JPH08259609A - Dispersion stabilizer for suspension polymerization of vinylic compound - Google Patents
Dispersion stabilizer for suspension polymerization of vinylic compoundInfo
- Publication number
- JPH08259609A JPH08259609A JP6771095A JP6771095A JPH08259609A JP H08259609 A JPH08259609 A JP H08259609A JP 6771095 A JP6771095 A JP 6771095A JP 6771095 A JP6771095 A JP 6771095A JP H08259609 A JPH08259609 A JP H08259609A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl
- dispersion stabilizer
- suspension polymerization
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はビニル系化合物の懸濁重
合用分散安定剤に関する。さらに詳しくは消泡効果に著
しく優れた塩化ビニルなどのビニル系化合物の懸濁重合
用分散安定剤に関する。FIELD OF THE INVENTION The present invention relates to a dispersion stabilizer for suspension polymerization of vinyl compounds. More specifically, it relates to a dispersion stabilizer for suspension polymerization of vinyl compounds such as vinyl chloride, which has an excellent antifoaming effect.
【0002】[0002]
【従来の技術】工業的に塩化ビニル系樹脂などのビニル
系重合体を製造する場合には、水性媒体中で分散安定剤
の存在下で塩化ビニルなどのビニル系化合物を分散さ
せ、油溶性触媒を用いて重合を行う懸濁重合が広く実施
されている。一般に、ビニル系重合体の品質を支配する
因子としては、重合率、水−モノマー比、重合温度、触
媒の種類および量、重合槽の型式、撹拌速度あるいは分
散安定剤の種類などが挙げられるが、なかでも分散安定
剤の種類による影響が非常に大きい。2. Description of the Related Art When a vinyl polymer such as a vinyl chloride resin is industrially produced, a vinyl compound such as vinyl chloride is dispersed in an aqueous medium in the presence of a dispersion stabilizer to obtain an oil-soluble catalyst. Suspension polymerization in which polymerization is carried out using is widely used. In general, factors that control the quality of vinyl polymers include polymerization rate, water-monomer ratio, polymerization temperature, type and amount of catalyst, type of polymerization tank, stirring speed or type of dispersion stabilizer. Among them, the influence of the type of dispersion stabilizer is extremely large.
【0003】ビニル系化合物の懸濁重合用分散安定剤に
要求される性能としては、得られるビニル系重合体粒
子の粒径分布をできるだけシャープにする働きのあるこ
と、可塑剤の吸収速度を大きくして加工性を容易に
し、重合体粒子中に残存する塩化ビニルなどのモノマー
の除去を容易にし、かつ成形品中のフィッシュアイなど
の生成を防止するために、各重合体粒子を多孔性にする
働きがあること、充填比重の大きい重合体粒子を形成
する働きがあることなどが挙げられる。従来、ビニル系
化合物の懸濁重合用分散安定剤としては、メチルセルロ
ース、カルボキシメチルセルロースなどのセルロース誘
導体あるいは部分けん化ポリビニルアルコールなどが単
独または組み合わせて使用されている。しかしながら、
従来の分散安定剤は上記〜の要求性能を満たしてい
ないという問題があった。The performance required of a dispersion stabilizer for suspension polymerization of vinyl compounds is that it has the function of making the particle size distribution of the resulting vinyl polymer particles as sharp as possible, and increases the absorption rate of the plasticizer. Each polymer particle is made porous to facilitate processability, facilitate removal of monomers such as vinyl chloride remaining in the polymer particle, and prevent formation of fish eyes in the molded product. And the function of forming polymer particles having a high filling specific gravity. Conventionally, as a dispersion stabilizer for suspension polymerization of vinyl compounds, cellulose derivatives such as methyl cellulose and carboxymethyl cellulose, partially saponified polyvinyl alcohol and the like have been used alone or in combination. However,
The conventional dispersion stabilizers have a problem that they do not satisfy the above required performances.
【0004】塩化ビニルなどのビニル系化合物の懸濁重
合は、通常バッチ式で行われ、重合器中に水性媒体、分
散安定剤、重合開始剤およびビニル系化合物などを仕込
み、さらに必要とされる添加剤を加えた後、昇温して重
合反応を行わせるという方法が一般的である。最近で
は、生産性を向上させるために重合1バッチに要する時
間を短縮することが求められており、ビニル系化合物の
懸濁重合においてリフラックスコンデンサー等を設置し
て重合熱の除熱効率を高めたり、あらかじめ加熱した水
性媒体を仕込む方法(ホットチャージ法)により昇温時
間を短縮する方法が用いられている。しかしながら、従
来のビニル系化合物の懸濁重合用分散安定剤を用いた場
合には、重合中における発泡が激しいことから重合器内
の有効容積が減少して生産性が低下したり、リフラック
スコンデンサー付重合器を用いると温度コントロールが
できなくなったり、ホットチャージ法を用いるとビニル
系重合体粒子の多孔性が低下するという致命的欠点があ
った。一方、発泡を防止するために消泡剤等を添加する
と、生成するビニル系重合体粒子の熱安定性が低下する
という問題があった。Suspension polymerization of vinyl compounds such as vinyl chloride is usually carried out in a batch system, and an aqueous medium, a dispersion stabilizer, a polymerization initiator, a vinyl compound and the like are charged in a polymerization vessel and further required. After adding the additive, it is common to raise the temperature to carry out the polymerization reaction. Recently, in order to improve productivity, it is required to shorten the time required for one batch of polymerization, and in the suspension polymerization of vinyl compounds, a reflux condenser or the like may be installed to improve the heat removal efficiency of the polymerization heat. A method of shortening the temperature rising time by a method of charging a preheated aqueous medium (hot charging method) is used. However, when a conventional dispersion stabilizer for suspension polymerization of vinyl-based compounds is used, the foaming during the polymerization is severe, so the effective volume in the polymerization vessel decreases and the productivity decreases, and the reflux condenser is used. There was a fatal defect that the temperature could not be controlled by using the attached polymerization vessel, and the porosity of the vinyl polymer particles was lowered by using the hot charge method. On the other hand, when an antifoaming agent or the like is added to prevent foaming, there is a problem that the thermal stability of the vinyl polymer particles produced is lowered.
【0005】特開平01ー95104号〔公知文献
(a)〕には、けん化度40モル%以下で、側鎖にイオ
ン基を有するエチレン・ビニルエステル共重合体からな
る塩化ビニルの懸濁重合用分散助剤が記載されている。
しかしながら公知文献(a)に記載された分散助剤は単
独で使用した場合には、ビニル系化合物の懸濁重合の安
定性が確保できない。また該分散助剤を従来の部分けん
化ポリビニルアルコールと組み合わせて使用した場合に
は、リフラックスコンデンサー付き重合器内における発
泡性が激しいという問題があった。特開平03ー140
303号〔公知文献(b)〕には、けん化度40モル%
より大きく80モル%以下で、側鎖にイオン基を有する
エチレン・ビニルエステル共重合体からなる塩化ビニル
の懸濁重合用分散安定剤が記載されている。しかしなが
ら公知文献(b)に記載された分散安定剤を使用した場
合には、上記〜の要求性能は満足できるものの、リ
フラックスコンデンサー付き重合器内における発泡性が
激しいという問題があった。Japanese Patent Application Laid-Open No. 01-95104 [Publication (a)] discloses a suspension polymerization of vinyl chloride having an saponification degree of 40 mol% or less and an ethylene / vinyl ester copolymer having an ionic group in a side chain. Dispersion aids are described.
However, when the dispersion aid described in the known document (a) is used alone, the stability of suspension polymerization of vinyl compounds cannot be ensured. Further, when the dispersion aid is used in combination with a conventional partially saponified polyvinyl alcohol, there is a problem that the foamability in the polymerization vessel with the reflux condenser is severe. Japanese Patent Laid-Open No. 03-140
No. 303 [Publication (b)] shows that the degree of saponification is 40 mol%.
A dispersion stabilizer for suspension polymerization of vinyl chloride is described which is composed of an ethylene / vinyl ester copolymer having an ionic group in a side chain at a ratio of greater than 80 mol%. However, when the dispersion stabilizer described in the known document (b) is used, the above-mentioned required performances 1 to 4 are satisfied, but there is a problem that the foamability in the polymerization vessel with the reflux condenser is severe.
【0006】[0006]
【発明が解決しようとする課題】本発明の目的は、従来
の一般的なビニル系化合物の懸濁重合方法である常温の
水性媒体を重合器内に仕込む方法(コールドチャージ
法)および重合器内のジャケットまたはコイルにより重
合温度のコントロールを行う方法はもとより、コンデン
サー付重合器を使用する方法、ホットチャージ法および
コンデンサー付重合器を用いたホットチャージ法におい
ても、重合器内の消泡効果が著しく優れており、かつ前
記〜の要求特性を同時に満たす分散安定剤を提供す
ることにある。DISCLOSURE OF THE INVENTION An object of the present invention is to use a conventional general suspension polymerization method for vinyl compounds, that is, a method for charging an aqueous medium at room temperature into a polymerization vessel (cold charge method) and the inside of the polymerization vessel. The defoaming effect in the polymerization vessel is remarkable not only in the method of controlling the polymerization temperature by using the jacket or coil, but also in the method of using a polymerization vessel with a condenser, the hot charging method and the hot charging method using a polymerization vessel with a condenser. An object of the present invention is to provide a dispersion stabilizer which is excellent and simultaneously satisfies the above required properties.
【0007】[0007]
【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意検討を重ねた結果、エチレン単位の
含有量1〜24モル%およびけん化度が80モル%より
大の変性ポリビニルアルコール(A)からなるビニル系
化合物の懸濁重合用分散安定剤(以下、第一発明と略記
する);該変性ポリビニルアルコール(A)がさらにス
ルホン酸基、アミノ基、アンモニウム基、カルボキシル
基またはカチオン基を有する水溶性もしくは水分散性で
あるビニル系化合物の懸濁重合用分散安定剤(以下、第
二発明と略記する);および該変性ポリビニルアルコー
ル(A)ならびにけん化度60〜95モル%および重合
度600以上のポリビニルアルコール系重合体(B)
を、重量比で(A)成分/(B)成分が1/9〜8/2
の割合で混合してなるビニル系化合物の懸濁重合用分散
安定剤(以下、第三発明と略記する)を見出だし本発明
を完成させるに至った。すなわち、本発明の分散安定剤
を用いた場合には、従来の一般的なビニル系化合物の懸
濁重合方法である常温の水性媒体を重合器内に仕込む方
法(コールドチャージ法)および重合器内のジャケット
またはコイルにより重合温度のコントロールを行う方法
はもとより、コンデンサー付重合器を使用する方法、ホ
ットチャージ法およびコンデンサー付重合器を用いたホ
ットチャージ法においても、重合器内の消泡効果が著し
く優れており、かつ前記〜の要求特性を同時に満た
すことを見いだし、本発明を完成させるに到った。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that modified polyvinyls having an ethylene unit content of 1 to 24 mol% and a saponification degree of more than 80 mol%. Dispersion stabilizer for suspension polymerization of vinyl compound consisting of alcohol (A) (hereinafter abbreviated as the first invention); the modified polyvinyl alcohol (A) further contains sulfonic acid group, amino group, ammonium group, carboxyl group or A dispersion stabilizer for suspension polymerization of a water-soluble or water-dispersible vinyl compound having a cationic group (hereinafter abbreviated as the second invention); and the modified polyvinyl alcohol (A) and a saponification degree of 60 to 95 mol%. And a polyvinyl alcohol-based polymer (B) having a degree of polymerization of 600 or more
The weight ratio of (A) component / (B) component is 1/9 to 8/2.
The inventors have found a dispersion stabilizer for suspension polymerization of vinyl compounds (hereinafter abbreviated as the third invention), which is obtained by mixing the above components in a ratio of (3) to complete the present invention. That is, when the dispersion stabilizer of the present invention is used, a method of charging an aqueous medium at room temperature, which is a conventional general suspension polymerization method for vinyl compounds, into a polymerization vessel (cold charge method) and a polymerization vessel The defoaming effect in the polymerization vessel is remarkable not only in the method of controlling the polymerization temperature by using the jacket or coil, but also in the method of using a polymerization vessel with a condenser, the hot charging method and the hot charging method using a polymerization vessel with a condenser. They have found that they are excellent and simultaneously satisfy the required properties (1) to (3), and have completed the present invention.
【0008】最初に第一発明について説明する。本発明
の変性ポリビニルアルコール(A)のけん化度は80モ
ル%より大であり、好ましくは88〜99モル%で、更
に好ましくは92〜98モル%である。エチレン単位の
含有量は1〜24モル%であり、好ましくは1.5〜1
5モル%、更に好ましくは2〜9モル%である。重合度
に関しては特に制限はないが、3500以下が好まし
い。First, the first invention will be described. The modified polyvinyl alcohol (A) of the present invention has a saponification degree of more than 80 mol%, preferably 88 to 99 mol%, and more preferably 92 to 98 mol%. The content of ethylene units is 1 to 24 mol%, preferably 1.5 to 1
It is 5 mol%, more preferably 2 to 9 mol%. Although the degree of polymerization is not particularly limited, it is preferably 3500 or less.
【0009】本発明における変性ポリビニルアルコール
(A)は、ビニルエステルとエチレンとの共重合体をけ
ん化することにより得られる。ビニルエステルとして
は、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピ
バリン酸ビニル等が挙げられるが、酢酸ビニルが最も好
ましい。The modified polyvinyl alcohol (A) in the present invention is obtained by saponifying a copolymer of vinyl ester and ethylene. Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and the like, with vinyl acetate being most preferred.
【0010】また、変性ポリビニルアルコール(A)
は、本発明の効果を損なわない範囲で共重合可能なエチ
レン性不飽和単量体を共重合したものでも良い。このよ
うなエチレン性不飽和単量体としては、例えば、アクリ
ロニトリル、メタクリロニトリル、エチルビニルエーテ
ル、ブチルビニルエーテル、N−ビニルピロリドン、塩
化ビニル、臭化ビニル、フッ化ビニル、塩化ビニリデ
ン、フッ化ビニリデン、テトラフルオロエチレン、など
が挙げられる。また、チオール酢酸などのチオール化合
物の存在下で、酢酸ビニルなどのビニルエステル系単量
体を、エチレンと共重合し、それをけん化するという、
従来公知の方法によって得られる末端変性物も用いるこ
とができる。Further, modified polyvinyl alcohol (A)
May be a copolymer of ethylenically unsaturated monomers copolymerizable within a range that does not impair the effects of the present invention. Examples of such ethylenically unsaturated monomers include acrylonitrile, methacrylonitrile, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, And tetrafluoroethylene. In the presence of a thiol compound such as thiol acetic acid, a vinyl ester-based monomer such as vinyl acetate is copolymerized with ethylene to saponify it.
A terminal modified product obtained by a conventionally known method can also be used.
【0011】次に本発明の第二発明について説明する。
第二発明に用いられる変性ポリビニルアルコール(A)
は水溶性または水分散性であり、第一発明の変性ポリビ
ニルアルコール(A)に、スルホン酸基、アミノ基、ア
ンモニウム基、カルボキシル基またはカチオン基を導入
したものである。該イオン性基の変性量としては、0.
01モル%〜10モル%が好ましい。イオン性基の変性
方法は特に制限はないが、イオン性基を含有するモノマ
ーとエチレンおよびビニルエステルモノマーとの共重合
により得ることができる。さらに、その共重合体の部分
けん化物は、その共重合体を公知の方法により部分的に
けん化することにより得ることができる。Next, the second invention of the present invention will be described.
Modified polyvinyl alcohol (A) used in the second invention
Is water-soluble or water-dispersible and is obtained by introducing a sulfonic acid group, an amino group, an ammonium group, a carboxyl group or a cation group into the modified polyvinyl alcohol (A) of the first invention. The modified amount of the ionic group is 0.
01 mol% to 10 mol% is preferable. The method for modifying the ionic group is not particularly limited, but it can be obtained by copolymerizing a monomer containing an ionic group with ethylene and a vinyl ester monomer. Further, the partially saponified product of the copolymer can be obtained by partially saponifying the copolymer by a known method.
【0012】本方法において用いられるスルホン酸基を
有する重合性単量体としては特に制限はないが、たとえ
ば、エチレンスルホン酸、(メタ)アリルスルホン酸、
スルホアルキルマレート、スルホアルキル(メタ)アク
リルアミド、スルホアルキル(メタ)アクリレート、ア
クリルアミド−2−メチルプロパンスルホン酸などのス
ルホン酸含有単量体およびその塩が挙げられる。The polymerizable monomer having a sulfonic acid group used in the present method is not particularly limited, but for example, ethylene sulfonic acid, (meth) allyl sulfonic acid,
Examples thereof include sulfonic acid-containing monomers such as sulfoalkyl maleates, sulfoalkyl (meth) acrylamides, sulfoalkyl (meth) acrylates, and acrylamido-2-methylpropanesulfonic acid, and salts thereof.
【0013】また、アミノ基およびアンモニウム基とし
てはたとえば、N−(1、1ージメチルー3ージメチル
アミノプロピル)(メタ)アクリルアミド、N−(1、
1ージメチルー3ージメチルアミノブチル)(メタ)ア
クリルアミド、N−ビニルイミダゾール、2ーメチルー
N−ビニルイミダゾール、ビニルー3ージメチルアミノ
プロピルエーテル、ビニルー2ージメチルアミノエチル
エーテル、アリルー3ージメチルアミノプロピルエーテ
ル、アリルジメチルアミン、メタアリルジメチルアミ
ン、およびこれらの四級化した単量体等が挙げられる。As the amino group and ammonium group, for example, N- (1,1-dimethyl-3-dimethylaminopropyl) (meth) acrylamide, N- (1,
1-dimethyl-3-dimethylaminobutyl) (meth) acrylamide, N-vinylimidazole, 2-methyl-N-vinylimidazole, vinyl-3-dimethylaminopropyl ether, vinyl-2-dimethylaminoethyl ether, allyl-3-dimethylaminopropyl ether, allyl Examples thereof include dimethylamine, methallyldimethylamine, and quaternized monomers thereof.
【0014】また、カルボキシル基としてはたとえば、
クロトン酸、マレイン酸、フマル酸、イタコン酸、(メ
タ)アクリル酸、等が挙げられる。The carboxyl group is, for example,
Examples thereof include crotonic acid, maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid, and the like.
【0015】また、チオール酢酸、メルカプトプロピオ
ン酸などのチオール化合物の存在下で、酢酸ビニルなど
のビニルエステル系単量体を、エチレンと共重合し、そ
れをけん化するという、従来公知の方法によって得られ
る末端変性物も用いることができる。Further, a vinyl ester type monomer such as vinyl acetate is copolymerized with ethylene in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, and then saponified to obtain a conventionally known method. The end-modified product obtained can also be used.
【0016】次に本発明の第三発明について説明する。
第三発明において用いられる変性ポリビニルアルコール
(A)は、第一発明または第二発明において用いられる
変性ポリビニルアルコール(A)と同一のものが用いら
れる。第三発明におけるポリビニルアルコール系重合体
(B)のけん化度は60〜95モル%であり、65〜8
8モル%が好ましく、さらに68〜82モル%がより好
ましい。ポリビニルアルコール系重合体(B)の重合度
は、600以上であり、650〜3500がより好まし
く、680〜2500がさらにより好ましい。Next, the third invention of the present invention will be explained.
The modified polyvinyl alcohol (A) used in the third invention is the same as the modified polyvinyl alcohol (A) used in the first invention or the second invention. The degree of saponification of the polyvinyl alcohol-based polymer (B) in the third invention is 60 to 95 mol% and is 65 to 8
8 mol% is preferable, and 68 to 82 mol% is more preferable. The degree of polymerization of the polyvinyl alcohol polymer (B) is 600 or more, more preferably 650 to 3500, even more preferably 680 to 2500.
【0017】成分(A)と成分(B)の重量比(A)/
(B)は1/9〜8/2であり、3/7〜7/3がより
好ましく、6/4〜6/4がさらにより好ましい。Weight ratio of component (A) and component (B) (A) /
(B) is 1/9 to 8/2, more preferably 3/7 to 7/3, and even more preferably 6/4 to 6/4.
【0018】本発明においては、第一発明または第二発
明の分散安定剤にポリビニルアルコール系重合体(B)
が併用された形態も、分散安定剤という。本発明のポリ
ビニルアルコール系重合体(B)の製造方法には特に制
限はなく、従来公知のものが好適に用いられる。In the present invention, the polyvinyl alcohol polymer (B) is used as the dispersion stabilizer of the first invention or the second invention.
A form in which is used together is also called a dispersion stabilizer. The method for producing the polyvinyl alcohol polymer (B) of the present invention is not particularly limited, and conventionally known ones are preferably used.
【0019】次に第一発明〜第三発明の分散安定剤を用
いたビニル系化合物の懸濁重合によるビニル系重合体の
製造方法について説明する。ビニル系重合体の製造方法
において用いる水性媒体の温度は特に制限はなく、20
℃程度の冷水はもとより、90℃以上の温水も好適に用
いられる。この加熱水性媒体を構成する媒体は、純粋な
水のほかに、各種の添加成分を含有する水溶液あるいは
他の有機溶剤を含む水性媒体が挙げることができる。ま
た、加熱水性媒体を重合反応系に仕込む際の供給量は、
重合反応系を充分に加温できる量であればよい。また除
熱効率を高めるためにリフラックスコンデンサー付重合
器も好適に用いられる。ビニル系重合体の製造方法にお
いて、分散安定剤の使用量は特に制限はないが、通常ビ
ニル系化合物100重量部に対して5重量部以下であ
り、0.01〜1重量部が好ましく、0.02〜0.2
重量部がさらにより好ましい。本発明の分散安定剤は単
独で使用しても良いが、塩化ビニルなどのビニル系化合
物を水性媒体中で懸濁重合する際に通常使用されるメチ
ルセルロース、ヒドロキシエチルセルロース、ヒドロキ
シプロピルセルロース、ヒドロキシプロピルメチルセル
ロースなどの水溶性セルロースエーテル、ゼラチンなど
の水溶性ポリマー、ソルビタンモノラウレート、ソルビ
タントリオレート、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コポリマーな
どの油溶性乳化剤、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、
ラウリン酸ナトリウムなどの水溶性乳化剤などを併用し
ても良い。その添加量については特に制限はないが、塩
化ビニルなどのビニル系化合物100重量部当たり0.
01〜1.0重量部が好ましい。またけん化度60モル
%未満のいわゆるポリビニルエステル系分散助剤を本発
明の分散安定剤100重量部に対し1〜100重量部添
加することも可能である。この際分散助剤は無変性のも
のでも、また側鎖あるいは末端にカルボキシル基などの
イオン基を10モル%以下有するものであっても良い。Next, a method for producing a vinyl polymer by suspension polymerization of a vinyl compound using the dispersion stabilizers of the first to third inventions will be described. The temperature of the aqueous medium used in the method for producing a vinyl polymer is not particularly limited and may be 20
Not only cold water at about 0 ° C but also warm water at 90 ° C or higher is preferably used. Examples of the medium constituting the heated aqueous medium include pure water, an aqueous solution containing various additive components, and an aqueous medium containing other organic solvent. Further, the supply amount when charging the heating aqueous medium to the polymerization reaction system,
The amount may be such that the polymerization reaction system can be sufficiently heated. Further, a polymerization vessel with a reflux condenser is also preferably used in order to enhance the heat removal efficiency. In the method for producing a vinyl polymer, the amount of the dispersion stabilizer used is not particularly limited, but is usually 5 parts by weight or less, preferably 0.01 to 1 part by weight, and 0 to 100 parts by weight of the vinyl compound. .02-0.2
Even more preferred are parts by weight. Although the dispersion stabilizer of the present invention may be used alone, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose usually used in suspension polymerization of vinyl compounds such as vinyl chloride in an aqueous medium. Water-soluble cellulose ether such as, water-soluble polymer such as gelatin, sorbitan monolaurate, sorbitan trioleate, glycerin tristearate, oil-soluble emulsifier such as ethylene oxide propylene oxide block copolymer, polyoxyethylene sorbitan monolaurate, polyoxyethylene Glycerin oleate,
You may use together water-soluble emulsifiers, such as sodium laurate. The amount of addition is not particularly limited, but it is 0. 0 per 100 parts by weight of vinyl compound such as vinyl chloride.
01 to 1.0 parts by weight is preferable. It is also possible to add 1 to 100 parts by weight of a so-called polyvinyl ester dispersion aid having a saponification degree of less than 60 mol% to 100 parts by weight of the dispersion stabilizer of the present invention. In this case, the dispersion aid may be unmodified or may have an ionic group such as a carboxyl group in its side chain or terminal at 10 mol% or less.
【0020】その他各種添加剤も必要に応じて加えるこ
とができる。各種添加剤としては、例えばアセトアルデ
ヒド、ブチルアルデヒド、トリクロロエチレン、パーク
ロロエチレンあるいはメルカプタン類などの重合度調節
剤、フェノール化合物、イオウ化合物、N−オキシド化
合物などの重合禁止剤などが挙げられる。また、pH調
整剤、スケール防止剤、架橋剤などを加えることも任意
であり、上記の添加剤を複数併用しても差し支えない。
一方、重合開始剤も、従来塩化ビニルなどのビニル系化
合物の重合に使用されているものでよく、これには例え
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などのパーカーボネー
ト化合物、t−ブチルパーオキシネオデカネート、α−
クミルパーオキシネオデカネート、t−ブチルパーオキ
シネオデカネートなどのパーエステル化合物、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
ートなどの過酸化物、2,2′−アゾビスイソブチロニ
トリル、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)などのアゾ化合物などが挙げられ、さらにはこれ
らに過硫酸カリウム、過硫酸アンモニウム、過酸化水素
などを組み合わせて使用することもできる。Various other additives can be added as required. Examples of the various additives include polymerization degree regulators such as acetaldehyde, butyraldehyde, trichloroethylene, perchloroethylene or mercaptans, and polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds. Further, it is optional to add a pH adjuster, a scale inhibitor, a cross-linking agent and the like, and a plurality of the above-mentioned additives may be used in combination.
On the other hand, the polymerization initiator may also be one conventionally used for the polymerization of vinyl compounds such as vinyl chloride, and examples thereof include diisopropyl peroxydicarbonate and di-2-
Percarbonate compounds such as ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate, t-butyl peroxyneodecanate, α-
Perester compounds such as cumyl peroxyneodecanate and t-butyl peroxyneodecanate, acetylcyclohexylsulfonyl peroxide, 2,4,4-
Peroxides such as trimethylpentyl-2-peroxyphenoxyacetate, 2,2'-azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile,
Examples thereof include azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile), and these can also be used in combination with potassium persulfate, ammonium persulfate, hydrogen peroxide and the like.
【0021】本発明の分散安定剤を用いて懸濁重合する
ことのできるビニル系化合物としては、具体的には塩化
ビニル単独のほか、塩化ビニルを主体とする単量体混合
物(塩化ビニル50重量%以上)が包含され、この塩化
ビニルと共重合されるコモノマーとしては、酢酸ビニ
ル、プロピオン酸ビニルなどのビニルエステル、(メ
タ)アクリル酸メチル、(メタ)アクリル酸エチルなど
の(メタ)アクリル酸エステル、エチレン、プロピレン
などのオレフィン、無水マレイン酸、アクリロニトリ
ル、イタコン酸、スチレン、塩化ビニリデン、ビニルエ
ーテル、その他塩化ビニルと共重合可能な単量体が例示
される。さらには、塩化ビニルを含まない上記ビニル系
化合物の単独重合や共重合に当たっても、本発明の分散
安定剤を用いることができる。本発明の分散安定剤を用
いて懸濁重合するに当たって、各成分の仕込み割合、重
合温度などは、従来塩化ビニルなどのビニル系化合物の
懸濁重合で採用されている条件に準じて定めればよい。
また、ビニル系化合物、重合開始剤、分散安定剤、加熱
水性媒体およびその他添加物の仕込み順序や比率につい
ては、なんら制限されない。また、温水を用いると同時
に、ビニル系化合物を重合器に仕込む前にビニル系化合
物を加熱しておく方法も好適に用いられる。The vinyl compound which can be suspension-polymerized by using the dispersion stabilizer of the present invention is specifically vinyl chloride alone or a monomer mixture containing vinyl chloride as a main component (vinyl chloride 50% by weight). % Or more) and as a comonomer to be copolymerized with this vinyl chloride, vinyl acetate, vinyl ester such as vinyl propionate, and (meth) acrylic acid such as methyl (meth) acrylate and ethyl (meth) acrylate can be used. Examples thereof include esters, olefins such as ethylene and propylene, maleic anhydride, acrylonitrile, itaconic acid, styrene, vinylidene chloride, vinyl ether, and other monomers copolymerizable with vinyl chloride. Furthermore, the dispersion stabilizer of the present invention can be used even in homopolymerization or copolymerization of the above vinyl compound containing no vinyl chloride. In carrying out suspension polymerization using the dispersion stabilizer of the present invention, the charging ratio of each component, the polymerization temperature, etc. may be determined according to the conditions conventionally used in suspension polymerization of vinyl compounds such as vinyl chloride. Good.
Further, the order and ratio of the vinyl compound, the polymerization initiator, the dispersion stabilizer, the heated aqueous medium and the other additives are not limited at all. Further, a method in which hot water is used and at the same time the vinyl compound is heated before charging the vinyl compound into the polymerization vessel is also suitably used.
【0022】[0022]
【実施例】以下実施例をあげて本発明をさらに詳しく説
明するが、本発明はこれらの実施例によってなんら限定
されるものではない。なお、以下の実施例において
「%」および「部」は特に断りのない限り、「重量%」
および「重量部」を意味する。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, "%" and "part" are "% by weight" unless otherwise specified.
And "parts by weight".
【0023】参考例 (エチレン変性PVAの製造)撹拌機、窒素導入口、エ
チレン導入口および開始剤添加口を備えた100L加圧
反応槽に酢酸ビニル50kgおよび、メタノール9.2
kgを仕込み、60℃に昇温した後30分間窒素バブリ
ングにより系中を窒素置換した。次いで反応槽圧力が6
kg/cm2 になるようにエチレンを導入仕込みした。開始
剤として2、2’ーアゾビス(4ーメトキシー2、4ー
ジメチルバレロニトリル)をメタノールに溶解した濃度
1. 4g/L溶液を調製し、窒素ガスによるバブリングを
行って窒素置換した。上記の反応槽内温を60℃に調整
した後、上記の開始剤溶液56mLを注入し、重合を開
始した。重合中はエチレンを導入して反応槽圧力を6 k
g/cm2 に、重合温度を60℃に維持し、上記の開始剤溶
液を180mL/ hrで連続添加した。6時間後に重合
率が40%に達したところで冷却して重合を停止した。
反応槽を解放して脱エチレンしたあと窒素ガスをバブリ
ングして脱エチレンを完全に行った。次いで減圧下に未
反応酢酸ビニルモノマーを除去し、メタノール溶液とし
た。20%に調整した該溶液にモル比(NaOHのモル数/
ポリ酢酸ビニルのモル数)0.045 のNaOHメタノール溶液
(10%濃度)を添加してけん化した。得られた変性P
VAのけん化度は94.2モル%であった。Reference Example (Production of ethylene-modified PVA) 50 kg of vinyl acetate and 9.2% of methanol in a 100 L pressure reaction tank equipped with a stirrer, a nitrogen inlet, an ethylene inlet and an initiator inlet.
After charging kg, the temperature was raised to 60 ° C., and then the system was replaced with nitrogen by nitrogen bubbling for 30 minutes. Next, the reactor pressure is 6
Ethylene was introduced and charged so as to be kg / cm 2 . A 2,4′-azobis (4-methoxy-2,4-dimethylvaleronitrile) solution as an initiator was dissolved in methanol to prepare a 1.4 g / L concentration solution, which was bubbled with nitrogen gas to substitute nitrogen. After adjusting the temperature inside the reaction tank to 60 ° C., 56 mL of the above initiator solution was injected to start polymerization. During the polymerization, ethylene was introduced to increase the reactor pressure to 6 k.
The polymerization temperature was maintained at 60 ° C. at g / cm 2 , and the above initiator solution was continuously added at 180 mL / hr. After 6 hours, when the degree of polymerization reached 40%, the polymerization was stopped by cooling.
The reaction vessel was opened to remove ethylene, and nitrogen gas was bubbled to completely remove ethylene. Then, the unreacted vinyl acetate monomer was removed under reduced pressure to obtain a methanol solution. The molar ratio of the solution adjusted to 20% (the number of moles of NaOH /
Saponification was carried out by adding a methanol solution of NaOH (molar number of polyvinyl acetate) 0.045 (10% concentration). Obtained modified P
The degree of saponification of VA was 94.2 mol%.
【0024】重合、未反応酢酸ビニルモノマーを除去し
て得られたPVAcのメタノール溶液をnーヘキサンに
沈殿、アセトンで溶解する再沈精製を3回行った後、6
0℃で減圧乾燥して精製PVAcを得た。該PVAcの
アルカリ消費量を測定して求めたエチレン変性量は5.
5モル%であった。上記のPVAcのメタノール溶液を
アルカリモル比0.2 でけん化した後、メタノールソック
スレーを3日間実施し、次いで乾燥して精製変性PVA
を得た。該変性PVAの平均重合度を常法のJIS K
6726に準じて測定したところ1400であった。Polymerization, a methanol solution of PVAc obtained by removing unreacted vinyl acetate monomer was precipitated in n-hexane, and reprecipitation purification was carried out by dissolving with acetone.
It was dried under reduced pressure at 0 ° C. to obtain purified PVAc. The ethylene modification amount obtained by measuring the alkali consumption of the PVAc is 5.
It was 5 mol%. The above-mentioned methanol solution of PVAc is saponified at an alkali molar ratio of 0.2, then subjected to methanol soxhlet for 3 days, and then dried to obtain purified modified PVA.
I got The average degree of polymerization of the modified PVA is determined according to JIS K
It was 1400 as measured according to 6726.
【0025】実施例1〜6、比較例1〜3 (塩化ビニルの重合)リフラックスコンデンサー付のグ
ラスライニング製オートクレーブに、表1に示した分散
安定剤を溶かした脱イオン水1部およびジイソプロピル
パーオキシジカーボネートの70%トルエン溶液0.0
4部を仕込み、オートクレーブ内を50mmHgとなる
まで脱気して酸素を除いたのち、撹拌下で85℃の温水
39部および塩化ビニルモノマー30部を同時に仕込ん
だ。仕込みが終了した時点での液面は重合器の底面から
60%の高さであり、内温は57℃であった。その後内
温を57℃保ち重合を継続した。重合開始時、オートク
レーブ内の圧力は7.3kg/cm2 Gであったが、重
合開始6時間後に4.2kg/cm2 Gとなった時点で
重合を停止し、未反応の塩化ビニルモノマーをパージ
し、内容物を取り出し脱水乾燥した。塩化ビニル重合体
の重合収率は85%であり、平均重合度は1050であ
った。重合性の評価結果および塩化ビニル樹脂の性能評
価結果を下記の方法により評価し、その結果を表2に示
す。Examples 1 to 6 and Comparative Examples 1 to 3 (Polymerization of vinyl chloride) In a glass-lined autoclave equipped with a reflux condenser, 1 part of deionized water prepared by dissolving the dispersion stabilizer shown in Table 1 and diisopropyl peroxide. Oxydicarbonate 70% toluene solution 0.0
After charging 4 parts and degassing the inside of the autoclave to 50 mmHg to remove oxygen, 39 parts of warm water at 85 ° C. and 30 parts of vinyl chloride monomer were simultaneously charged under stirring. The liquid level at the end of the charging was 60% above the bottom of the polymerization vessel, and the internal temperature was 57 ° C. After that, the internal temperature was kept at 57 ° C. to continue the polymerization. At the start of the polymerization, the pressure in the autoclave was 7.3 kg / cm 2 G, but the polymerization was stopped 6 hours after the start of the polymerization and reached 4.2 kg / cm 2 G, and the unreacted vinyl chloride monomer was removed. After purging, the contents were taken out and dehydrated and dried. The polymerization yield of the vinyl chloride polymer was 85%, and the average degree of polymerization was 1050. Polymerization evaluation results and vinyl chloride resin performance evaluation results were evaluated by the following methods, and the results are shown in Table 2.
【0026】(1)可塑剤吸収性 プラストグラフに接続されたプラネタリーミキサーに、
得られた塩化ビニル重合体粉末400gを入れ、60r
pmで撹拌しながら予熱(4分)して88℃としたの
ち、これにジオクチルフタレートを200g添加し、添
加時からトルクの下降した時点まで時間を可塑剤吸収性
(分)とした。 (2)CPA(Cold Plasticizer A
bsorption:冷可塑剤吸収量)ASTM−D3
367−75に記載された方法より、23℃におけるジ
オクチルフタレートの吸収量を測定した。 (3)発泡性評価 重合終了時に重合器内の発泡状態を目視により観察し、
以下の記号で示す。 ◎:発泡なし ○:重合器の底面から62〜65%の高さにまで泡が認
められた。 △:重合器の底面から66〜70%の高さにまで泡が認
められた。 ▲:重合器の底面から90〜100%の高さにまで泡が
認められた。 ×:重合器の底面から100%の高さにまで泡が認めら
れ、さらにリフラックスコンデンサーに泡が詰まってい
た。(1) Absorption of plasticizer In a planetary mixer connected to a plastograph,
Put 400 g of the obtained vinyl chloride polymer powder into 60 r
After preheating (4 minutes) while stirring at pm to 88 ° C., 200 g of dioctyl phthalate was added to this, and the time from the time of addition to the time point when the torque decreased was defined as the plasticizer absorbability (minute). (2) CPA (Cold Plasticizer A)
bsorption: cold plasticizer absorption amount) ASTM-D3
The absorption amount of dioctyl phthalate at 23 ° C. was measured by the method described in 367-75. (3) Evaluation of foaming property At the end of the polymerization, the foaming state in the polymerization vessel was visually observed,
It is indicated by the following symbols. ⊚: No foaming ◯: Bubbles were observed up to a height of 62 to 65% from the bottom of the polymerization vessel. B: Bubbles were observed up to a height of 66 to 70% from the bottom of the polymerization vessel. A: Bubbles were recognized up to a height of 90 to 100% from the bottom of the polymerization vessel. X: Bubbles were recognized up to a height of 100% from the bottom of the polymerization vessel, and the reflux condenser was also clogged with bubbles.
【0027】[0027]
【表1】 [Table 1]
【0028】[0028]
【表2】 [Table 2]
【0029】[0029]
【発明の効果】本発明の分散安定剤を使用してビニル系
化合物、特に塩化ビニルを懸濁重合して得られたビニル
系重合体は、粒子の粒径分布がシャープで、充填比重が
大きく、可塑剤の吸収速度が大きくて加工性が良好であ
り、重合体粒子中に残存する塩化ビニルなどのモノマー
の除去が容易であり、かつ各重合体粒子が多孔性である
ことから成形品中のフィッシュアイが少ない。さらに、
重合中における発泡がすくないことから、重合温度の制
御が容易であり、発泡に起因するスケールの付着が少な
い。The vinyl polymer obtained by suspension polymerization of a vinyl compound, particularly vinyl chloride, using the dispersion stabilizer of the present invention has a sharp particle size distribution and a large packing specific gravity. , The plasticizer has a high absorption rate and good processability, it is easy to remove monomers such as vinyl chloride remaining in the polymer particles, and each polymer particle is porous, so Has less fish eyes. further,
Since the foaming during the polymerization is small, it is easy to control the polymerization temperature and the adhesion of scale due to the foaming is small.
Claims (3)
よびけん化度が80モル%より大の変性ポリビニルアル
コールからなるビニル系化合物の懸濁重合用分散安定
剤。1. A dispersion stabilizer for suspension polymerization of a vinyl compound, which comprises a modified polyvinyl alcohol having an ethylene unit content of 1 to 24 mol% and a saponification degree of more than 80 mol%.
基、アミノ基、アンモニウム基、カルボキシル基または
カチオン基を有する水溶性もしくは水分散性である請求
項1記載のビニル系化合物の懸濁重合用分散安定剤。2. The dispersion stabilizer for suspension polymerization of vinyl compounds according to claim 1, wherein the modified polyvinyl alcohol is water-soluble or water-dispersible having a sulfonic acid group, an amino group, an ammonium group, a carboxyl group or a cationic group. .
ビニルアルコール(A)ならびにけん化度60〜95モ
ル%および重合度600以上のポリビニルアルコール系
重合体(B)を、重量比で(A)成分/(B)成分が1
/9〜8/2の割合で混合してなるビニル系化合物の懸
濁重合用分散安定剤。3. The modified polyvinyl alcohol (A) according to claim 1 or 2, and the polyvinyl alcohol polymer (B) having a saponification degree of 60 to 95 mol% and a polymerization degree of 600 or more in a weight ratio of (A). Component / (B) component is 1
A dispersion stabilizer for suspension polymerization of a vinyl compound, which is mixed at a ratio of / 9 to 8/2.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP06771095A JP3474304B2 (en) | 1995-03-27 | 1995-03-27 | Dispersion stabilizer for suspension polymerization of vinyl compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP06771095A JP3474304B2 (en) | 1995-03-27 | 1995-03-27 | Dispersion stabilizer for suspension polymerization of vinyl compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08259609A true JPH08259609A (en) | 1996-10-08 |
JP3474304B2 JP3474304B2 (en) | 2003-12-08 |
Family
ID=13352796
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---|---|---|---|
JP06771095A Expired - Fee Related JP3474304B2 (en) | 1995-03-27 | 1995-03-27 | Dispersion stabilizer for suspension polymerization of vinyl compounds |
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1995
- 1995-03-27 JP JP06771095A patent/JP3474304B2/en not_active Expired - Fee Related
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