JP2003238606A - Method for producing vinyl chloride resin - Google Patents
Method for producing vinyl chloride resinInfo
- Publication number
- JP2003238606A JP2003238606A JP2002044457A JP2002044457A JP2003238606A JP 2003238606 A JP2003238606 A JP 2003238606A JP 2002044457 A JP2002044457 A JP 2002044457A JP 2002044457 A JP2002044457 A JP 2002044457A JP 2003238606 A JP2003238606 A JP 2003238606A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- dispersant
- chloride resin
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
【０００１】
【発明の属する技術分野】本発明は、塩化ビニル系樹脂
の製造方法に関する。さらに詳しくは、経済的に重合で
き、嵩比重の高い高重合度の塩化ビニル系樹脂の製造方
法に関する。
【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、還流凝縮器、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。
【０００３】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及び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という一連の操作で
重合されている。
【０００４】この懸濁重合では、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ヘ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。
【０００５】
【発明が解決しようとする課題】これらの問題点を解決
するために、分散剤としてポリビニルアルコール、セル
ロース、ポリエチレンオキサイド、ポリビニルピロリド
ン等を併用する方法が種々提案されている（例えば、特
開昭６０−１５８２０６号公報、特開昭６１−１１５９
０８号公報、特開平１−２５６５０４号公報、特開平１
−２６８７０２号公報等）。
【０００６】しかしながら、これらの方法では嵩比重の
高い、即ち、成形性の良い塩化ビニル系樹脂は得られな
かった。
【０００７】特開平５−１２５１０５号公報には嵩比重
の高い塩化ビニル系径樹脂を得る重合方法が提案されて
いる。即ち、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２００万〜８００万のポリエチレ
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。
【０００８】しかしながら、上記重合方法では、重合度
が１２００よりも低い低重合度の塩化ビニル系樹脂では
嵩比重の高い樹脂が得られるが、重合度が１２００〜２
０００の高重合度の塩化ビニル系樹脂では嵩比重の高い
樹脂が得られなかった。
【０００９】本発明の目的は、上記欠点に鑑み、経済的
に重合でき、嵩比重の高い高重合度の塩化ビニル系樹脂
を得ることのできる製造方法を提供することにある。
【００１０】
【課題を解決するための手段】本発明の塩化ビニル系樹
脂の製造方法は、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（Ａ）、ヒド
ロキシプロピルメチルセルロース（Ｂ）、粘度平均分子
量が２００万〜８００万のポリエチレンオキサイド
（Ｃ）及びヒドロキシプロピルセルロース（Ｄ）を添加
し、重合温度４０〜５５℃で重合することを特徴とす
る。
【００１１】
【発明の実施の形態】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。
【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。
【００１３】本発明において分散剤は、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
（Ａ）、ヒドロキシプロピルメチルセルロース（Ｂ）、
粘度平均分子量が２００万〜８００万のポリエチレンオ
キサイド（Ｃ）及びヒドロキシプロピルセルロース
（Ｄ）が併用される。
【００１４】上記部分ケン化ポリビニルアルコール
（Ａ）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樹脂
の嵩比重が低くなり、ケン化度が高くなると得られる塩
化ビニル系樹脂の粒度分布が広くなったり、フィッシュ
アイが発生したり、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。
【００１５】上記ヒドロキシプロピルメチルセルロース
（Ｂ）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
ポキシル基含有量が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。
【００１６】上記ポリエチレンオキサイド（Ｃ）は、粘
度平均分子量が低くなると得られる塩化ビニル系樹脂の
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。
【００１７】上記ヒドロキシプロピルセルロース（Ｄ）
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、ヒドロ
キシプロポキシル基含有量が５３〜７８重量％で２０℃
における２重量％水溶液の粘度が３〜１０ｃｐｓのもの
が好適に使用される。
【００１８】部分ケン化ポリビニルアルコール（Ａ）と
ヒドロキシプロピルメチルセルロース（Ｂ）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。
【００１９】ポリエチレンオキサイド（Ｃ）とヒドロキ
シプロピルセルロース（Ｄ）の添加量は、ビニル系単量
体１００重量部に対し０．００２〜０．０８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。
【００２０】又、ポリエチレンオキサイド（Ｃ）とヒド
ロキシプロピルセルロース（Ｄ）の添加量は、部分ケン
化ポリビニルアルコール（Ａ）及びヒドロキシプロピル
メチルセルロース（Ｂ）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０．１〜０．８である。
【００２１】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及びヒドロキシプロピルセルロース
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。
【００２２】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：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−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。
【００２３】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。
【００２４】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。
【００２５】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。
【００２６】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。
【００２７】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。
【００２８】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。
【００２９】本発明においては、重合度１２００〜２０
００の高重合度の塩化ビニル系樹脂を製造するのである
から、懸濁重合は40〜55℃で行う。
【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。
【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。
【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。
【００３３】
【実施例】次に本発明の実施例を説明する。
【００３４】「実施例１、２、比較例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２００重量部と、表１に示した所定
量の、ケン化度７２モル％の部分ケン化ポリビニルアル
コール（以下、「ＰＶＡ」）、ヒドロキシプロピルメチ
ルセルロース（以下、「ＨＰＭＣ」）、粘度平均分子量
が４５０万のポリエチレンオキサイド（以下、「ＰＥ
Ｏ」）及びヒドロキシプロピルセルロース（以下、「Ｈ
ＰＣ」）を供給、攪拌して各成分を溶解した。次いで、
α−クミルパーオキシネオデカノエート０．０４５重量
部とｔ−ブチルパーオキシネオデカノエート０．０４５
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、昇温を開始し、重
合器内を５１℃に昇温して重合反応を開始した。
【００３５】還流凝縮器には反応系が５１℃に昇温した
直後から水を循環し、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。重合器内の圧力が
０．１ＭＰａ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４時間であった。
【００３６】「比較例２」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２００重量部と、表１に示した所定量の、ＰＶＡ、Ｈ
ＰＭＣ及びＰＥＯを供給、攪拌して各成分を溶解した。
次いで、α−クミルパーオキシネオデカノエート０．０
２５重量部とｔ−ブチルパーオキシネオデカノエート
０．０４５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、昇温を
開始し、重合器内を５１℃に昇温して重合反応を開始し
た。
【００３７】還流凝縮器には水を循環することなく懸濁
重合を行った。重合器内の圧力が０．１ＭＰａ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７時間であっ
た。
【００３８】得られた塩化ビニル樹脂の平均重合度、嵩
比重及び粒度分布を測定し、結果を表１に示した。尚、
測定方法は以下の通りである。
（１）平均重合度 ＪＩＳ Ｋ６７２１に準拠して測定
した。
（２）嵩比重 ＪＩＳ Ｋ６７２１に準拠して測定し
た。
（３）粒度分布
ＪＩＳ Ｚ８８０１に準拠し、６０、１００、１５０及
び２００メッシュの標準箭を使用し、節に残った塩化ビ
ニル樹脂粒子の比率（重量％）を測定した。
【００３９】
【表１】【００４０】
【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、経済的に重合でき、嵩比重
の高い高重合度（１２００〜２０００）の塩化ビニル系
樹脂を得ることができる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride resin. More specifically, the present invention relates to a method for producing a vinyl chloride resin having a high bulk density and a high degree of polymerization, which can be economically polymerized. 2. Description of the Related Art Usually, a vinyl chloride monomer is polymerized by a batch type aqueous suspension polymerization method using a polymerization apparatus equipped with a jacket for heating and cooling, a reflux condenser, a stirrer, and the like. It is done in. That is, an aqueous medium, a vinyl chloride monomer, a dispersant, and a polymerization initiator are charged into a polymerization vessel, and the temperature is raised to a predetermined polymerization temperature to carry out a suspension polymerization reaction. From the point in time, cooling water was passed through the jacket and the reflux condenser, and the polymerization temperature was maintained at a predetermined temperature to advance the suspension polymerization. After the polymerization was completed, unreacted vinyl chloride monomer was recovered and the vinyl chloride polymer Is polymerized by a series of operations of taking out. [0004] In this suspension polymerization, foaming of the polymerization reaction product at the time of preparation causes fish eyes to occur, scales adhere to the inside of the polymerization vessel due to foaming or scattering of the polymerization reaction product, and coarse-grained products increase. However, there was a defect that the slow heating capability was reduced. [0005] In order to solve these problems, various methods have been proposed in which polyvinyl alcohol, cellulose, polyethylene oxide, polyvinylpyrrolidone, and the like are used in combination as a dispersant (for example, Japanese Patent Laid-Open Publication No. HEI 10-163556). JP-A-60-158206, JP-A-61-1159
08, JP-A-1-256504, JP-A-1
-268702). However, these methods have failed to provide a vinyl chloride resin having a high bulk specific gravity, that is, a good moldability. Japanese Patent Application Laid-Open No. 5-125105 proposes a polymerization method for obtaining a vinyl chloride resin having a high bulk specific gravity. That is, when suspension polymerization is performed, a partially saponified polyvinyl alcohol having a saponification degree of 68 to 76 mol%, a polyethylene oxide having a weight average molecular weight of 2,000,000 to 8,000,000, and hydroxypropyl methylcellulose are used in combination as a dispersant. Methods for producing polymers have been proposed. However, in the above polymerization method, a resin having a high bulk specific gravity can be obtained with a vinyl chloride resin having a low polymerization degree lower than 1200, but a polymerization degree of 1200 to 2
With a vinyl chloride resin having a high polymerization degree of 000, a resin having a high bulk specific gravity could not be obtained. An object of the present invention is to provide a method for producing a vinyl chloride resin which can be economically polymerized and has a high bulk density and a high degree of polymerization in view of the above-mentioned drawbacks. [0010] The method for producing a vinyl chloride resin of the present invention uses a polymerization vessel equipped with a reflux condenser.
When a vinyl monomer mainly composed of a vinyl chloride monomer is subjected to suspension polymerization with a polymerization initiator in an aqueous medium containing a dispersant, the degree of saponification is 68 to 76 as the dispersant.
Mol% of partially saponified polyvinyl alcohol (A), hydroxypropylmethylcellulose (B), polyethylene oxide (C) having a viscosity average molecular weight of 2,000,000 to 8,000,000 and hydroxypropylcellulose (D) were added, and the polymerization temperature was 40 to 55. It is characterized in that it is polymerized at ℃ DETAILED DESCRIPTION OF THE INVENTION The vinyl monomer used in the present invention is mainly composed of a vinyl chloride monomer. That is, it is a mixture of a vinyl chloride monomer and a polymerizable vinyl monomer mainly containing the vinyl chloride monomer or containing the vinyl chloride monomer as a main component (including 50% by weight or more). Examples of the vinyl monomer include vinyl esters such as vinyl acetate and vinyl propionate:
(Meth) acrylates 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. In the present invention, the dispersant has a saponification degree of 68.
~ 76 mol% of partially saponified polyvinyl alcohol (A), hydroxypropyl methylcellulose (B),
Polyethylene oxide (C) having a viscosity average molecular weight of 2,000,000 to 8,000,000 and hydroxypropylcellulose (D) are used in combination. In the partially saponified polyvinyl alcohol (A), when the degree of saponification decreases, the scale tends to adhere to the inner wall of the polymerization vessel, and the bulk specific gravity of the obtained vinyl chloride resin decreases, and the degree of saponification increases. The resulting vinyl chloride resin has a wide particle size distribution, generates fish eyes, deteriorates gelling properties, and reduces workability. used. As the hydroxypropylmethylcellulose (B), any of those conventionally used in aqueous suspension polymerization of a vinyl chloride monomer can be used.
A methoxy group content of 19 to 30% by weight, a hydroxypropoxyl 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. When the viscosity average molecular weight of the above-mentioned polyethylene oxide (C) is low, the bulk specific gravity of the obtained vinyl chloride resin is low. When the viscosity exceeds 8 million, the viscosity average molecular weight is 2,000,000 to 8,000,000 because it is not commercially available. Is used. The above hydroxypropyl cellulose (D)
Any of those conventionally used for aqueous suspension polymerization of a vinyl chloride monomer can be used, but the hydroxypropoxyl group content is 53 to 78% by weight and 20 ° C.
Preferably, a 2% by weight aqueous solution having a viscosity of 3 to 10 cps is used. The amounts of the partially saponified polyvinyl alcohol (A) and hydroxypropylmethylcellulose (B) are each 0.0 to 100 parts by weight of the vinyl monomer.
Preferably from 0.5 to 0.2 parts by weight, more preferably from 0.0 to 0.2 parts by weight.
1 to 0.1 part by weight. The amounts of polyethylene oxide (C) and hydroxypropylcellulose (D) added are preferably 0.002 to 0.08 parts by weight, more preferably 0.01 to 0 parts by weight, per 100 parts by weight of the vinyl monomer. 0.05 parts by weight. The amounts of polyethylene oxide (C) and hydroxypropylcellulose (D) added are each 0.1% based on the amounts of partially saponified polyvinyl alcohol (A) and hydroxypropylmethylcellulose (B).
It is preferably added at a ratio of from 0.5 to 1, more preferably from 0.1 to 0.8. In the present invention, in addition to the above dispersant, any dispersant conventionally used in aqueous suspension polymerization of a vinyl chloride monomer may be used in combination. Examples thereof include partially saponified polyvinyl alcohol having a degree of saponification other than 68 to 76 mol%, cellulose derivatives other than hydroxypropylmethylcellulose and hydroxypropylcellulose, polyacrylic acid derivatives, alkyl ethers of polyethylene oxide, sorbitan fatty acid esters, Methyl vinyl ether and the like can be mentioned. The polymerization initiator used in the present invention includes:
A polymerization initiator generally used in suspension polymerization of vinyl monomers may be used, for example, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate. And the like peroxycarbonate compounds: α-
Peroxyester compounds such as cumylperoxyneodecanate, t-butylperoxyneodecanate, and t-hexylperoxyneodecanate: acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxy Peroxides such as phenoxyacetate: azo compounds such as azobis-2,4-dimethylvaleronitrile and azobis (4-methoxy-2,4-dimethylvaleronitrile) may be used, and may be used alone, Two or more kinds may be used in combination. If the amount of the polymerization initiator is too small, the polymerization does not proceed sufficiently, and if it is too large, an abnormal reaction is likely to occur.
5 to 0.1 part by weight is preferred. The method of adding the polymerization initiator may be a method generally used in the suspension polymerization of vinyl monomers. For example, the polymerization initiator may be dissolved in an organic solvent or dispersed in an aqueous medium. And an emulsion or suspension,
There is a method of adding together with or after charging the aqueous medium and / or dispersant. Also, after charging the vinyl-based monomer, it may be press-fitted with a pump. Furthermore, polymerization regulators, chain transfer agents, pH regulators, gelling improvers, antistatic agents, and polymer scale adhesion inhibitors conventionally used in the suspension polymerization of vinyl monomers. Etc. may be added. In the present invention, a vinyl monomer mainly composed of a vinyl chloride monomer is subjected to suspension polymerization in an aqueous medium containing a dispersant using a polymerization vessel provided with a reflux condenser. The reflux condenser is a device for cooling and condensing a gas vaporized from a liquid layer to return to a liquid state to remove heat of polymerization, and a conventionally known device is used. As the suspension polymerization method, any method used in the conventional suspension polymerization of vinyl monomers may be employed. For example, (1) an aqueous medium and a dispersant are charged into a polymerization vessel. Then, a polymerization initiator was charged, and then the inside of the polymerization vessel was degassed under vacuum, and then a vinyl monomer was charged.The obtained suspension polymerization solution was heated to a predetermined polymerization initiation temperature to perform a polymerization reaction.
From the time when the reaction heat is generated, cooling water is passed through a reflux condenser to cool the mixture, and the polymerization is maintained at a predetermined temperature to promote the polymerization. (2) An aqueous medium and a dispersant are charged into the polymerization vessel, and After degassing in vacuum, a vinyl monomer is charged, and then a polymerization initiator is charged, and the obtained suspension polymerization solution is heated to a predetermined polymerization initiation temperature to carry out a polymerization reaction, and when the reaction heat is generated Then, cooling water is passed through a reflux condenser to cool the mixture, and the polymerization is allowed to proceed while maintaining the polymerization temperature at a predetermined temperature. At the same time, the polymerization monomer was charged, then the polymerization initiator was charged, and the obtained suspension polymerization solution was heated to a predetermined polymerization initiation temperature to carry out a polymerization reaction. Cool through cooling water to maintain the polymerization temperature at the specified temperature and proceed with polymerization So, after the polymerization, and a method of taking out the vinyl chloride polymer is recovered vinyl chloride monomer and the like. In this case, the temperature may be raised before charging the aqueous medium and the dispersant, or may be performed before charging the vinyl monomer. In the present invention, the degree of polymerization is from 1200 to 20.
Since a vinyl chloride resin having a high degree of polymerization of 00 is produced, the suspension polymerization is carried out at 40 to 55 ° C. In order to suppress foaming of the reaction system, it is preferable to add an antifoaming agent at or after the addition of the polymerization initiator. As the antifoaming agent, any antifoaming agent conventionally used in aqueous suspension polymerization can be used. For example, silicone oils such as polysiloxane, dimethylpolysiloxane, diphenylpolysiloxane and the like can be used. And aliphatic or aromatic alcohols having 10 to 30 carbon atoms. The amount of the defoaming agent to be added may be appropriately determined as needed. If it is too large, it may adversely affect the particle size distribution and porosity of the obtained polymer, and if it is severe, an abnormal reaction may occur. Therefore, the amount is preferably 0.001 to 0.05 part by weight based on 100 parts by weight of the vinyl monomer. Next, an embodiment of the present invention will be described. Examples 1 and 2 and Comparative Example 1 200 parts by weight of water were placed 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. A predetermined amount of partially saponified polyvinyl alcohol having a saponification degree of 72 mol% (hereinafter, “PVA”), hydroxypropylmethylcellulose (hereinafter, “HPMC”), polyethylene oxide having a viscosity average molecular weight of 4.5 million (hereinafter, “PE”)
O ") and hydroxypropylcellulose (hereinafter" H ").
PC ”) was supplied and stirred to dissolve each component. Then
0.045 parts by weight of α-cumyl peroxy neodecanoate and 0.045 parts of t-butyl peroxy neodecanoate
After the addition of parts by weight, the air in the polymerization vessel was removed, 100 parts by weight of the vinyl chloride monomer was charged, the temperature was raised, and the temperature in the polymerization vessel was raised to 51 ° C. to initiate the polymerization reaction. Water was circulated to the reflux condenser immediately after the temperature of the reaction system was raised to 51 ° C., and suspension polymerization was carried out by setting so as to remove 60% of the polymerization reaction heat. When the pressure in the polymerization vessel decreased by 0.1 MPa, the unreacted vinyl chloride monomer was recovered, dehydrated and dried to obtain a vinyl chloride polymer. The reaction time was 4 hours. Comparative Example 2 A 600 liter polymerization vessel equipped with a reflux condenser having a heat transfer area of 0.5 m 2 and a stirring blade was prepared.
200 parts by weight of water and a predetermined amount of PVA, H
PMC and PEO were supplied and stirred to dissolve each component.
Then, α-cumyl peroxy neodecanoate 0.0
After adding 25 parts by weight and 0.045 parts by weight of t-butyl peroxy neodecanoate, the air in the polymerization vessel was removed, and 100 parts by weight of a vinyl chloride monomer was charged. The temperature inside was raised to 51 ° C. to start the polymerization reaction. The suspension polymerization was carried out without circulating water in the reflux condenser. When the pressure in the polymerization vessel decreased by 0.1 MPa, the unreacted vinyl chloride monomer was recovered, dehydrated and dried to obtain a vinyl chloride polymer. The reaction time was 7 hours. The average degree of polymerization, bulk specific gravity and particle size distribution of the obtained vinyl chloride resin were measured, and the results are shown in Table 1. still,
The measuring method is as follows. (1) Average degree of polymerization Measured according to JIS K6721. (2) Bulk specific gravity Measured according to JIS K6721. (3) Particle Size Distribution According to JIS Z8801, the ratio (% by weight) of the vinyl chloride resin particles remaining in the nodes was measured using a standard gauge of 60, 100, 150 and 200 mesh. [Table 1] The method for producing the vinyl chloride polymer of the present invention is as described above, so that it can be economically polymerized and has a high bulk density and a high degree of polymerization (1200 to 2000). A resin can be obtained.
Claims (1)
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（Ａ）、ヒドロ
キシプロピルメチルセルロース（Ｂ）、粘度平均分子量
が２００万〜８００万のポリエチレンオキサイド（Ｃ）
及びヒドロキシプロピルセルロース（Ｄ）を添加し、重
合温度４０〜５５℃で重合することを特徴とする塩化ビ
ニル系樹脂の製造方法。Claims 1. Polymerization of a vinyl monomer mainly composed of a vinyl chloride monomer in an aqueous medium containing a dispersant using a polymerization vessel equipped with a reflux condenser. When the suspension polymerization is carried out using a dispersant, as the dispersant, partially saponified polyvinyl alcohol (A) having a saponification degree of 68 to 76 mol%, hydroxypropylmethylcellulose (B), polyethylene having a viscosity average molecular weight of 2,000,000 to 8,000,000 Oxide (C)
And a hydroxypropylcellulose (D), and polymerizing at a polymerization temperature of 40 to 55 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002044457A JP2003238606A (en) | 2002-02-21 | 2002-02-21 | Method for producing vinyl chloride resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002044457A JP2003238606A (en) | 2002-02-21 | 2002-02-21 | Method for producing vinyl chloride resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003238606A true JP2003238606A (en) | 2003-08-27 |
Family
ID=27783837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002044457A Pending JP2003238606A (en) | 2002-02-21 | 2002-02-21 | Method for producing vinyl chloride resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003238606A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012102296A1 (en) * | 2011-01-25 | 2012-08-02 | 住友大阪セメント株式会社 | Ultraviolet shielding composite particles and method for producing same, dispersing liquid, water-based dispersion, and oil-based dispersion containing ultraviolet shielding composite particles, and cosmetics |
| WO2012114441A1 (en) | 2011-02-21 | 2012-08-30 | 電気化学工業株式会社 | Dispersant for suspension polymerization, vinyl chloride resin and method for producing same |
| WO2015037683A1 (en) | 2013-09-13 | 2015-03-19 | 株式会社クラレ | Vinyl alcohol polymer, thickener, stabilizer for emulsion polymerization, stabilizer for suspension polymerization, coating agent, coating, sizing agent for fibers, and method for producing sized yarn and textile |
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2002
- 2002-02-21 JP JP2002044457A patent/JP2003238606A/en active Pending
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|---|---|---|---|---|
| WO2012102296A1 (en) * | 2011-01-25 | 2012-08-02 | 住友大阪セメント株式会社 | Ultraviolet shielding composite particles and method for producing same, dispersing liquid, water-based dispersion, and oil-based dispersion containing ultraviolet shielding composite particles, and cosmetics |
| JPWO2012102296A1 (en) * | 2011-01-25 | 2014-06-30 | 住友大阪セメント株式会社 | Ultraviolet shielding composite particles, production method thereof, dispersion containing ultraviolet shielding composite particles, aqueous dispersion, oil dispersion, and cosmetic |
| US9168208B2 (en) | 2011-01-25 | 2015-10-27 | Sumitomo Osaka Cement Co., Ltd. | Ultraviolet-shielding composite particles, method for manufacturing the same, ultraviolet-shielding composite particle-containing dispersion liquid, aqueous dispersion element, oil-based dispersion element and cosmetic material |
| JP6028570B2 (en) * | 2011-01-25 | 2016-11-16 | 住友大阪セメント株式会社 | Ultraviolet shielding composite particles, production method thereof, dispersion containing ultraviolet shielding composite particles, aqueous dispersion, oil dispersion, and cosmetic |
| WO2012114441A1 (en) | 2011-02-21 | 2012-08-30 | 電気化学工業株式会社 | Dispersant for suspension polymerization, vinyl chloride resin and method for producing same |
| WO2015037683A1 (en) | 2013-09-13 | 2015-03-19 | 株式会社クラレ | Vinyl alcohol polymer, thickener, stabilizer for emulsion polymerization, stabilizer for suspension polymerization, coating agent, coating, sizing agent for fibers, and method for producing sized yarn and textile |
| US9751968B2 (en) | 2013-09-13 | 2017-09-05 | Kuraray Co., Ltd. | Vinyl alcohol polymer, thickening agent, stabilizer for emulsion polymerization, stabilizer for suspension polymerization, coating agent, coated article, sizing agent for fibers, sized yarn, and production method of textile |
| WO2017094698A1 (en) | 2015-12-04 | 2017-06-08 | 日本酢ビ・ポバール株式会社 | Dispersion assis5tant for suspension polymerization, method for producing vinyl polymer in which said assistant is used, and vinyl chloride resin |
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