリロニトリル、スチレン、塩化ビニリデンなど
があげられる。Examples of the vinyl monomer include vinyl esters such as vinyl acetate and vinyl propionate;
Examples thereof include (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate; olefins such as ethylene and propylene; (meth) acrylic acid, maleic anhydride, acrylonitrile, styrene, vinylidene chloride and the like.
【００１３】本発明で使用される分散剤は、粘度平均分
子量が２００万〜８００万のポリエチレンオキサイド
（Ａ）、ケン化度が６８〜７６モル％の部分ケン化ポリ
ビニルアルコール（Ｂ）及びヒドロキシプロピルメチル
セルロース（Ｃ）が併用される。The dispersant used in the present invention is polyethylene oxide (A) having a viscosity average molecular weight of 2 to 8 million, partially saponified polyvinyl alcohol (B) having a saponification degree of 68 to 76 mol%, and hydroxypropyl. Methyl cellulose (C) is used in combination.
【００１４】上記ポリエチレンオキサイド（Ａ）は、粘
度平均分子量が低くなると得られる塩化ビニル系重合体
の嵩比重が低くなり、８００万を超えるものは市販され
ていないので粘度平均分子量が２００万〜８００万のも
のが使用される。When the viscosity average molecular weight of the above-mentioned polyethylene oxide (A) is low, the bulk specific gravity of the vinyl chloride polymer obtained is low, and those having a viscosity average molecular weight of more than 8 million are not commercially available. Thousands are used.
【００１５】上記部分ケン化ポリビニルアルコール
（Ｂ）は、ケン化度が低くなると重合器の内壁にスケー
ルが付着しやすくなると共に得られる塩化ビニル系重合
体の嵩比重が低くなり、ケン化度が高くなると得られる
塩化ビニル系重合体の嵩比重が低くなったり、粒度分布
が広くなったり、ゲル化性が悪くなって加工性が低下し
たりするので、ケン化度が６８〜７６モル％のものが使
用される。When the degree of saponification of the partially saponified polyvinyl alcohol (B) is low, the scale easily adheres to the inner wall of the polymerization vessel and the bulk specific gravity of the vinyl chloride polymer obtained is low, so that the degree of saponification is low. If it becomes higher, the bulk specific gravity of the obtained vinyl chloride-based polymer becomes lower, the particle size distribution becomes wider, the gelation property deteriorates, and the processability decreases, so that the saponification degree is 68 to 76 mol%. Stuff used.
【００１６】上記ヒドロキシプロピルメチルセルロース
（Ｃ）は、塩化ビニル単量体を水性懸濁重合する際に従
来から使用されている任意のものが使用可能であるが、
メトキシ基含有量が１９〜３０重量％、ヒドロキシプロ
ピル基含有量が４〜１５重量％、そして２０℃における
２重量％水溶液の粘度が５〜４０００ｃｐｓのものが好
適に使用される。As the hydroxypropylmethyl cellulose (C), any of those conventionally used for aqueous suspension polymerization of vinyl chloride monomers can be used.
A methoxy group content of 19 to 30% by weight, a hydroxypropyl group content of 4 to 15% by weight, and a 2% by weight aqueous solution at 20 ° C. having a viscosity of 5 to 4000 cps are preferably used.
【００１７】ポリエチレンオキサイド（Ａ）の添加量
は、ビニル系単量体１００重量部に対し０．００５〜
０．０８重量部が好ましく、より好ましくは０．０１〜
０．０５重量部である。The amount of polyethylene oxide (A) added is 0.005 to 100 parts by weight of the vinyl monomer.
0.08 parts by weight is preferable, and more preferably 0.01 to
It is 0.05 part by weight.
【００１８】部分ケン化ポリビニルアルコール（Ｂ）と
ヒドロキシプロピルメチルセルロース（Ｃ）の添加量
は、それぞれビニル系単量体１００重量部に対し０．０
０５〜０．２重量部が好ましく、より好ましくは０．０
１〜０．１重量部である。The amounts of the partially saponified polyvinyl alcohol (B) and hydroxypropylmethyl cellulose (C) added are each 0.0 per 100 parts by weight of the vinyl monomer.
05-0.2 parts by weight is preferable, more preferably 0.0
1 to 0.1 parts by weight.
【００１９】又、ポリエチレンオキサイド（Ａ）の添加
量は、部分ケン化ポリビニルアルコール（Ｂ）及びヒド
ロキシプロピルメチルセルロース（Ｃ）の添加量に対
し、それぞれ０．０５〜１の割合で添加されるのが好ま
しく、より好ましくは０．１〜０．５である。The amount of polyethylene oxide (A) added is 0.05 to 1 with respect to the amount of partially saponified polyvinyl alcohol (B) and hydroxypropylmethyl cellulose (C). It is more preferably 0.1 to 0.5.
【００２０】尚、本発明では、上記分散剤の他に塩化ビ
ニル単量体を水性懸濁重合する際に従来から使用されて
いる任意の分散剤が併用されてもよく、このような分散
剤としては、例えば、ケン化度が６８〜７６モル％以外
の部分ケン化ポリビニルアルコール、ヒドロキシプロピ
ルメチルセルロース以外のセルロース誘導体、ポリアク
リル酸誘導体、ポリエチレンオキサイドのアルキルエー
テル、ソルビタン脂肪酸エステル、ポリメチルビニルエ
ーテル等があげられる。In the present invention, in addition to the above-mentioned dispersant, any dispersant conventionally used in aqueous suspension polymerization of vinyl chloride monomer may be used in combination. As, for example, partially saponified polyvinyl alcohol having a saponification degree other than 68 to 76 mol%, cellulose derivatives other than hydroxypropylmethyl cellulose, polyacrylic acid derivatives, alkyl ethers of polyethylene oxide, sorbitan fatty acid esters, polymethyl vinyl ether, etc. can give.
【００２１】本発明で使用される重合開始剤としては、
ビニル系単量体の懸濁重合で一般に使用されている重合
開始剤が使用されればよく、例えば、ジイソプロピルパ
ーオキシカーボネート、ジ−２−エチルヘキシルパーオ
キシカーボネート、ジエトキシエチルパーオキシカーボ
ネート等のパーオキシカーボネート化合物；α−クミル
パーオキシネオデカネート、ｔ−ブチルパーオキシネオ
デカネート、ｔ−ブチルパーオキシピバレート、ｔ−ヘ
キシ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
サイド、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；過硫酸カリウム、過硫酸アンモニウム、過酸化水素
などが上げられ、単独で使用されてもよいし、２種以上
が併用されてもよい。The polymerization initiator used in the present invention includes
A polymerization initiator generally used in suspension polymerization of vinyl-based monomers may be used, and examples thereof include peroxidic acid such as diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and diethoxyethyl peroxycarbonate. Oxycarbonate compounds; peroxyester compounds such as α-cumylperoxyneodecanate, t-butylperoxyneodecanate, t-butylperoxypivalate, t-hexylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide , Peroxides such as 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate; azobis-
Azo compounds such as 2,4-dimethylvaleronitrile and azobis (4-methoxy-2,4-dimethylvaleronitrile); potassium persulfate, ammonium persulfate, hydrogen peroxide, etc. may be used alone or may be used alone. Two or more kinds may be used in combination.
【００２２】又、重合開始剤の添加量は、少ないと重合
が充分に進まず、多過ぎると異常反応を起こしやすくな
るので、ビニル系単量体１００重量部に対し、０．０１
５〜０．１重量部が好ましい。If the amount of the polymerization initiator added is small, the polymerization will not proceed sufficiently, and if it is too large, an abnormal reaction will be likely to occur.
5 to 0.1 parts by weight is preferable.
【００２３】重合開始剤の添加方法もビニル系単量体の
懸濁重合で一般に使用されている方法が採用されればよ
く、例えば、重合開始剤を有機溶剤に溶解するか、水性
媒体に分散してエマルション又はサスペンジョンとし、
水性媒体及び／又は分散剤と一緒に或いはこれらを仕込
んだ後に添加する方法が上げられる。又、ビニル系単量
体の仕込み後にポンプで圧入してもよい。As a method for adding the polymerization initiator, a method generally used in suspension polymerization of vinyl monomers may be adopted. For example, the polymerization initiator is dissolved in an organic solvent or dispersed in an aqueous medium. To make an emulsion or suspension,
The method of adding together with the aqueous medium and / or the dispersant or after charging these is mentioned. Also, after charging the vinyl-based monomer, it may be press-fitted with a pump.
【００２４】更に、従来からビニル系単量体の懸濁重合
の際に使用されている重合調整剤、連鎖移動剤、ｐＨ調
整剤、ゲル化改良剤、帯電防止剤、重合体スケール付着
防止剤等が添加されてもよい。Further, a polymerization regulator, a chain transfer agent, a pH regulator, a gelation improving agent, an antistatic agent, a polymer scale anti-adhesion agent which have been conventionally used in suspension polymerization of vinyl monomers. Etc. may be added.
【００２５】本発明においては、還流凝縮器を備えた重
合器を用いて、塩化ビニル単量体を主体とするビニル系
単量体を、分散剤を含有する水性媒体中で懸濁重合す
る。還流凝縮器は液層から気化したガスを冷却して凝縮
させ液体状態に戻して重合熱を除去するための装置であ
り、従来公知のものが使用される。In the present invention, a vinyl monomer mainly containing vinyl chloride monomer is suspension polymerized in an aqueous medium containing a dispersant, using a polymerization vessel equipped with a reflux condenser. The reflux condenser is an apparatus for cooling the vaporized gas from the liquid layer and condensing it to return it to a liquid state to remove the heat of polymerization, and a conventionally known one is used.
【００２６】懸濁重合方法は、従来のビニル系単量体の
懸濁重合の際に採用されている方法が採用されればよ
く、例えば、（１）重合器に水性媒体と分散剤を仕込
み、次いで重合開始剤を仕込み、続いて重合器内を真空
脱気した後ビニル系単量体を仕込み、得られた懸濁重合
液を所定の重合開始温度まで昇温して重合反応を行い、
反応熱が出てきた時点から還流凝縮器に冷却水を通して
冷却し、重合温度を所定温度に維持して重合を進行さ
せ、（２）重合器に水性媒体と分散剤を仕込み、重合器
内を真空脱気した後ビニル系単量体を仕込み、次いで重
合開始剤を仕込み、得られた懸濁重合液を所定の重合開
始温度まで昇温して重合反応を行い、反応熱が出てきた
時点から還流凝縮器に冷却水を通して冷却し、重合温度
を所定温度に維持して重合を進行させ、又は、（３）重
合器内を真空脱気した後、重合器に水性媒体と分散剤と
ビニル系単量体を同時に仕込み、次いで重合開始剤を仕
込み、得られた懸濁重合液を所定の重合開始温度まで昇
温して重合反応を行い、反応熱が出てきた時点から還流
凝縮器に冷却水を通して冷却し、重合温度を所定温度に
維持して重合を進行させ、重合終了後、塩化ビニル単量
体を回収すると共に塩化ビニル重合体を取り出す方法等
が上げられる。The suspension polymerization method may be the same as that used in the conventional suspension polymerization of vinyl-based monomers. For example, (1) a polymerization vessel is charged with an aqueous medium and a dispersant. , Then charged with a polymerization initiator, followed by vacuum degassing of the inside of the polymerization vessel, then charged with a vinyl-based monomer, and the suspension polymerization solution obtained was heated to a predetermined polymerization start temperature to carry out a polymerization reaction,
From the time when the heat of reaction comes out, cooling water is passed through the reflux condenser to cool, the polymerization temperature is maintained at a predetermined temperature to proceed with the polymerization, and (2) the aqueous medium and the dispersant are charged into the polymerization vessel, After deaeration in vacuum, charging a vinyl-based monomer, then charging a polymerization initiator, heating the obtained suspension polymerization solution to a predetermined polymerization initiation temperature to carry out a polymerization reaction, and when heat of reaction comes out. Cooling water is passed through the reflux condenser to keep the polymerization temperature at a predetermined temperature to proceed with the polymerization, or (3) the inside of the polymerization vessel is deaerated in vacuum, and then the aqueous medium, the dispersant and vinyl are placed in the polymerization vessel. The system monomers are charged at the same time, then the polymerization initiator is charged, the suspension polymerization liquid obtained is heated to a predetermined polymerization initiation temperature to carry out the polymerization reaction, and when the reaction heat comes out, the reflux condenser is charged into the reflux condenser. Cooling through cooling water to maintain the polymerization temperature at the specified temperature and proceed with the polymerization. So, after the polymerization, and a method of taking out the vinyl chloride polymer is recovered vinyl chloride monomer and the like.
【００２７】又、この場合昇温は水性媒体と分散剤の仕
込み前から行われてもよいし、ビニル系単量体の仕込み
前から行われてもよい。In this case, the temperature may be raised before charging the aqueous medium and the dispersant, or before charging the vinyl monomer.
【００２８】本発明においては、上記分散剤の添加が２
回に分けて行われる。即ち、重合開始剤の添加前にポリ
エチレンオキサイド（Ａ）、及び部分ケン化ポリビニル
アルコール（Ｂ）とヒドロキシプロピルメチルセルロー
ス（Ｃ）のいずれか一方を添加し、重合開始剤の添加後
に部分ケン化ポリビニルアルコール（Ｂ）とヒドロキシ
プロピルメチルセルロース（Ｃ）のうち他方を添加す
る。In the present invention, the addition of the above dispersant is 2
It is divided into two times. That is, polyethylene oxide (A) and either one of partially saponified polyvinyl alcohol (B) and hydroxypropylmethyl cellulose (C) are added before the addition of the polymerization initiator, and the partially saponified polyvinyl alcohol after the addition of the polymerization initiator. The other of (B) and hydroxypropylmethylcellulose (C) is added.
【００２９】部分ケン化ポリビニルアルコール（Ｂ）と
ヒドロキシプロピルメチルセルロース（Ｃ）のうち他方
は重合開始剤の添加後の任意の時に添加されればよい
が、重合開始剤の添加直後から、ビニル系単量体の重合
率が１０重量％になるまでの間に添加されるのが好まし
い。重合率が１０重量％を超えて添加すると、分散状態
が悪くなり粗大粒の増加又は異常反応を起こしやすくな
るので好ましくない。The other of the partially saponified polyvinyl alcohol (B) and the hydroxypropylmethyl cellulose (C) may be added at any time after the addition of the polymerization initiator. It is preferably added until the polymerization rate of the monomer reaches 10% by weight. If the polymerization rate is more than 10% by weight, the dispersed state becomes poor and coarse particles increase or abnormal reaction easily occurs, which is not preferable.
【００３０】又、反応系の発泡を抑止するために重合開
始剤の添加時又はその後に消泡剤を添加するのが好まし
い。Further, in order to suppress the foaming of the reaction system, it is preferable to add an antifoaming agent at the time of adding the polymerization initiator or thereafter.
【００３１】上記消泡剤としては、従来から水性懸濁重
合の際に使用されている任意の消泡剤が使用可能であ
り、例えば、ポリシロキサン、ジメチルポリシロキサ
ン、ジフェニルポリシロキサンなどのシリコーンオイル
類、炭素数が１０〜３０の脂肪族又は芳香族のアルコー
ル類等があげられる。As the above defoaming agent, any defoaming agent conventionally used in aqueous suspension polymerization can be used. For example, silicone oil such as polysiloxane, dimethylpolysiloxane and diphenylpolysiloxane. Examples thereof include aliphatic or aromatic alcohols having 10 to 30 carbon atoms.
【００３２】上記消泡剤の添加量は、必要に応じて適宜
決定されればよいが、多過ぎると得られる重合体の粒度
分布や空隙率に悪影響を及ぼし、ひどい時には異常反応
をおこすことがあるので、ビニル系単量体１００重量部
に対し、０．００１〜０．０５重量部が好ましい。The amount of the antifoaming agent to be added may be appropriately determined as necessary, but if it is too large, it adversely affects the particle size distribution and porosity of the polymer obtained, and when it is severe, it may cause an abnormal reaction. Therefore, 0.001 to 0.05 parts by weight is preferable to 100 parts by weight of the vinyl monomer.
【００３３】[0033]
【発明の実施の形態】次に本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００３４】（実施例１）伝熱面積が０．５ｍ2の還流
凝縮器と攪拌羽根を備えた６００リットルの重合器に、
水１３０重量部、ヒドロキシプロピルメチルセルロース
０．０５重量部及び粘度平均分子量が４５０万のポリエ
チレンオキサイド０．０２重量部を供給、攪拌して各成
分を溶解した。次いで、ジ−２−エチルヘキシルパーオ
キシジカーボネート０．０６２重量部を添加した後、重
合器内の空気を取り除いて塩化ビニル単量体１００重量
部を仕込み、その後、ケン化度７２モル％の部分ケン化
ポリビニルアルコール０．０５重量部とジメチルポリシ
ロキサン０．０１重量部を添加すると同時に昇温を開始
し、重合器内を５８℃に昇温して重合反応を開始した。Example 1 In a 600 liter polymerization vessel equipped with a reflux condenser having a heat transfer area of 0.5 m 2 and a stirring blade,
130 parts by weight of water, 0.05 part by weight of hydroxypropylmethylcellulose and 0.02 part by weight of polyethylene oxide having a viscosity average molecular weight of 4.5 million were supplied and stirred to dissolve each component. Next, after adding 0.062 parts by weight of di-2-ethylhexyl peroxydicarbonate, the air in the polymerization vessel was removed and 100 parts by weight of vinyl chloride monomer was charged, and then the portion having a saponification degree of 72 mol% was added. Simultaneously with the addition of 0.05 part by weight of saponified polyvinyl alcohol and 0.01 part by weight of dimethylpolysiloxane, the temperature was raised and the temperature in the polymerization vessel was raised to 58 ° C. to start the polymerization reaction.
【００３５】部分ケン化ポリビニルアルコールを添加し
た際の懸濁重合液の温度は４０℃であり、還流凝縮器に
は水を循環し、重合反応熱の６０％を除去するように設
定して、懸濁重合を行った。The temperature of the suspension polymerization liquid when the partially saponified polyvinyl alcohol was added was 40 ° C., water was circulated through the reflux condenser, and it was set so as to remove 60% of the heat of polymerization reaction. Suspension polymerization was performed.
【００３６】重合器内の圧力が０．２ＭＰａ低下した時
点で未反応塩化ビニル単量体を回収し、脱水・乾燥して
塩化ビニル重合体を得た。反応時間は３．５時間であっ
た。When the pressure inside the polymerization vessel dropped by 0.2 MPa, the unreacted vinyl chloride monomer was recovered, dehydrated and dried to obtain a vinyl chloride polymer. The reaction time was 3.5 hours.
【００３７】（実施例２）重合器に、水１３０重量部、
ケン化度７２モル％の部分ケン化ポリビニルアルコール
０．０５重量部及び粘度平均分子量が４５０万のポリエ
チレンオキサイド０．０２重量部を供給、攪拌して各成
分を溶解した。次いで、ジ−２−エチルヘキシルパーオ
キシジカーボネート０．０６２重量部を添加した後、重
合器内の空気を取り除いて塩化ビニル単量体１００重量
部を仕込み、その後、ヒドロキシプロピルメチルセルロ
ース０．０５重量部とジメチルポリシロキサン０．０１
重量部を添加すると同時に昇温を開始し、重合器内を５
８℃に昇温して重合反応を開始した以外は実施例１で行
ったと同様にして重合した。(Example 2) In a polymerization vessel, 130 parts by weight of water,
0.05 part by weight of partially saponified polyvinyl alcohol having a degree of saponification of 72 mol% and 0.02 part by weight of polyethylene oxide having a viscosity average molecular weight of 4.5 million were supplied and stirred to dissolve each component. Next, after adding 0.062 parts by weight of di-2-ethylhexyl peroxydicarbonate, the air in the polymerization vessel was removed and 100 parts by weight of vinyl chloride monomer was charged, and then 0.05 parts by weight of hydroxypropylmethyl cellulose. And dimethylpolysiloxane 0.01
At the same time as the addition of parts by weight, the temperature starts to be increased to 5
Polymerization was carried out in the same manner as in Example 1 except that the temperature was raised to 8 ° C. to start the polymerization reaction.
【００３８】（実施例３）塩化ビニル単量体１００重量
部の仕込み後、ジメチルポリシロキサン０．０１重量部
を添加すると同時に昇温を開始し、重合器内を５８℃に
昇温して重合反応を開始すると共に、５８℃に昇温した
直後ヒドロキシプロピルメチルセルロース０．０５重量
部を添加した以外は実施例２で行ったと同様にして重合
した。(Example 3) After charging 100 parts by weight of vinyl chloride monomer, 0.01 parts by weight of dimethylpolysiloxane was added, and at the same time, the temperature started to be increased, and the temperature in the polymerization vessel was raised to 58 ° C. for polymerization. Polymerization was carried out in the same manner as in Example 2 except that 0.05 part by weight of hydroxypropylmethyl cellulose was added immediately after the reaction was started and the temperature was raised to 58 ° C.
【００３９】（実施例４）重合器に、水１３０重量部、
ケン化度７２モル％の部分ケン化ポリビニルアルコール
０．０５重量部及び粘度平均分子量が４５０万のポリエ
チレンオキサイド０．０２重量部を供給、攪拌して各成
分を溶解した。次いで、重合器内の空気を取り除いて塩
化ビニル単量体１００重量部を仕込んだ後、ジ−２−エ
チルヘキシルパーオキシジカーボネート０．０６２重量
部を添加し、更に、その後、ヒドロキシプロピルメチル
セルロース０．０５重量部とジメチルポリシロキサン
０．０１重量部を添加すると同時に昇温を開始し、重合
器内を５８℃に昇温して重合反応を開始した以外は実施
例２で行ったと同様にして重合した。Example 4 In a polymerization vessel, 130 parts by weight of water,
0.05 part by weight of partially saponified polyvinyl alcohol having a degree of saponification of 72 mol% and 0.02 part by weight of polyethylene oxide having a viscosity average molecular weight of 4.5 million were supplied and stirred to dissolve each component. Next, after removing the air in the polymerization vessel and charging 100 parts by weight of vinyl chloride monomer, 0.062 parts by weight of di-2-ethylhexyl peroxydicarbonate was added, and then hydroxypropylmethyl cellulose was added. Polymerization was carried out in the same manner as in Example 2 except that the addition of 05 parts by weight and 0.01 parts by weight of dimethylpolysiloxane was started to raise the temperature at the same time, and the temperature inside the polymerization vessel was raised to 58 ° C. to start the polymerization reaction. did.
【００４０】（実施例５）重合器内の空気を取り除いて
水１３０重量部、ケン化度７２モル％の部分ケン化ポリ
ビニルアルコール０．０５重量部、粘度平均分子量が４
５０万のポリエチレンオキサイド０．０２重量部及び塩
化ビニル単量体１００重量部を仕込んだ後、ジ−２−エ
チルヘキシルパーオキシジカーボネート０．０６２重量
部を添加し、次いで、ヒドロキシプロピルメチルセルロ
ース０．０５重量部とジメチルポリシロキサン０．０１
重量部を添加すると同時に昇温を開始し、重合器内を５
８℃に昇温して重合反応を開始した以外は実施例２で行
ったと同様にして重合した。(Example 5) 130 parts by weight of water was removed from the polymerization vessel, 0.05 part by weight of partially saponified polyvinyl alcohol having a saponification degree of 72 mol% and a viscosity average molecular weight of 4
After charging 500,000 parts by weight of polyethylene oxide (0.02 parts by weight) and vinyl chloride monomer (100 parts by weight), di-2-ethylhexyl peroxydicarbonate (0.062 parts by weight) was added, and then hydroxypropylmethyl cellulose 0.05. Parts by weight and dimethylpolysiloxane 0.01
At the same time as the addition of parts by weight, the temperature starts to be increased to 5
Polymerization was performed in the same manner as in Example 2 except that the temperature was raised to 8 ° C. to start the polymerization reaction.
【００４１】（実施例６）ジメチルポリシロキサンを添
加しない以外は実施例１で行ったと同様にして重合し
た。Example 6 Polymerization was carried out in the same manner as in Example 1 except that dimethylpolysiloxane was not added.
【００４２】（実施例７）ジメチルポリシロキサンを添
加しない以外は実施例５で行ったと同様にして重合し
た。Example 7 Polymerization was carried out in the same manner as in Example 5 except that dimethylpolysiloxane was not added.
【００４３】（比較例１）重合器に、水１３０重量部、
ケン化度７２モル％の部分ケン化ポリビニルアルコール
０．０５重量部、ヒドロキシプロピルメチルセルロース
０．０５重量部及び粘度平均分子量が４５０万のポリエ
チレンオキサイド０．０２重量部を供給、攪拌して各成
分を溶解した。次いで、ジ−２−エチルヘキシルパーオ
キシジカーボネート０．０６２重量部を添加した後、重
合器内の空気を取り除いて塩化ビニル単量体１００重量
部を仕込み、その後、昇温を開始し、重合器内を５８℃
に昇温して重合反応を開始した以外は実施例１で行った
と同様にして重合した。Comparative Example 1 130 parts by weight of water was placed in a polymerization vessel.
0.05 parts by weight of partially saponified polyvinyl alcohol having a saponification degree of 72 mol%, 0.05 parts by weight of hydroxypropylmethyl cellulose and 0.02 parts by weight of polyethylene oxide having a viscosity average molecular weight of 4.5 million are supplied and stirred to mix the components. Dissolved. Next, after adding 0.062 parts by weight of di-2-ethylhexyl peroxydicarbonate, the air in the polymerization vessel was removed and 100 parts by weight of vinyl chloride monomer was charged, and then the temperature was started and the polymerization vessel was started. 58 ° C inside
Polymerization was carried out in the same manner as in Example 1 except that the temperature was raised to 0 to start the polymerization reaction.
【００４４】（比較例２）ジメチルポリシロキサン０．
０１重量部を昇温開始直前に添加した以外は比較例１で
行ったと同様にして重合した。Comparative Example 2 Dimethylpolysiloxane 0.
Polymerization was carried out in the same manner as in Comparative Example 1 except that 01 part by weight was added immediately before the start of temperature increase.
【００４５】昇温時の泡立ち状態及び反応終了後のスケ
ール付着状態を観察し、得られた塩化ビニル重合体のフ
ィッシュアイ及び粗粒化度を測定し結果を表１及び表２
に示した。尚、観察条件及び測定方法は下記の通りであ
る。The foaming state at the time of temperature rise and the scale adhering state after the reaction were observed, the fish eyes and the degree of coarsening of the obtained vinyl chloride polymer were measured, and the results are shown in Tables 1 and 2.
It was shown to. The observation conditions and measurement method are as follows.
【００４６】（１）泡立ち状態
重合器の内部観察用のぞき窓から、昇温時の懸濁液の状
態を目視で観察した。
○・・・泡の発生がなく、懸濁液の動きが活発な状態
△・・・泡の発生は少しあるが、懸濁液の動きがある状
態
×・・・泡の発生が多く、懸濁液の動きがない状態(1) Foaming state The state of the suspension at the time of temperature rise was visually observed through the observation window for observing the inside of the polymerization vessel. ○: Suspension is active with no bubbles generated △: Bubbles are slightly generated, but suspension is moving ×: Many bubbles are generated When the suspension does not move
【００４７】（２）スケール付着状態
塩化ビニル重合体を重合器から取り出した後、重合器の
内部にスケールが付着している状態を目視で観察した。
○・・・スケールの付着なし
△・・・スケールの付着少量あり
×・・・スケールの付着多量あり(2) Scale Adhesion State After the vinyl chloride polymer was taken out from the polymerization vessel, the state in which scale was attached inside the polymerization vessel was visually observed. ○: No scale adhered △: Small scale adhered ×: Large scale adhered
【００４８】（３）フィッシュアイ
得られた塩化ビニル重合体１００重量部、ジオクチルフ
タレート５０重量部、ステアリン酸バリウム０．５重量
部、ステアリン酸亜鉛０．５重量部、二酸化チタン０．
５重量部及びカーボンブラック０．１重量部よりなる混
合物を６インチロールに供給し、１４０℃で５分間混練
した後、厚さ０．３ｍｍのシートを得た。得られたシー
トの１００ｃｍ2の中にある透明粒子の数を計数した。(3) Fish Eye 100 parts by weight of the obtained vinyl chloride polymer, 50 parts by weight of dioctyl phthalate, 0.5 part by weight of barium stearate, 0.5 part by weight of zinc stearate, titanium dioxide 0.1 part by weight.
A mixture of 5 parts by weight and 0.1 parts by weight of carbon black was fed to a 6-inch roll and kneaded at 140 ° C. for 5 minutes to obtain a sheet having a thickness of 0.3 mm. The number of transparent particles in 100 cm 2 of the obtained sheet was counted.
【００４９】（４）粗粒化度
ＪＩＳ Ｚ８８０１に準拠し、４２メッシュの標準篩を
使用し、篩に残った塩化ビニル重合体粒子の比率（重量
％）を測定した。(4) Coarseness degree According to JIS Z8801, a 42 mesh standard sieve was used and the ratio (% by weight) of vinyl chloride polymer particles remaining on the sieve was measured.
【００５０】[0050]
【表１】 [Table 1]
【００５１】[0051]
【表２】 [Table 2]
【００５２】[0052]
【発明の効果】本発明の塩化ビニル系重合体の製造方法
は、上述の通りであるから、重合の際にスケールの付着
が少なくて経済的に重合でき、得られた塩化ビニル系重
合体はフィッシュアイが少なく、粗粒品も少ない。EFFECT OF THE INVENTION Since the method for producing a vinyl chloride polymer of the present invention is as described above, it is possible to economically polymerize with less adhesion of scale during the polymerization, and the obtained vinyl chloride polymer is There are few fish eyes and few coarse-grained products.
フロントページの続き Ｆターム(参考） 4J011 AA05 AA08 AB03 DA03 DB12 DB32 JA06 JA07 JA08 JA18 JB02 JB03 JB08 PA25 PA47 PA99 PB40 PC02 PC03 PC07Continued front page F-term (reference) 4J011 AA05 AA08 AB03 DA03 DB12 DB32 JA06 JA07 JA08 JA18 JB02 JB03 JB08 PA25 PA47 PA99 PB40 PC02 PC03 PC07
Claims (3)
化ビニル単量体を主体とするビニル系単量体を、分散剤
を含有する水性媒体中で重合開始剤によって懸濁重合す
るに際し、前記分散剤が粘度平均分子量が２００万〜８
００万のポリエチレンオキサイド（Ａ）、ケン化度が６
８〜７６モル％の部分ケン化ポリビニルアルコール
（Ｂ）及びヒドロキシプロピルメチルセルロース（Ｃ）
よりなり、重合開始剤の添加前にポリエチレンオキサイ
ド（Ａ）、及び部分ケン化ポリビニルアルコール（Ｂ）
とヒドロキシプロピルメチルセルロース（Ｃ）のいずれ
か一方を添加し、重合開始剤の添加後に部分ケン化ポリ
ビニルアルコール（Ｂ）とヒドロキシプロピルメチルセ
ルロース（Ｃ）のうち他方を添加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 polymerization reactor equipped with a reflux condenser is used to suspension-polymerize a vinyl-based monomer mainly containing vinyl chloride monomer with a polymerization initiator in an aqueous medium containing a dispersant. At this time, the dispersant has a viscosity average molecular weight of 2 to 8
1,000,000 polyethylene oxide (A), saponification degree 6
8-76 mol% partially saponified polyvinyl alcohol (B) and hydroxypropyl methylcellulose (C)
Consisting of polyethylene oxide (A) and partially saponified polyvinyl alcohol (B) before the addition of the polymerization initiator.
And hydroxypropylmethylcellulose (C) are added, and after addition of the polymerization initiator, the other of partially saponified polyvinyl alcohol (B) and hydroxypropylmethylcellulose (C) is added. Method for producing polymer.
を添加することを特徴とする請求項１記載の塩化ビニル
系重合体の製造方法。2. The method for producing a vinyl chloride polymer according to claim 1, wherein an antifoaming agent is added during or after the addition of the polymerization initiator.
とヒドロキシプロピルメチルセルロース（Ｃ）のうちの
他方を、ビニル系単量体の重合率が１０重量％までに添
加することを特徴とする請求項１又は２記載の塩化ビニ
ル系重合体の製造方法。3. Partially saponified polyvinyl alcohol (B)
3. The method for producing a vinyl chloride-based polymer according to claim 1, wherein the other one of the hydroxypropylmethyl cellulose (C) and the other is added up to a polymerization rate of the vinyl-based monomer of up to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001183412A JP2003002911A (en) | 2001-06-18 | 2001-06-18 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001183412A JP2003002911A (en) | 2001-06-18 | 2001-06-18 | Method for producing vinyl chloride polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003002911A true JP2003002911A (en) | 2003-01-08 |
Family
ID=19023364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001183412A Pending JP2003002911A (en) | 2001-06-18 | 2001-06-18 | Method for producing vinyl chloride polymer |
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| Country | Link |
|---|---|
| JP (1) | JP2003002911A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298750A (en) * | 2004-04-15 | 2005-10-27 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersant for suspension polymerization |
| JP2007284510A (en) * | 2006-04-14 | 2007-11-01 | Shin Dai-Ichi Vinyl Corp | Method for producing vinyl chloride-based polymer |
| JP2011246541A (en) * | 2010-05-25 | 2011-12-08 | Mitsubishi Rayon Co Ltd | Method for producing styrene acrylic resin for toner |
| KR20150026543A (en) * | 2013-09-03 | 2015-03-11 | 주식회사 엘지화학 | Method for preparing PVC |
-
2001
- 2001-06-18 JP JP2001183412A patent/JP2003002911A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298750A (en) * | 2004-04-15 | 2005-10-27 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersant for suspension polymerization |
| JP4632151B2 (en) * | 2004-04-15 | 2011-02-16 | 日本合成化学工業株式会社 | Dispersant for suspension polymerization |
| JP2007284510A (en) * | 2006-04-14 | 2007-11-01 | Shin Dai-Ichi Vinyl Corp | Method for producing vinyl chloride-based polymer |
| JP2011246541A (en) * | 2010-05-25 | 2011-12-08 | Mitsubishi Rayon Co Ltd | Method for producing styrene acrylic resin for toner |
| KR20150026543A (en) * | 2013-09-03 | 2015-03-11 | 주식회사 엘지화학 | Method for preparing PVC |
| KR101687440B1 (en) | 2013-09-03 | 2016-12-16 | 주식회사 엘지화학 | Method for preparing PVC |
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