JPH0867705A - Production of vinyl chloride polymer - Google Patents
Production of vinyl chloride polymerInfo
- Publication number
- JPH0867705A JPH0867705A JP20683394A JP20683394A JPH0867705A JP H0867705 A JPH0867705 A JP H0867705A JP 20683394 A JP20683394 A JP 20683394A JP 20683394 A JP20683394 A JP 20683394A JP H0867705 A JPH0867705 A JP H0867705A
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- Prior art keywords
- vinyl chloride
- weight
- parts
- polymer
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【発明の詳細な説明】
【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。さらに詳しくは、播種乳化重合による
ペースト用塩化ビニル系重合体の製造方法に関する。
【０００２】
【従来の技術】従来、ペースト用塩化ビニル系重合体は
一般に水溶性の重合開始剤を用いて塩化ビニル系単量体
を乳化重合させるか、あるいは塩化ビニル系単量体を予
め機械的に均一且つ微細化し、水性媒体中に分散させて
均質化処理した後に懸濁重合させる微細懸濁重合法によ
り製造されている。また、上記重合法において種子重合
体を使用するいわゆる播種重合法、つまり播種微細懸濁
重合法や播種乳化重合法がある。従来からの播種乳化重
合法は、塩化ビニル系単量体を水、乳化剤、水溶性重合
開始剤を用いて重合させる乳化重合で種子重合体の水性
分散液を製造し、続いて、該水性分散液を用いてさら
に、塩化ビニル系単量体、水、乳化剤、水溶性重合開始
剤を加え撹拌下で重合させ、比較的粒径分布の狭く、平
均約１μ程度の塩化ビニル系重合体粒子の水性分散液を
生成する方法である。特開平5-271313号公報には、塩化
ビニル系単量体、水、アニオン系乳化剤又はノニオン系
乳化剤、油溶性重合開始剤およびその他の重合助剤を高
せん断下で均質化させた後、撹拌下で重合させる微細懸
濁重合法により種子重合体の水性分散液を製造し、続い
て該水性分散液を用いてさらに、塩化ビニル系単量体、
水、乳化剤、水溶性重合開始剤を加え撹拌下で重合させ
る播種乳化重合法により重合体濃度４０％程度の水性分
散液を得る方法が記載されている。
【０００３】
【発明が解決しようとする課題】該水性分散液からペー
スト用塩化ビニル系樹脂とするには、まず水性分散液を
噴霧乾燥させる必要があるので、水性分散液は、高濃度
ほど望ましい。しかし、該水性分散液は高濃度になると
塩化ビニル系重合体粒子が互いに会合し易くなり、つま
り不安定になる。そこでこれを防ぐためには、乳化剤を
多量に用いることになる。しかし、乳化剤が多量に塩化
ビニル系重合体に混在すると塩化ビニル系樹脂ペースト
とした際その耐水白化性が低下するので好ましくない。
そこで、乳化剤の使用量を極力抑え、なるべく重合体濃
度の高い水性分散液を製造する重合方法を提供する。
【０００４】
【課題を解決するための手段】本発明は、塩化ビニル単
独又は塩化ビニルとこれと共重合可能な単量体（以下塩
化ビニル系単量体）を、種子重合体の存在下で播種乳化
重合させる塩化ビニル系重合体の製造方法において、該
種子重合体が、塩化ビニル系単量体を該単量体１００重
量部当たり直鎖脂肪族高級アルコールを１．０〜６．０
重量部存在下、油溶性重合開始剤を用い、アニオン性乳
化剤を含む水性媒体中で微細懸濁重合させて得られた重
合体であることを特徴とする塩化ビニル系重合体の製造
方法である。
【０００５】本発明において塩化ビニル系単量体として
は、塩化ビニル単独または塩化ビニルとこれと共重合可
能な単量体からなる単量体混合物である。塩化ビニル以
外の他の単量体としては、エチレン、プロピレンおよび
α−ブテンのようなオレフィン、酢酸ビニル、プロピオ
ン酸ビニル、ラウリル酸ビニルおよびステアリル酸ビニ
ルのようなビニルエステル、アクリル酸、メタクリル酸
およびイタコン酸のような不飽和酸およびそのエステ
ル、メチルビニルエーテル、オクチルビニルエーテルお
よびラウリルビニルエーテルのようなビニルエーテル、
マレイン酸、フマール酸ならびにそれらの無水物または
それらのエステル、芳香族ビニル、不飽和ニトリル等が
挙げられる。
【０００６】本発明で用いる播種乳化重合法とは、あら
かじめ微細懸濁重合法によって得られた重合開始剤を含
有する種子重合体を作り、この種子重合体を用いて続い
てさらに単量体を乳化重合する方法であり、この方法自
体は、前述の特開平5-271313号公報にも記載されている
ごとく、公知なものである。
【０００７】種子重合体を得る微細懸濁重合法は、周知
の微細懸濁重合法を用いる。つまり、塩化ビニル系単量
体を、油溶性重合開始剤、アニオン性乳化剤を含む水性
媒体とともにホモジナイザー等を用いて予め均質化処理
した後重合させる方法である。
【０００８】特に、本発明では、この際直鎖脂肪族高級
アルコールを存在させる。該直鎖脂肪族高級アルコール
としては、炭素数１０〜１８の直鎖脂肪族高級アルコー
ルであり、具体的には、デシルアルコール、ウンデシル
アルコール、ラウリルアルコール、トリデシルアルコー
ル、ミリスチルアルコール、セチルアルコール、ステア
リルアルコールが例示される。その量は単量体１００重
量部あたり１．０〜６．０重量部である。この量が少な
いと播種乳化重合時の途中で水性分散液が凝集しやす
く、また多過ぎてもその量の割には効果は望めない。
【０００９】種子重合体を得る微細懸濁重合法で用いる
油溶性重合開始剤としては、塩化ビニル系単量体の重合
に通常用いられるものの内その１０時間半減温度が３０
〜５５℃のものが適している。
【００１０】該油溶性重合開始剤の例としては、ジ-2-
エチルヘキシルパーオキシジカーボネート（１０時間半
減温度４５℃）、２，４−ジクロロベンゾイルパーオキ
シド（５４℃）、ジ-1- メチルヘプチルパーオキシジカ
ーボネート（４４℃）、ｔ−ブチルパーオキシヘプタノ
エート（５０℃）、ｔ−ブチル パーオキシネオヘキサ
ノエート（５４℃）などがあり、これらは、単独または
二種類以上組み合わせて用いられる。
【００１１】なお、その量は、塩化ビニル系単量体１０
０重量部当たり、０．０１〜０．５重量部である。この
量が過少だと、種子重合体を得る微細懸濁重合時の重合
が遅延するし、過多だと微細懸濁重合自体の重合の制御
が困難となる。
【００１２】種子重合体を得る微細懸濁重合法で用いる
アニオン性乳化剤は、周知のものでよく、例えば高級ア
ルコール硫酸エステルのアルカリ金属塩及びアンモニウ
ム塩、アルキルベンゼンスルホン酸のアルカリ金属塩及
びアンモニウム塩等であり、これらの１種又は２種以上
が使用される。
【００１３】該乳化剤の使用量としては該単量体１００
重量部当たり、０．３〜２．０重量部、特に０．５〜
１．５重量部が好適である。
【００１４】水性媒体を形成する水は、ことさら特異な
量ではなく、単量体１００重量部当たり約５０〜３００
重量部である。なお、上記以外に水性媒体を形成する重
合助剤として、硫酸ナトリウム及び重炭酸ナトリウム等
の粒径調整剤、連鎖移動剤、重合抑制剤が使用できる。
【００１５】播種乳化重合は、前述の種子重合体を含む
水性媒体に、新たに重合させる塩化ビニル系単量体、ア
ニオン性乳化剤、水溶性重合開始剤、必要に応じて水を
加え撹拌下で重合させる方法である。これらの量比は、
最終的につまり前述の種子重合体を含む水性媒体に伴わ
れるものを含めて、該塩化ビニル系単量体１００重量部
当たり該種子重合体５〜３０重量部、アニオン性乳化剤
０．３〜１．０重量部を含む水性媒体５０〜８５重量部
とする。
【００１６】該種子重合体の量が不足すると、水性分散
液の分散状態が不安定になったり、微細な新粒子が発生
して得られた重合体からのペーストゾルが高粘度とな
り、逆に過多だと、播種乳化重合の比率が低くなり、生
産性が低くなる。
【００１７】播種乳化重合でのアニオン性乳化剤の種類
は、前述のものと同様である。該乳化剤は、重合の進行
に伴って逐次追加添加するのが粒径分布を均一にするの
に好ましい。この量が、過少だと、水性媒体の乳化状態
が不安定となり、過多だと得られた重合体からなるペー
スト加工品の性状なかでも耐水白化性が低下する。従っ
て、該塩化ビニル系単量体１００重量部当たりアニオン
性乳化剤は、好ましくは、０．５〜１．０重量部であ
る。
【００１８】播種乳化重合で用いる水溶性重合開始剤と
しては、周知のものでよい。例えば、過酸化水素、過酸
化ナトリウムのごとき過酸化物：過硫酸ナトリウム、過
硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩：さ
らにこれらと亜硫酸塩、アスコルビン酸、ナトリウムホ
ルムアルデヒドスルホキシレートなどの還元剤からなる
レドックス開始剤などがある。該開始剤は、初期に一括
添加してもよいが、重合速度をみて逐次添加するのが重
合が制御し易い。
【００１９】播種乳化重合で水性媒体を形成する水の量
が過少だと単量体や重合体の濃度が高すぎて重合途中で
凝集する恐れがあり、過多だと目的とする高濃度化を達
成しない。
【００２０】播種乳化重合での温度は、３０℃〜６５℃
が適している。
【００２１】播種乳化重合が終了後は、周知の方法つま
り取り出した重合体を含む水性媒体を、噴霧乾燥し、得
られた粉粒体に可塑剤を混練してペーストゾルとする。
【００２２】
【発明の効果】本発明によれば、少量のアニオン性乳化
剤で、塩化ビニル系重合体粒子を高濃度で含む水性媒体
を得ることが出来る。このことにより、ペースト加工に
より得られる製品は、耐水白化性も良好である。その
他、高濃度の安定した水性媒体が得られるため、重合終
了後に未反応の単量体を回収する際、高温の条件で行え
効率が良く、しかも、水性媒体の乾燥時の熱エネルギー
も少なくて済む利点もある。
【００２３】
【実施例】以下に、本発明を具体的に説明するために実
施例を揚げるが、本発明はこれらに限定されるものでは
ない。実施例中の評価項目は以下の方法による。
・重合安定性：得られた重合体の微粒懸濁液を６０メッ
シュの金網で濾過し、金網上の凝集物を取得し、及び重
合槽内壁の付着物をかき取り合わせて重量を測定し、仕
込み単量体１００重量部に対する凝集体重量で表した。
・重合体粒径：レーザー散乱粒径分布測定装置を用いて
測定した。
・水性媒体中の固形物濃度：液２ｇを１０５℃で２時間
加熱し蒸発乾固させその重量比から計算濃度（％）を求
めた。
・水性媒体の乳化安定性：撹拌翼の長さ８５ｍｍの撹拌
機付き５Ｌのフラスコ（内径１５８ｍｍ）にポリマーを
含む水性媒体５Ｋｇを入れ、７０℃で、２７５ｒｐｍで
撹拌し、撹拌開始から液表面が流動しなくなるまでの時
間（分）を測定した。
・耐水白化試験：重合体を含む水性媒体を噴霧乾燥し、
得られた重合体粉末１００重量部に２−エチルヘキシル
フタレート５５重量部、安定剤２重量部を加えライカイ
機で混練してペーストゾルとした。該ペーストゾルを３
００μのコーターでガラス板上に手で引き延ばした後、
２２０℃で５分間加熱溶融した。そのシートを脱イオン
水中に常温で４時間浸せきし、該シートのヘイズ値をJI
S K7105-1981に準拠して測定した。
【００２４】実施例で用いた高級アルコールは、その表
示として、Ｃ12：ラウリルアルコール、Ｃ14：ミリスチ
ルアルコール、Ｃ16：セチルアルコール、Ｃ18：ステア
リルアルコールである。その量は、塩化ビニル系単量体
１００重量部当たりの重量部で表した。
【００２５】微細懸濁重合及び播種乳化重合とも重合槽
は、１００Ｌのグラスライニング製で、その内壁面に
は、スケール付着防止剤として、１−ナフトールスルフ
ィド化合物を０．１５ｇ／ｍ2 塗布したものを用いた。
【００２６】参考例１〜３（種子重合体の製造）
撹拌機付きの槽に脱イオン水２２５重量部，ドデシルベ
ンゼンスルホン酸ナトリウム０．６重量部、表１に示す
種類と量の高級アルコール、ジ-2- エチルへキシルパー
オキシジカーボネート０．０５重量部を仕込み脱気した
後、塩化ビニル単量体１００重量部を仕込み、二段加圧
式高圧ポンプで分散均質化した。次に、この分散液を脱
気済の重合槽に移液し、４９℃まで昇温して重合を開始
した。約８時間後、圧力が０．５Ｋｇ／ｃｍ2 低下した
ので重合終了とし未反応の単量体を除去して内容物を取
り出した。
【００２７】実施例１
表２に記載の種子重合体を７重量部含む水性媒体、種子
重合体を含む水性媒体の水量と合わせて８０重量部とな
るだけの脱イオン水を仕込み脱気した後、塩化ビニル単
量体１００重量部を重合槽に仕込み、４９℃まで昇温し
て、過酸化水素水（濃度０．０８重量％）とナトリウム
ホルムアルデヒドスルホキシレート水溶液（濃度０．６
重量％）を少量づつ添加して重合を開始し、以降重合速
度に見合わせて合計前者０．００３重量部、後者０．０
１重量部を連続的に添加していった。 さらに重合率
１０％に達してから重合終了までの間、ドデシルベンゼ
ンスルホン酸ナトリウムの水溶液（濃度６重量％）を合
計０．３６重量部、連続添加した。約１０時間後、圧力
が０．５ｋｇ／ｃｍ2 低下したので重合終了とし未反応
の単量体を除去して内容物を取り出した。播種乳化重合
の結果及び該ペーストゾルの評価結果を表２に示す。
【００２８】実施例２
表２に記載の種子重合体を１１重量部含む水性媒体、種
子重合体を含む水性媒体の水量と合わせて６０重量部と
なるだけの脱イオン水を用いたこと、５５℃まで昇温し
て重合を開始したこと、ドデシルベンゼンスルホン酸ナ
トリウムの水溶液に代えてラウリル硫酸ナトリウムを合
計０．６５重量部、連続添加したこと以外は、実施例１
と同様におこなった。播種乳化重合の結果及び該ペース
トゾルの評価結果を表２に示す。
【００２９】比較例１
表２に記載の種子重合体を用いた以外は、実施例１と同
様に行った。重合終了後重合槽を開放したら内容物が凝
集していた。
【００３０】比較例２
表２に記載の種子重合体を１１重量部含む水性媒体、ラ
ウリル硫酸ナトリウムを合計１．３重量部とした以外
は、実施例２と同様に行った。播種乳化重合の結果及び
該ペーストゾルの評価結果を表２に示す。
【００３１】
【表１】
【００３２】
【表２】 Description: FIELD OF THE INVENTION The present invention relates to a method for producing a vinyl chloride polymer. More specifically, it relates to a method for producing a vinyl chloride polymer for paste by seeded emulsion polymerization. Conventionally, vinyl chloride-based polymers for pastes are generally prepared by emulsion-polymerizing vinyl chloride-based monomers using a water-soluble polymerization initiator, or by vinyl chloride-based monomers being preliminarily machined. It is manufactured by a fine suspension polymerization method in which it is uniformly homogenized, dispersed in an aqueous medium, homogenized, and then suspension polymerized. Further, there is a so-called seeding polymerization method using a seed polymer in the above-mentioned polymerization method, that is, a seeding fine suspension polymerization method and a seeding emulsion polymerization method. The conventional seeded emulsion polymerization method is to produce an aqueous dispersion of a seed polymer by emulsion polymerization in which a vinyl chloride monomer is polymerized with water, an emulsifier and a water-soluble polymerization initiator, and then the aqueous dispersion is prepared. Using the liquid, vinyl chloride monomer, water, an emulsifier, and a water-soluble polymerization initiator are further added and the mixture is polymerized under stirring to obtain a vinyl chloride polymer particle having a relatively narrow particle size distribution and an average of about 1 μm. This is a method for producing an aqueous dispersion. In JP-A-5-271313, vinyl chloride monomer, water, anionic emulsifier or nonionic emulsifier, after homogenizing the oil-soluble polymerization initiator and other polymerization aids under high shear, stirring. An aqueous dispersion of a seed polymer is produced by a fine suspension polymerization method in which polymerization is performed below, and subsequently, using the aqueous dispersion, a vinyl chloride-based monomer,
A method for obtaining an aqueous dispersion having a polymer concentration of about 40% by a seed emulsion polymerization method in which water, an emulsifier, and a water-soluble polymerization initiator are added and polymerization is carried out under stirring is described. In order to form a vinyl chloride resin for paste from the aqueous dispersion, it is necessary to spray-dry the aqueous dispersion first. Therefore, the higher the concentration of the aqueous dispersion, the better. . However, when the concentration of the aqueous dispersion becomes high, the vinyl chloride polymer particles easily associate with each other, that is, become unstable. Therefore, in order to prevent this, a large amount of emulsifier is used. However, if a large amount of an emulsifier is mixed in the vinyl chloride polymer, the water whitening resistance of the vinyl chloride resin paste is lowered, which is not preferable.
Then, the polymerization method which suppresses the usage-amount of an emulsifier as much as possible and manufactures an aqueous dispersion liquid whose polymer concentration is as high as possible is provided. In the present invention, vinyl chloride alone or vinyl chloride and a monomer copolymerizable therewith (hereinafter referred to as vinyl chloride-based monomer) are added in the presence of a seed polymer. In the method for producing a vinyl chloride polymer by seeding emulsion polymerization, the seed polymer comprises a vinyl chloride monomer in an amount of 1.0 to 6.0 of a linear aliphatic higher alcohol per 100 parts by weight of the monomer.
A method for producing a vinyl chloride-based polymer, which is a polymer obtained by finely suspension polymerizing in an aqueous medium containing an anionic emulsifier using an oil-soluble polymerization initiator in the presence of parts by weight. . In the present invention, the vinyl chloride-based monomer is vinyl chloride alone or a monomer mixture of vinyl chloride and a monomer copolymerizable therewith. Other monomers besides vinyl chloride include olefins such as ethylene, propylene and α-butene, vinyl acetates such as vinyl acetate, vinyl propionate, vinyl laurate and vinyl stearate, acrylic acid, methacrylic acid and Unsaturated acids and their esters such as itaconic acid, vinyl ethers such as methyl vinyl ether, octyl vinyl ether and lauryl vinyl ether,
Maleic acid, fumaric acid, their anhydrides or their esters, aromatic vinyls, unsaturated nitriles and the like can be mentioned. In the seeded emulsion polymerization method used in the present invention, a seed polymer containing a polymerization initiator obtained in advance by a fine suspension polymerization method is prepared, and then this seed polymer is used to further add a monomer. This is a method of emulsion polymerization, and this method itself is a known method as described in the above-mentioned JP-A-5-713313. As a fine suspension polymerization method for obtaining a seed polymer, a well-known fine suspension polymerization method is used. That is, it is a method in which a vinyl chloride-based monomer is homogenized with an aqueous medium containing an oil-soluble polymerization initiator and an anionic emulsifier in advance using a homogenizer and then polymerized. In the present invention, in particular, a linear aliphatic higher alcohol is present at this time. The linear aliphatic higher alcohol is a linear aliphatic higher alcohol having 10 to 18 carbon atoms, and specifically, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, Stearyl alcohol is exemplified. The amount is 1.0 to 6.0 parts by weight per 100 parts by weight of the monomer. If this amount is too small, the aqueous dispersion is likely to aggregate during the seed emulsion polymerization, and if too large, no effect can be expected for the amount. As the oil-soluble polymerization initiator used in the fine suspension polymerization method for obtaining a seed polymer, among those usually used for the polymerization of vinyl chloride-based monomers, its 10-hour half-life temperature is 30.
Those of ˜55 ° C. are suitable. Examples of the oil-soluble polymerization initiator include di-2-
Ethylhexyl peroxydicarbonate (10 hour half-life temperature 45 ° C), 2,4-dichlorobenzoyl peroxide (54 ° C), di-1-methylheptyl peroxydicarbonate (44 ° C), t-butyl peroxyheptanoate (50 ° C.), t-butyl peroxyneohexanoate (54 ° C.) and the like, and these are used alone or in combination of two or more kinds. The amount of the vinyl chloride-based monomer is 10
It is 0.01 to 0.5 parts by weight per 0 parts by weight. If this amount is too small, the polymerization during the fine suspension polymerization for obtaining the seed polymer will be delayed, and if it is too large, it will be difficult to control the polymerization of the fine suspension polymerization itself. The anionic emulsifier used in the fine suspension polymerization method for obtaining a seed polymer may be a well-known one, for example, alkali metal salts and ammonium salts of higher alcohol sulfuric acid esters, alkali metal salts and ammonium salts of alkylbenzene sulfonic acid, etc. And one or more of these are used. The amount of the emulsifier used is 100% of the monomer.
0.3 to 2.0 parts by weight, especially 0.5 to
1.5 parts by weight is preferred. The water forming the aqueous medium is not in a very specific amount, but is about 50 to 300 per 100 parts by weight of the monomer.
Parts by weight. In addition to the above, a particle size adjusting agent such as sodium sulfate and sodium bicarbonate, a chain transfer agent, or a polymerization inhibitor can be used as a polymerization aid forming an aqueous medium. In seeded emulsion polymerization, a vinyl chloride monomer to be newly polymerized, an anionic emulsifier, a water-soluble polymerization initiator and, if necessary, water are added to an aqueous medium containing the above-mentioned seed polymer under stirring. It is a method of polymerizing. The ratio of these quantities is
Finally, that is, 5 to 30 parts by weight of the seed polymer and 100 to 100 parts by weight of the vinyl chloride-based monomer, including those associated with an aqueous medium containing the above-mentioned seed polymer, an anionic emulsifier 0.3 to 1 50 to 85 parts by weight of the aqueous medium containing 0.0 part by weight. When the amount of the seed polymer is insufficient, the dispersion state of the aqueous dispersion becomes unstable, and fine new particles are generated, so that the paste sol from the polymer has a high viscosity, and conversely. If it is too large, the proportion of seeded emulsion polymerization will be low and the productivity will be low. The type of anionic emulsifier used in seeded emulsion polymerization is the same as described above. It is preferable that the emulsifier is added successively as the polymerization progresses so as to make the particle size distribution uniform. If this amount is too small, the emulsified state of the aqueous medium will be unstable, and if it is too large, the water-whitening resistance will deteriorate, among other properties of the paste processed product made of the obtained polymer. Therefore, the amount of the anionic emulsifier is preferably 0.5 to 1.0 part by weight per 100 parts by weight of the vinyl chloride monomer. The water-soluble polymerization initiator used in the seeded emulsion polymerization may be a known one. For example, peroxides such as hydrogen peroxide and sodium peroxide: persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate: from these and further reducing agents such as sulfite, ascorbic acid and sodium formaldehyde sulfoxylate. There are redox initiators and so on. The initiator may be added all at once at the initial stage, but it is easier to control the polymerization if it is added sequentially in view of the polymerization rate. If the amount of water forming the aqueous medium in the seeded emulsion polymerization is too small, the concentration of the monomer or polymer may be too high, and there is a risk of aggregation during the polymerization. Will not achieve. The temperature in seeded emulsion polymerization is 30 ° C to 65 ° C.
Is suitable. After the seeded emulsion polymerization is completed, a well-known method, that is, an aqueous medium containing the polymer taken out is spray-dried, and the obtained granular material is kneaded with a plasticizer to obtain a paste sol. According to the present invention, an aqueous medium containing a high concentration of vinyl chloride polymer particles can be obtained with a small amount of anionic emulsifier. As a result, the product obtained by paste processing also has good resistance to water whitening. In addition, since a stable high-concentration aqueous medium can be obtained, when the unreacted monomer is recovered after the completion of the polymerization, it can be performed under high temperature conditions with good efficiency, and the thermal energy for drying the aqueous medium is small. There is also an advantage. EXAMPLES Examples will be given below to specifically explain the present invention, but the present invention is not limited thereto. The evaluation items in the examples are as follows. -Polymerization stability: The obtained fine particle suspension of the polymer is filtered through a 60-mesh wire net to obtain agglomerates on the wire net, and the deposits on the inner wall of the polymerization tank are scraped together to measure the weight, and then charged. It was expressed as the weight of the aggregate relative to 100 parts by weight of the monomer. -Polymer particle size: Measured using a laser scattering particle size distribution measuring device. Solid concentration in aqueous medium: 2 g of the liquid was heated at 105 ° C. for 2 hours, evaporated to dryness, and the calculated concentration (%) was calculated from the weight ratio. Emulsion stability of aqueous medium: 5 Kg of the aqueous medium containing the polymer was placed in a 5 L flask (inner diameter 158 mm) equipped with a stirrer having a stirring blade length of 85 mm, and the mixture was stirred at 70 ° C. at 275 rpm, and the liquid surface started from the start of stirring. The time (minutes) until it stopped flowing was measured. Water resistance whitening test: spray drying an aqueous medium containing a polymer,
To 100 parts by weight of the obtained polymer powder, 55 parts by weight of 2-ethylhexyl phthalate and 2 parts by weight of a stabilizer were added, and the mixture was kneaded with a raikai machine to obtain a paste sol. 3 times the paste sol
After hand-drawing on a glass plate with a 00μ coater,
It was melted by heating at 220 ° C. for 5 minutes. Immerse the sheet in deionized water at room temperature for 4 hours and change the haze value of the sheet to JI.
It was measured according to S K7105-1981. The higher alcohols used in the examples are C 12 : lauryl alcohol, C 14 : myristyl alcohol, C 16 : cetyl alcohol, and C 18 : stearyl alcohol. The amount is expressed in parts by weight per 100 parts by weight of the vinyl chloride-based monomer. In both the fine suspension polymerization and the seed emulsion polymerization, the polymerization tank is made of 100 liter glass lining, and the inner wall surface is coated with 0.15 g / m 2 of 1-naphthol sulfide compound as a scale adhesion preventing agent. Was used. Reference Examples 1 to 3 (Production of Seed Polymer) 225 parts by weight of deionized water, 0.6 part by weight of sodium dodecylbenzenesulfonate, a higher alcohol of the type and amount shown in Table 1, in a tank equipped with a stirrer. After charging 0.05 parts by weight of di-2-ethylhexyl peroxydicarbonate and degassing, 100 parts by weight of vinyl chloride monomer was charged and the mixture was homogenized by dispersion with a two-stage pressure type high pressure pump. Next, this dispersion liquid was transferred to a degassed polymerization tank and heated to 49 ° C. to start polymerization. After about 8 hours, the pressure dropped by 0.5 Kg / cm 2 , so the polymerization was terminated and the unreacted monomers were removed and the contents were taken out. Example 1 After adding 7 parts by weight of the seed polymer described in Table 2 and 80 parts by weight of deionized water together with the amount of water in the aqueous medium containing the seed polymer, deaeration was carried out. Then, 100 parts by weight of vinyl chloride monomer was charged into a polymerization tank, the temperature was raised to 49 ° C., and hydrogen peroxide solution (concentration 0.08% by weight) and sodium formaldehyde sulfoxylate aqueous solution (concentration 0.6
(% By weight) is added little by little to start the polymerization, and thereafter the total amount of the former is 0.003 parts by weight and the latter is 0.0
1 part by weight was continuously added. Further, from the time the polymerization rate reached 10% to the end of the polymerization, a total of 0.36 parts by weight of an aqueous solution of sodium dodecylbenzenesulfonate (concentration 6% by weight) was continuously added. After about 10 hours, the pressure dropped by 0.5 kg / cm 2 , so the polymerization was terminated and unreacted monomers were removed and the contents were taken out. Table 2 shows the results of seed emulsion polymerization and the evaluation results of the paste sol. Example 2 An aqueous medium containing 11 parts by weight of the seed polymer shown in Table 2 was used, and deionized water was used in an amount of 60 parts by weight together with the amount of water in the aqueous medium containing the seed polymer. Example 1 except that the temperature was raised to 0 ° C. to start the polymerization and that a total of 0.65 parts by weight of sodium lauryl sulfate was continuously added in place of the aqueous solution of sodium dodecylbenzenesulfonate.
Same as above. Table 2 shows the results of seed emulsion polymerization and the evaluation results of the paste sol. Comparative Example 1 Example 1 was repeated except that the seed polymer shown in Table 2 was used. When the polymerization tank was opened after completion of the polymerization, the contents were aggregated. Comparative Example 2 The procedure of Example 2 was repeated, except that the aqueous medium containing 11 parts by weight of the seed polymer shown in Table 2 and a total of 1.3 parts by weight of sodium lauryl sulfate were used. Table 2 shows the results of seed emulsion polymerization and the evaluation results of the paste sol. [Table 1] [Table 2]
Claims (1)
重合可能な単量体（以下塩化ビニル系単量体）を、種子
重合体の存在下で播種乳化重合させる塩化ビニル系重合
体の製造方法において、該種子重合体が、塩化ビニル系
単量体を該単量体１００重量部当たり直鎖脂肪族高級ア
ルコールを１．０〜６．０重量部存在下、油溶性重合開
始剤を用い、アニオン性乳化剤を含む水性媒体中で微細
懸濁重合させて得られた重合体であることを特徴とする
塩化ビニル系重合体の製造方法。 【請求項２】該油溶性重合開始剤がその１０時間半減温
度が３０〜５５℃のものであることを特徴とする〔請求
項１〕に記載の製造方法。 【請求項３】該播種乳化重合において、塩化ビニル系単
量体１００重量部当たり、該種子重合体を５〜３０重量
部用いることを特徴とする〔請求項１〕に記載の製造方
法。 【請求項４】該播種乳化重合において、塩化ビニル系単
量体１００重量部当たり、アニオン性乳化剤０．３〜
１．０重量部を含む水性媒体５０〜８５重量部を用いる
ことを特徴とする〔請求項１〕に記載の製造方法。Claims: 1. Chlorination in which seeding emulsion polymerization of vinyl chloride alone or vinyl chloride and a monomer copolymerizable therewith (hereinafter referred to as vinyl chloride monomer) is carried out in the presence of a seed polymer. In the method for producing a vinyl polymer, the seed polymer is an oil containing a vinyl chloride monomer in an amount of 1.0 to 6.0 parts by weight of a linear aliphatic higher alcohol per 100 parts by weight of the monomer. A process for producing a vinyl chloride-based polymer, which is a polymer obtained by finely suspension polymerizing in an aqueous medium containing an anionic emulsifier using a soluble polymerization initiator. 2. The method according to claim 1, wherein the oil-soluble polymerization initiator has a 10-hour half-life temperature of 30 to 55 ° C. 3. The method according to claim 1, wherein 5 to 30 parts by weight of the seed polymer is used per 100 parts by weight of the vinyl chloride-based monomer in the seed emulsion polymerization. 4. In the seeded emulsion polymerization, an anionic emulsifier of 0.3 to 100 parts by weight per 100 parts by weight of a vinyl chloride monomer is used.
50-85 parts by weight of an aqueous medium containing 1.0 part by weight is used, and the production method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20683394A JP3419098B2 (en) | 1994-08-31 | 1994-08-31 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20683394A JP3419098B2 (en) | 1994-08-31 | 1994-08-31 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0867705A true JPH0867705A (en) | 1996-03-12 |
| JP3419098B2 JP3419098B2 (en) | 2003-06-23 |
Family
ID=16529832
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20683394A Expired - Lifetime JP3419098B2 (en) | 1994-08-31 | 1994-08-31 | Method for producing vinyl chloride polymer |
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| Country | Link |
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| JP (1) | JP3419098B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10212304A (en) * | 1997-01-29 | 1998-08-11 | Shindaiichi Enbi Kk | Production of vinyl chloride polymer latex |
| KR100264944B1 (en) * | 1996-08-27 | 2000-09-01 | 엘프 아토켐 소시에떼아노님 | Bipopulated latex of polymers based on vinyl chloride, processes for the production thereof and application thereof in plastisols exhibiting improved rheology |
| JP2004323861A (en) * | 2004-08-11 | 2004-11-18 | Shin Dai-Ichi Vinyl Corp | Method for manufacturing vinyl chloride polymer latex |
| WO2013032142A2 (en) * | 2011-09-02 | 2013-03-07 | (주) 엘지화학 | Highly functional polymerizing additive and method for preparing a vinyl chloride-based seed using same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101536036B1 (en) * | 2012-09-20 | 2015-07-13 | 주식회사 엘지화학 | Polymerization method of polyvinyl chloride having low cost and high efficiency |
-
1994
- 1994-08-31 JP JP20683394A patent/JP3419098B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100264944B1 (en) * | 1996-08-27 | 2000-09-01 | 엘프 아토켐 소시에떼아노님 | Bipopulated latex of polymers based on vinyl chloride, processes for the production thereof and application thereof in plastisols exhibiting improved rheology |
| JPH10212304A (en) * | 1997-01-29 | 1998-08-11 | Shindaiichi Enbi Kk | Production of vinyl chloride polymer latex |
| JP2004323861A (en) * | 2004-08-11 | 2004-11-18 | Shin Dai-Ichi Vinyl Corp | Method for manufacturing vinyl chloride polymer latex |
| WO2013032142A2 (en) * | 2011-09-02 | 2013-03-07 | (주) 엘지화학 | Highly functional polymerizing additive and method for preparing a vinyl chloride-based seed using same |
| WO2013032142A3 (en) * | 2011-09-02 | 2013-06-13 | (주) 엘지화학 | Highly functional polymerizing additive and method for preparing a vinyl chloride-based seed using same |
| JP2014521823A (en) * | 2011-09-02 | 2014-08-28 | エルジー・ケム・リミテッド | High-functional polymerization additive and method for producing vinyl chloride seed using the same |
| US9163134B2 (en) | 2011-09-02 | 2015-10-20 | Lg Chem, Ltd. | Highly functional additive for polymerization and method for preparing vinyl chloride seeds using the same |
| DE112012003654B4 (en) | 2011-09-02 | 2020-06-18 | Lg Chem, Ltd. | Process for producing a vinyl chloride seed, vinyl chloride seed and paste vinyl chloride resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3419098B2 (en) | 2003-06-23 |
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