JP3340492B2 - Dispersion aid for suspension polymerization of vinyl compounds - Google Patents

Dispersion aid for suspension polymerization of vinyl compounds

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Publication number
JP3340492B2
JP3340492B2 JP03539693A JP3539693A JP3340492B2 JP 3340492 B2 JP3340492 B2 JP 3340492B2 JP 03539693 A JP03539693 A JP 03539693A JP 3539693 A JP3539693 A JP 3539693A JP 3340492 B2 JP3340492 B2 JP 3340492B2
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JP
Japan
Prior art keywords
polymerization
vinyl
degree
suspension polymerization
dispersion
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.)
Expired - Fee Related
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JP03539693A
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Japanese (ja)
Other versions
JPH05345805A (en
Inventor
重喜 高田
均 丸山
直樹 藤原
和俊 寺田
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Kuraray Co Ltd
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Kuraray Co Ltd
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Publication of JPH05345805A publication Critical patent/JPH05345805A/en
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Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【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
合用分散助剤,ビニル系化合物の懸濁重合用分散安定剤
およびビニル系重合体の製造方法に関し、詳しくは塩化
ビニル等のビニル系化合物の懸濁重合にあたって、少量
の使用で高い分散力を有し、しかも得られるビニル系重
合体粒子を多孔性にする能力に優れた分散助剤,分散安
定剤およびビニル系重合体の製造方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion aid for suspension polymerization of vinyl compounds, a dispersion stabilizer for suspension polymerization of vinyl compounds, and a method for producing a vinyl polymer. Of dispersion aids, dispersion stabilizers, and vinyl polymers that have high dispersing power with a small amount of use in the suspension polymerization of vinyl compounds, and have excellent ability to make the resulting vinyl polymer particles porous. About the method.

【0002】[0002]

【従来の技術および発明が解決しようとする課題】従来
から、工業的に塩化ビニル系樹脂等のビニル系重合体を
製造する場合、水性媒体中で分散安定剤の存在下に塩化
ビニルモノマー等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法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,攪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ことが知られている。
2. Description of the Related Art Conventionally, when a vinyl polymer such as a vinyl chloride resin is industrially produced, a vinyl chloride monomer or the like is produced in an aqueous medium in the presence of a dispersion stabilizer. A suspension polymerization method in which a vinyl compound is dispersed and polymerization is performed using an oil-soluble catalyst has been widely practiced. In general, factors governing the quality of a vinyl polymer include a polymerization rate, a water-monomer ratio, a polymerization temperature, a type and amount of a catalyst, a type of a polymerization tank, a stirring speed, and a type of a dispersion stabilizer. It is known that the effect 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、(i)少量の使用で高い分散
力を示し、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、(ii)可塑剤
の吸収速度を大きくして加工性を容易にするため、およ
び重合体粒子中に残存する塩化ビニルモノマー等の除去
を容易にするため、さらには成型品中のフィッシュアイ
などの生成を防止するため各重合体粒子をできるだけ均
一にしかも多孔性にする働きがあること、および(iii)
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。
The performance required of a dispersion stabilizer for suspension polymerization of a vinyl compound is as follows: (i) it exhibits high dispersing power when used in a small amount, and the particle size distribution of the obtained vinyl polymer particles is as sharp as possible. (Ii) In order to facilitate the processability by increasing the rate of plasticizer absorption, and to facilitate removal of vinyl chloride monomer and the like remaining in the polymer particles, and a molded article (Iii) has the function of making each polymer particle as uniform and porous as possible to prevent the formation of fish eyes and the like therein; and (iii)
It has a function of forming polymer particles having a large filling specific gravity.

【0004】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それぞれ単独または組み合わ
せて使用されている。例えば、特開昭52−11589
0号公報には、けん化価300〜500(けん化度37.
3〜69.7モル%に相当する)および平均分子量100
00〜30000(平均重合度140〜530に相当す
る)の部分けん化ポリビニルアルコールを分散助剤とし
て用いて塩化ビニルを懸濁重合する方法が開示されてい
る。また、特開昭55−112210号公報には、けん
化価505〜600(けん化度14.6〜36.3モル%に
相当する)および4%メタノール溶液の粘度が0.5〜2.
0cps(平均重合度550以下に相当する)の部分け
ん化ポリビニルアルコールを分散助剤として用いて塩化
ビニルを懸濁重合する方法が開示されている。しかしな
がら、これらの分散助剤は、得られた塩化ビニル重合体
粒子のポロシティー(多孔性)の点では若干の効果が見
られるが、塩化ビニル重合体粒子の充填比重が低下する
という致命的欠点があった。
Heretofore, as a dispersion stabilizer for suspension polymerization of a vinyl compound, a cellulose derivative such as methylcellulose, carboxymethylcellulose, or partially saponified polyvinyl alcohol has been used alone or in combination. For example, JP-A-52-11589
No. 0 discloses a saponification value of 300 to 500 (a saponification degree of 37.
3 to 69.7 mol%) and an average molecular weight of 100
A method of suspending and polymerizing vinyl chloride using a partially saponified polyvinyl alcohol having an average polymerization degree of 140 to 530 (corresponding to an average degree of polymerization of 140 to 530) is disclosed. JP-A-55-112210 discloses a saponification value of 505 to 600 (corresponding to a saponification degree of 14.6 to 36.3 mol%) and a 4% methanol solution having a viscosity of 0.5 to 2.5.
A method of suspending and polymerizing vinyl chloride using a partially saponified polyvinyl alcohol having 0 cps (equivalent to an average degree of polymerization of 550 or less) as a dispersing agent is disclosed. However, these dispersing aids have some effects in terms of the porosity of the obtained vinyl chloride polymer particles, but have the fatal disadvantage that the packing specific gravity of the vinyl chloride polymer particles is reduced. was there.

【0005】さらに、特開昭53−6392号公報に
は、けん化度40〜55モル%およびイソプロパノール
と水との混合溶剤(イソプロパノール:水=1:1)中
での4%粘度が5〜15mPas(平均重合度74〜7
80に相当する)である部分けん化ポリビニルアルコー
ルを分散助剤として用いて塩化ビニルを懸濁重合する方
法が開示されている。しかしながら、該公報記載の分散
助剤は、得られる塩化ビニル重合体粒子を多孔性にする
能力が低い、可塑剤吸収速度が遅い、あるいは残留ビニ
ルモノマーの除去が困難であるという欠点があった。ま
た、特開平2−167319号公報には、けん化度80
モル%,平均重合度3000のポリビニルアルコールと
けん化度40モル%,平均重合度3000のポリビニル
アルコールとからなる塩化ビニルの懸濁重合用分散剤が
開示されており、特開昭56−167745号公報に
は、けん化度65モル%以上,平均重合度100〜30
00のポリビニルアルコールを分散剤とし、けん化度2
0〜65モル%,平均重合度1000以下のポリビニル
エステルを分散質とする水性分散液が開示されており、
該水性分散液は、塩化ビニルの懸濁重合用分散助剤に使
用できる旨の記載がある。しかしながら、これらの公報
に記載されている分散剤を用いても、上述の問題(塩化
ビニル重合体粒子の多孔性が低く、充填比重が低い)は
充分には解決されない。さらに、WO91/15518
号公報には、けん化度60モル%以下,平均重合度50
〜3000の末端イオン性基変性ポリビニルエステル系
重合体を分散質とする水性分散液を、塩化ビニル等のビ
ニル系単量体の懸濁重合用分散助剤に用いることが開示
されている。しかしながら、この分散助剤を用いても、
解決しがたい問題(特に、塩化ビニル重合体の充填比重
が小さい)が数多く残されている。その他、特開昭52
−110797号公報には、けん化度30〜65モル
%,重合度60〜6000の部分けん化ポリビニルアル
コールからなる塩化ビニルの懸濁重合用分散助剤が開示
されている。しかしながら、この分散助剤を用いると、
得られる塩化ビニル重合体粒子のポロシティー(多孔
性)は若干改善されるが、充填比重が低く、可塑剤吸収
速度が低いという問題があった。
Further, JP-A-53-6392 discloses that a saponification degree of 40 to 55 mol% and a 4% viscosity in a mixed solvent of isopropanol and water (isopropanol: water = 1: 1) are 5 to 15 mPas. (Average degree of polymerization 74 to 7
No. 80 (corresponding to 80) is used as a dispersion aid to carry out suspension polymerization of vinyl chloride. However, the dispersing aids described in this publication have the disadvantage that the resulting vinyl chloride polymer particles have low ability to make them porous, have a low plasticizer absorption rate, or have difficulty removing residual vinyl monomers. Japanese Patent Application Laid-Open No. 2-167319 discloses a saponification degree of 80.
JP-A-56-167745 discloses a dispersant for suspension polymerization of vinyl chloride, comprising polyvinyl alcohol having an average degree of polymerization of 3000 mol% and polyvinyl alcohol having a degree of saponification of 40 mol% and an average degree of polymerization of 3000. Has a degree of saponification of 65 mol% or more and an average degree of polymerization of 100 to 30.
Of polyvinyl alcohol having a degree of saponification of 2
An aqueous dispersion containing a polyvinyl ester having a dispersoid of 0 to 65 mol% and an average degree of polymerization of 1000 or less is disclosed,
There is a description that the aqueous dispersion can be used as a dispersion aid for suspension polymerization of vinyl chloride. However, even when the dispersants described in these publications are used, the above-mentioned problem (the vinyl chloride polymer particles have low porosity and low packing specific gravity) cannot be sufficiently solved. Further, WO 91/15518
JP-A No. 2000-214, the saponification degree is 60 mol% or less, the average polymerization degree is 50 mol%.
It is disclosed that an aqueous dispersion having a terminal ionic group-modified polyvinyl ester polymer of ~ 3000 as a dispersoid is used as a dispersion aid for suspension polymerization of vinyl monomers such as vinyl chloride. However, even with this dispersion aid,
Many problems that cannot be solved (especially, the packing specific gravity of the vinyl chloride polymer is small) remain. In addition, JP 52
Japanese Patent Publication No. 110797 discloses a dispersion aid for suspension polymerization of vinyl chloride comprising partially saponified polyvinyl alcohol having a saponification degree of 30 to 65 mol% and a polymerization degree of 60 to 6000. However, when this dispersing aid is used,
Although the porosity of the obtained vinyl chloride polymer particles is slightly improved, there is a problem that the packing specific gravity is low and the plasticizer absorption rate is low.

【0006】[0006]

【課題を解決するための手段】このような状況の下に、
本発明者らは、上記問題を克服してよりすぐれた懸濁重
合用の分散助剤および分散安定剤を開発すべく鋭意研究
を重ねた結果、けん化度60モル%以下,平均重合度4
000以上であり、かつ平均粒子径100μm以下のポ
リビニルエステル系重合体(以下、PVES系重合体と
略記することがある)を分散質とする水性分散液が、目
的とする性能を有する分散助剤となることを見出した。
また、それを用いた分散安定剤が目的とする性能を有す
るものになることを同時に見出した。本発明はこのよう
な知見に基いて完成したものである。
[Means for Solving the Problems] Under such circumstances,
The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems and to develop better dispersion aids and dispersion stabilizers for suspension polymerization. As a result, the degree of saponification was 60 mol% or less, and the average degree of polymerization was 4%.
An aqueous dispersion having a dispersoid of a polyvinyl ester-based polymer having a mean particle diameter of 100 μm or less (hereinafter sometimes abbreviated as a PVES-based polymer) having a target performance of at least 000 I found that.
It has also been found that a dispersion stabilizer using the same has the desired performance. The present invention has been completed based on such findings.

【0007】すなわち、本発明は、けん化度60モル%
以下および平均重合度4000以上であり、かつ平均粒
子径が100μm以下のポリビニルエステル系重合体を
分散質とする水性分散液からなるビニル系化合物の懸濁
重合用分散助剤(A)を提供するとともに、該分散助剤
(A)および重合度500以上の水溶性高分子(B)か
らなり、固形分換算の配合割合が成分(A)5〜70重
量%および成分(B)30〜95重量%であるビニル系
化合物の懸濁重合用分散安定剤を提供するものである。
さらに、本発明は、上記の分散安定剤を用いてビニル系
化合物を懸濁重合することを特徴とするビニル系重合体
の製造方法を提供するものである。
That is, the present invention provides a saponification degree of 60 mol%
The present invention provides a dispersion aid (A) for suspension polymerization of a vinyl compound comprising an aqueous dispersion containing a polyvinyl ester polymer having a mean degree of polymerization of 4000 or more and a mean particle diameter of 100 μm or less as a dispersoid. And the dispersing agent (A) and the water-soluble polymer (B) having a degree of polymerization of 500 or more. % Of a dispersion stabilizer for suspension polymerization of a vinyl compound.
Further, the present invention provides a method for producing a vinyl polymer, which comprises subjecting a vinyl compound to suspension polymerization using the above-mentioned dispersion stabilizer.

【0008】本発明による分散助剤は、上記のようにP
VES系重合体を分散質とする水性分散液であり、該P
VES系重合体は、平均重合度4000以上、好ましく
は7000以上、さらに好ましくは10000以上のも
のである。PVES系重合体の平均重合度の上限につい
ては、特に制限はないが、該重合体の製造上の観点か
ら、40000以下が好ましく、35000以下がより
好ましい。ここで、PVES系重合体の平均重合度は、
PVES系重合体を完全にけん化した後、アセチル化し
てポリ酢酸ビニルとした後、30℃におけるアセトン溶
液中の極限粘度数から、次式により求めた粘度平均重合
度(P)で表したものである。 P=(〔η〕×103 /7.94)(1/0.62) また、PVES系重合体のけん化度は、60モル%以下
であり、好ましくは40モル%以下、さらに好ましくは
15モル%以下、最も好ましくは0〜5モル%、特に0
モル%である。ここで、けん化度とは、ビニルエステル
成分のけん化度を意味し、他の成分を共重合している場
合はその成分は含まない。けん化度は従来公知の化学分
析法や核磁気共鳴分析法などにより分析できる。このP
VES系重合体を構成するビニルエステル単位として
は、様々なビニルエステル化合物に由来する単位がある
が、例えば酢酸ビニル,ギ酸ビニル,プロピオン酸ビニ
ル,酪酸ビニル,イソ酪酸ビニル,ピバリン酸ビニル,
カプリル酸ビニル,バーサチック酸ビニルなどに由来す
るビニルエステル単位が挙げられるが、これらのビニル
エステル系単位のなかでも工業的には酢酸ビニル単位が
好ましい。本発明のPVES系重合体は、その分子中に
イオン基,親水性基,親油性基を10モル%以下含むこ
とは何ら妨げるものではない。また、分散質の平均粒子
径は、100μm以下であり、好ましくは30μm以
下、さらに好ましくは10μm以下、一層好ましくは2
μm以下、より好ましくは1μm以下、特に好ましくは
0.5μm以下である。なお、分散質の平均粒子径は、固
体として測定する場合はふるい法により、水性分散液と
して測定する場合は光透過式粒度分布測定器,沈降式粒
度分布測定器あるいは動的光散乱粒度分布測定器を用い
て測定される。
The dispersing aid according to the present invention comprises P
An aqueous dispersion containing a VES polymer as a dispersoid,
The VES-based polymer has an average degree of polymerization of 4000 or more, preferably 7,000 or more, and more preferably 10,000 or more. The upper limit of the average degree of polymerization of the PVES polymer is not particularly limited, but is preferably 40,000 or less, more preferably 35,000 or less, from the viewpoint of production of the polymer. Here, the average degree of polymerization of the PVES polymer is
After completely saponifying the PVES polymer, it is acetylated to polyvinyl acetate, and is expressed by a viscosity average degree of polymerization (P) obtained from the limiting viscosity number in an acetone solution at 30 ° C. by the following formula. is there. P = ([η] × 10 3 /7.94) (1 / 0.62) The saponification degree of the PVES polymer is 60 mol% or less, preferably 40 mol% or less, more preferably 15 mol%. Below, most preferably 0 to 5 mol%, especially 0
Mol%. Here, the degree of saponification means the degree of saponification of the vinyl ester component, and when another component is copolymerized, the component is not included. The degree of saponification can be analyzed by a conventionally known chemical analysis method or nuclear magnetic resonance analysis method. This P
Examples of the vinyl ester unit constituting the VES polymer include units derived from various vinyl ester compounds. Examples thereof include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, and the like.
Examples include vinyl ester units derived from vinyl caprylate, vinyl versatate, and the like. Of these vinyl ester units, vinyl acetate units are industrially preferred. The PVES-based polymer of the present invention does not prevent the molecule from containing an ionic group, a hydrophilic group and a lipophilic group in an amount of 10 mol% or less. The average particle size of the dispersoid is 100 μm or less, preferably 30 μm or less, more preferably 10 μm or less, and further preferably 2 μm or less.
μm or less, more preferably 1 μm or less, particularly preferably
0.5 μm or less. The average particle size of the dispersoid is measured by a sieving method when measured as a solid, and when measured as an aqueous dispersion, a light transmission type particle size distribution analyzer, a sedimentation type particle size distribution analyzer, or a dynamic light scattering particle size distribution measurement. It is measured using an instrument.

【0009】本発明に用いるPVES系重合体を製造す
るには、通常公知の方法、例えば塊状重合,溶液重合,
懸濁重合,エマルジョン重合,分散重合のいずれの方法
も採用し得るが、工業的には溶液重合,エマルジョン重
合,分散重合が好ましい。また重合プロセスとしては、
回分法,半回分法,連続法いずれのプロセスにおいても
製造可能である。このPVES系重合体が部分けん化物
である場合には、ポリビニルエステルをけん化してPV
ES系重合体を得ることができる。具体的には通常公知
の方法、すなわちアルカリけん化,酸けん化のいずれも
採用できるが、工業的にはメタノール溶媒で水酸化ナト
リウムやナトリウムメトキシドを触媒としたメタノール
分解が最も有利である。けん化温度は特に制限はない
が、得られるPVES系重合体の着色防止という観点か
ら、20〜60℃で行うのが好ましい。また触媒とする
水酸化ナトリウムやナトリウムメトキシドの量は、ビニ
ルエステル単位1モルに対して通常0.2モル以下が得ら
れるPVES系重合体の着色防止や酢酸ナトリウムの量
を低く抑えるという点から好ましい。
In order to produce the PVES polymer used in the present invention, generally known methods such as bulk polymerization, solution polymerization,
Any of suspension polymerization, emulsion polymerization, and dispersion polymerization can be employed, but industrially, solution polymerization, emulsion polymerization, and dispersion polymerization are preferred. In addition, as the polymerization process,
It can be manufactured by any of batch, semi-batch, and continuous processes. When the PVES polymer is partially saponified, the polyvinyl ester is saponified to form PV
An ES polymer can be obtained. Specifically, any of the generally known methods, that is, either alkali saponification or acid saponification can be employed, but industrially, methanol decomposition using sodium hydroxide or sodium methoxide as a catalyst in a methanol solvent is most advantageous. The saponification temperature is not particularly limited, but is preferably from 20 to 60 ° C from the viewpoint of preventing coloring of the obtained PVES-based polymer. The amount of sodium hydroxide or sodium methoxide used as a catalyst is usually 0.2 mol or less per 1 mol of a vinyl ester unit in order to prevent discoloration of a PVES polymer and to keep the amount of sodium acetate low. preferable.

【0010】本発明におけるPVES系重合体を分散質
とする水性分散液は、分散質の平均粒子径が100μm
以下であれば、その製法はいずれの方法でもよい。例え
ば懸濁重合,エマルジョン重合,分散重合により得られ
た水性分散液をそのまま用いる方法、あるいはこれらの
水性分散液をスラリー状でけん化する方法が可能であ
る。また、一旦PVES系重合体あるいは部分けん化P
VES系重合体として単離した後、ジェットミル粉砕な
どで機械的に粉砕する方法、あるいはイオン系,ノニオ
ン系界面活性剤、または一般公知のポリビニルアルコー
ル(以下、PVAと略記する)などを、本発明の性能を
低下させない程度添加して、分散質の平均粒子径が10
0μm以下の水性分散液を得る方法などが可能である。
また、上述のPVES系重合体を一旦単離し、一般公知
の分散安定剤とともに溶剤に溶解し、攪拌下に水に投入
することにより水性分散液を得る方法も可能である。ま
た、水性分散液の濃度に関しては特に制限はない。
In the present invention, the aqueous dispersion containing a PVES polymer as a dispersoid has an average particle diameter of 100 μm.
Any method may be used as long as the method is as follows. For example, a method in which an aqueous dispersion obtained by suspension polymerization, emulsion polymerization, or dispersion polymerization is used as it is, or a method in which these aqueous dispersions are saponified in a slurry state, is possible. Also, once a PVES polymer or partially saponified P
After isolation as a VES polymer, a method of mechanical pulverization by jet mill pulverization or the like, or an ionic or nonionic surfactant, or a generally known polyvinyl alcohol (hereinafter abbreviated as PVA), etc. The dispersoid has an average particle size of 10
A method of obtaining an aqueous dispersion of 0 μm or less is possible.
It is also possible to obtain an aqueous dispersion by isolating the above-mentioned PVES polymer once, dissolving it in a solvent together with a generally known dispersion stabilizer, and adding it to water with stirring. There is no particular limitation on the concentration of the aqueous dispersion.

【0011】次に、本発明のビニル系化合物の懸濁重合
用分散安定剤(C)について説明する。本発明の分散安
定剤(C)は、上記の分散助剤(A)および重合度50
0以上の水溶性高分子(B)からなり、固形分換算の配
合割合が成分(A)5〜70重量%および成分(B)3
0〜95重量%であるものである。ここで、水溶性高分
子(B)としては、重合度が500以上であれば特に制
限はないが、従来公知のビニル系化合物の懸濁重合用の
分散剤(あるいは分散安定剤)が好ましく、なかでも、
けん化度が60モル%より大きく90モル%以下であっ
て平均重合度が500以上のPVA系重合体が特に好ま
しい。また、従来公知のヒドロキシプロピルセルロー
ス,メチルセルロース等のセルロース誘導体の使用も可
能である。これらの水溶性高分子(B)は主分散剤とし
て機能する。本発明の分散安定剤(C)において、上記
分散助剤(A)の配合割合は5重量%未満では、その添
加効果が小さく、また70重量%を超えると、重合安定
性に悪影響を及ぼす場合がある。
Next, the dispersion stabilizer (C) for suspension polymerization of a vinyl compound of the present invention will be described. The dispersion stabilizer (C) of the present invention comprises the above-mentioned dispersion aid (A) and a polymerization degree of 50.
0 or more water-soluble polymer (B), and the compounding ratio in terms of solid content is 5 to 70% by weight of component (A) and component (B) 3
0-95% by weight. Here, the water-soluble polymer (B) is not particularly limited as long as the degree of polymerization is 500 or more, and a conventionally known dispersant (or dispersion stabilizer) for suspension polymerization of a vinyl compound is preferable. Above all,
PVA-based polymers having a degree of saponification of more than 60 mol% and 90 mol% or less and an average degree of polymerization of 500 or more are particularly preferred. It is also possible to use conventionally known cellulose derivatives such as hydroxypropylcellulose and methylcellulose. These water-soluble polymers (B) function as main dispersants. In the dispersion stabilizer (C) of the present invention, if the compounding ratio of the above-mentioned dispersing aid (A) is less than 5% by weight, the effect of addition is small, and if it exceeds 70% by weight, the polymerization stability is adversely affected. There is.

【0012】本発明の分散安定剤(C)のさらに好まし
い態様として、固形分換算で上記の分散安定剤(C)1
00重量部に対して、けん化度60モル%以下および平
均重合度1000以下のPVES系重合体(D)を5〜
100重量部含有する分散安定剤(E)が挙げられる。
PVES系重合体(D)のけん化度は、60モル%以下
であり、15〜55モル%が好ましく、25〜45モル
%がより好ましい。PVES系重合体の平均重合度は、
1000以下であり、600以下が好ましく、150〜
550がより好ましい。このPVES系重合体(D)
は、カルボン酸基,スルホン酸基,アミノ基またはそれ
らの塩、あるいは各種イオン基で変性されたものでもよ
い。
As a further preferred embodiment of the dispersion stabilizer (C) of the present invention, the above-mentioned dispersion stabilizer (C) 1
5 parts by weight of PVES polymer (D) having a saponification degree of 60 mol% or less and an average polymerization degree of 1000 or less based on 100 parts by weight.
100 parts by weight of a dispersion stabilizer (E).
The saponification degree of the PVES polymer (D) is 60 mol% or less, preferably 15 to 55 mol%, and more preferably 25 to 45 mol%. The average degree of polymerization of the PVES polymer is
1000 or less, preferably 600 or less, 150 to
550 is more preferred. This PVES polymer (D)
May be those modified with a carboxylic acid group, a sulfonic acid group, an amino group or a salt thereof, or various ionic groups.

【0013】次に、本発明によるビニル系重合体の製造
方法について説明する。本発明の方法は、本発明の分散
安定剤(C)を用いてビニル系化合物を懸濁重合するこ
とを特徴とするものである。本発明の分散安定剤(C)
を用いてビニル系化合物を懸濁重合(例えば塩化ビニル
を単独またはこれを主体とし、これと共重合しうるモノ
マーとの混合物を懸濁重合)する際には、通常、水媒体
に分散安定剤を添加し、塩化ビニルまたはこれと共重合
しうるモノマーとの混合物を分散させ、油溶性触媒の存
在下で行われる。分散安定剤は、上記の分散助剤(A)
と水溶性高分子(B)を別々に加えてもよいし、両者を
混合した後加えてもよい。また、本発明の分散安定剤
(C)を用いると、昇温時間を短縮する目的で40℃以
上の加熱水媒体を重合反応系へ仕込む場合であっても、
フィッシュアイが少なく、可塑剤吸収性,脱モノマー性
の良好な高品質のビニル系重合体を得ることができる。
Next, a method for producing a vinyl polymer according to the present invention will be described. The method of the present invention is characterized in that a vinyl compound is subjected to suspension polymerization using the dispersion stabilizer (C) of the present invention. Dispersion stabilizer (C) of the present invention
When a vinyl compound is subjected to suspension polymerization (for example, suspension polymerization of a vinyl chloride alone or a mixture of a monomer and a monomer copolymerizable therewith), a dispersion stabilizer is usually added to an aqueous medium. And dispersing the mixture with vinyl chloride or a monomer copolymerizable therewith, and the reaction is carried out in the presence of an oil-soluble catalyst. The dispersion stabilizer is the dispersion aid (A) described above.
And the water-soluble polymer (B) may be added separately, or may be added after mixing both. Further, when the dispersion stabilizer (C) of the present invention is used, even when a heated aqueous medium of 40 ° C. or more is charged into the polymerization reaction system for the purpose of shortening the temperature rising time,
A high-quality vinyl polymer having few fish eyes and good plasticizer absorption and demonomerization properties can be obtained.

【0014】本発明の分散安定剤(C)は、重合原料で
あるビニル系化合物に対して、通常は固形分換算で0.0
05〜1重量%、好ましくは0.01〜0.5重量%の範囲
で使用される。懸濁重合に際して用いられる触媒は、油
溶性の触媒であればいずれでもよく、例えばベンゾイル
パーオキサイド,ラウロイルパーオキサイド,ジイソプ
ロピルパーオキシジカーボネート,2,2’−アゾビス
イソブチロニトリル,2,2’−アゾビス−2,4−ジ
メチルバレロニトリルあるいはこれらの混合物が使用さ
れる。また、重合温度は、一般には30〜70℃程度の
範囲から選択される。本発明の分散安定剤(C)を用い
てビニル系化合物を懸濁重合する際には、カチオン性,
ノニオン性の各種界面活性剤を1種又は2種以上併用し
てもよい。また、添加剤として、ポリメタクリル酸メチ
ル,ポリスチレンなどを少量添加することもできる。
The dispersion stabilizer (C) of the present invention is usually used in an amount of 0.0 as solids based on the amount of the vinyl compound as a raw material for polymerization.
It is used in the range of 0.05 to 1% by weight, preferably 0.01 to 0.5% by weight. The catalyst used in the suspension polymerization may be any oil-soluble catalyst, for example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, 2,2′-azobisisobutyronitrile, 2,2 '-Azobis-2,4-dimethylvaleronitrile or mixtures thereof are used. The polymerization temperature is generally selected from the range of about 30 to 70 ° C. When suspension polymerization of a vinyl compound is carried out using the dispersion stabilizer (C) of the present invention, cationic polymerization,
One or two or more nonionic surfactants may be used in combination. Further, a small amount of polymethyl methacrylate, polystyrene, or the like can be added as an additive.

【0015】本発明の方法で重合されるビニル系化合物
としては、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、アクリル酸メチル,アクリル酸エチルなどのアク
リル酸エステルもしくはメタクリル酸エステル、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
上記ビニル化合物の単独重合や共重合にあたっても、本
発明の方法を適用することは可能である。以上主として
塩化ビニルの重合について説明したが、本発明の分散助
剤(A)および分散安定剤(C)は必ずしも塩化ビニル
の懸濁重合用に限定されるものではなく、スチレン,メ
タクリレートなどのビニル系化合物の懸濁重合用にも用
いられる。
The vinyl compound to be polymerized by the method of the present invention includes, in addition to vinyl chloride alone, a monomer mixture mainly composed of vinyl chloride (50% by weight or more of vinyl chloride). Examples of comonomers to be polymerized include vinyl esters such as vinyl acetate and vinyl propionate, acrylates or methacrylates such as methyl acrylate and ethyl acrylate, olefins such as ethylene and propylene, maleic anhydride, acrylonitrile, and itaconic acid. , Styrene, vinylidene chloride, vinyl ether and other monomers copolymerizable with vinyl chloride. Further, the method of the present invention can be applied to homopolymerization or copolymerization of the above vinyl compound containing no vinyl chloride. Although the polymerization of vinyl chloride has been mainly described above, the dispersion aid (A) and the dispersion stabilizer (C) of the present invention are not necessarily limited to suspension polymerization of vinyl chloride. It is also used for suspension polymerization of system compounds.

【0016】[0016]

【実施例】以下に実施例をあげて本発明をさらに詳しく
説明するが、本発明の分散助剤および分散安定剤はこれ
らの実施例のみに限定されるものではない。以下の実施
例において、「部」は「重量部」を示す。 実施例1〜11および比較例1〜5 第1表に示す分散助剤(A)(ポリ酢酸ビニル)および
主分散剤(B)(PVA)よりなる分散安定剤(C)を
使用して塩化ビニルの懸濁重合を下記方法で実施した。
成分(A)の水性分散液の調整方法は、成分(B)の水
への溶解時に攪拌下で成分(A)の粉末を添加して分散
させた(以下の実施例および比較例において同じ)。す
なわち、30リットルのグラスライニングオートクレー
ブに脱イオン水50部,第1表に示す主分散剤(B)
(PVA)の2重量%水溶液の所定量,分散助剤(A)
(ポリ酢酸ビニル)の2重量%水性分散液の所定量およ
びジイソプロピルパーオキシジカーボネートの50重量
%トルエン溶液0.009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後、塩
化ビニルモノマーを30部仕込み、攪拌下に57℃に昇
温して重合を行った。重合開始時、オートクレーブ内の
圧力は8.5kg/cm2 Gであったが、重合開始7時間
後に4.5kg/cm2 Gとなったので、この時点で重合
を停止し、未反応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。得られた塩化ビニル樹脂の
重合収率は88%であり、平均重合度は1050であっ
た。分散安定剤の物性と使用量および得られた塩化ビニ
ル樹脂の性能を第1表に示す。
The present invention will be described in more detail with reference to the following examples, but the dispersion aid and the dispersion stabilizer of the present invention are not limited to these examples. In the following examples, "parts" indicates "parts by weight". Examples 1 to 11 and Comparative Examples 1 to 5 Using a dispersion stabilizer (C) composed of a dispersing aid (A) (polyvinyl acetate) and a main dispersant (B) (PVA) shown in Table 1 The suspension polymerization of vinyl was carried out by the following method.
The method for preparing the aqueous dispersion of the component (A) was such that the powder of the component (A) was added and dispersed under stirring when the component (B) was dissolved in water (the same in the following Examples and Comparative Examples). . That is, in a 30 liter glass-lined autoclave, 50 parts of deionized water, the main dispersant (B) shown in Table 1 were used.
A predetermined amount of a 2% by weight aqueous solution of (PVA), a dispersing aid (A)
A predetermined amount of a 2% by weight aqueous dispersion of (polyvinyl acetate) and 0.009 part of a 50% by weight toluene solution of diisopropyl peroxydicarbonate were charged, and the inside of the autoclave was degassed until the pressure became 50 mmHg to remove oxygen. Then, 30 parts of a vinyl chloride monomer was charged, and the temperature was raised to 57 ° C. with stirring to carry out polymerization. At the start of the polymerization, the pressure in the autoclave was 8.5 kg / cm 2 G, but after 7 hours from the start of the polymerization, the pressure became 4.5 kg / cm 2 G. At this point, the polymerization was stopped and unreacted vinyl chloride was added. The monomer was purged, and the contents were taken out and dehydrated and dried. The polymerization yield of the obtained vinyl chloride resin was 88%, and the average polymerization degree was 1,050. Table 1 shows the physical properties and amounts of the dispersion stabilizer and the performance of the obtained vinyl chloride resin.

【0017】[0017]

【表1】 [Table 1]

【0018】[0018]

【表2】 [Table 2]

【0019】実施例12〜20および比較例6 第2表に示す主分散剤(B)および分散助剤(A)を使
用して塩化ビニルの懸濁重合を下記方法で実施した。す
なわち、30リットルのグラスライニングオートクレー
ブに第2表に示す主分散剤(B)(PVA)の2重量%
水溶液の所定量,分散助剤(A)(ポリ酢酸ビニル)の
2重量%水性分散液の所定量およびジイソプロピルパー
オキシジカーボネートの50重量%トルエン溶液0.00
9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後、塩化ビニル単量体30部
および63℃に加熱した脱イオン水45部を仕込み、攪
拌下に重合を行った。仕込み後の内温は57℃であっ
た。重合開始時、オートクレーブ内の圧力は8.5kg/
cm2 Gであったが、重合開始7時間後に4.5kg/c
2 Gとなったので、この時点で重合を停止し、未反応
塩化ビニル単量体をパージし、内容物を取り出し脱水乾
燥した。得られた塩化ビニル樹脂の重合収率は88%で
あり、平均重合度は1050であった。この塩化ビニル
樹脂の性能を第2表に示す。
Examples 12 to 20 and Comparative Example 6 Using the main dispersant (B) and the dispersing aid (A) shown in Table 2, suspension polymerization of vinyl chloride was carried out by the following method. That is, 2% by weight of the main dispersant (B) (PVA) shown in Table 2 was added to a 30-liter glass-lined autoclave.
A predetermined amount of an aqueous solution, a predetermined amount of a 2% by weight aqueous dispersion of a dispersing aid (A) (polyvinyl acetate), and a 50% by weight solution of diisopropyl peroxydicarbonate in toluene 0.000
After 9 parts were charged and the inside of the autoclave was degassed to 50 mmHg to remove oxygen, 30 parts of a vinyl chloride monomer and 45 parts of deionized water heated to 63 ° C. were charged, and polymerization was carried out with stirring. . The internal temperature after the charging was 57 ° C. At the start of polymerization, the pressure in the autoclave is 8.5 kg /
cm 2 G, but 4.5 kg / c after 7 hours from the start of polymerization.
Since a m 2 G, the polymerization at this point was stopped and the unreacted vinyl chloride monomer was purged, dehydration drying the content was taken out. The polymerization yield of the obtained vinyl chloride resin was 88%, and the average polymerization degree was 1,050. Table 2 shows the performance of the vinyl chloride resin.

【0020】[0020]

【表3】 [Table 3]

【0021】[0021]

【表4】 [Table 4]

【0022】実施例21〜25および比較例7〜8 第3表に示す主分散剤(A)(PVA)および分散助剤
(A)(ポリ酢酸ビニル)を使用した以外は、実施例1
〜11と同様にして塩化ビニルの懸濁重合を行った。得
られた塩化ビニル樹脂の性能を第3表に示す。
Examples 21 to 25 and Comparative Examples 7 to 8 Example 1 was repeated except that the main dispersants (A) (PVA) and the dispersing aid (A) (polyvinyl acetate) shown in Table 3 were used.
Suspension polymerization of vinyl chloride was carried out in the same manner as in Nos. 1 to 11. Table 3 shows the performance of the obtained vinyl chloride resin.

【0023】[0023]

【表5】 [Table 5]

【0024】[0024]

【表6】 [Table 6]

【0025】[0025]

【表7】 [Table 7]

【0026】なお、第1,2および3表における結果
は、下記の方法により測定したものである。 (1)平均粒子径 タイラーメッシュ基準の金網を使用して乾式篩分析によ
り測定した。 (2)充填比重 JIS K6721−1959に準拠して測定した。 (3)可塑剤吸収性 プラストグラフに接続させたプラネタリーミキサーを用
い、80℃に保った容器内に塩化ビニル樹脂100部,
ジオクチルフタレート50部を投入し、攪拌しながら各
時間毎の混練トルクを記録し、混練トルクが低下した点
における混練時間で表示する。 (4)残留塩化ビニルモノマー ヘッドスペースガスクロマトグラフにより塩化ビニル樹
脂中の塩化ビニルモノマー含有量を定量した。 (5)分散助剤の平均粒子径の測定は、大塚電子(株)
製:ELS−800(1μm未満の場合)または堀場
(株)製:CAPA−700(1〜30μmの場合)ま
たはセイシン企業(株)製:SKC−2000S(30
μmより大の場合)を用いた。 (6)フィッシュアイ測定法 重合により得られた塩化ビニル樹脂100重量部,三塩
基性硫酸鉛1重量部,ステアリン酸鉛1.5重量部,二酸
化チタン0.2重量部,カーボンブラック0.1重量部,ジ
オクチルフタレート50重量部を混合した組成物25g
を145℃のロールで5分間混練し、0.2mm厚のシー
トとして分取し、このシート100cm2 の透明粒子の
数をもって示した。
The results in Tables 1, 2 and 3 are measured by the following methods. (1) Average particle diameter The average particle diameter was measured by dry sieve analysis using a metal mesh based on Tyler mesh. (2) Filling specific gravity Measured in accordance with JIS K6721-1959. (3) Plasticizer absorbency Using a planetary mixer connected to a plastograph, 100 parts of vinyl chloride resin was placed in a container kept at 80 ° C.
50 parts of dioctyl phthalate is charged, and the kneading torque for each time is recorded while stirring, and the kneading time at the point where the kneading torque is reduced is indicated. (4) Residual vinyl chloride monomer The content of the vinyl chloride monomer in the vinyl chloride resin was determined by head space gas chromatography. (5) The average particle size of the dispersion aid is measured by Otsuka Electronics Co., Ltd.
ELS-800 (in case of less than 1 μm) or Horiba Co., Ltd .: CAPA-700 (in case of 1 to 30 μm) or Seishin Enterprise Co., Ltd .: SKC-2000S (30
μm). (6) Fisheye measurement method 100 parts by weight of vinyl chloride resin obtained by polymerization, 1 part by weight of tribasic lead sulfate, 1.5 parts by weight of lead stearate, 0.2 parts by weight of titanium dioxide, 0.1 parts of carbon black 25 parts by weight of a composition obtained by mixing 50 parts by weight of dioctyl phthalate
Was kneaded with a roll at 145 ° C. for 5 minutes to obtain a sheet having a thickness of 0.2 mm, which was indicated by the number of transparent particles of 100 cm 2 .

【0027】[0027]

【発明の効果】以上の説明から明らかなとおり、本発明
の分散助剤からなる分散安定剤は、従来の分散助剤およ
び分散安定剤に比べて、得られるビニル系重合体粒子を
多孔性にする能力が非常に高く、可塑吸収速度が高く、
残留塩化ビニルモノマーの除去が容易であり、かつ充填
比重が高いことなどのすぐれた性能を有する。また、得
られるビニル系重合体粒子は、粒子径が大きくその分布
がシャープで、取扱い時の粉の飛散が少なく、かつ成型
機などへのくい込み性が良いことなど、様々な点におい
てすぐれたものである。得られた塩化ビニル重合体粒子
中の残留塩化ビニルモノマー(発癌性物質)が少ないこ
とは、塩化ビニル重合体粒子を取り扱う作業者の塩化ビ
ニルモノマー被曝量が低下し、作業環境,作業衛生の観
点から重要である。また、得られた塩化ビニル重合体粒
子の可塑剤吸収速度が早いことは、成形時の可塑剤との
混練時間が短くても良いことを意味しており、塩化ビニ
ル樹脂の成形効率の観点から重要である。さらに、得ら
れた塩化ビニル重合体粒子の充填比重が高いことは、成
形機への仕込み効率が高くなることを意味し、塩化ビニ
ル樹脂の成形効率の観点から重要である。
As is apparent from the above description, the dispersion stabilizer comprising the dispersion aid of the present invention makes the obtained vinyl polymer particles more porous than the conventional dispersion aids and dispersion stabilizers. Very high ability, high plastic absorption rate,
It has excellent performance such as easy removal of residual vinyl chloride monomer and high filling specific gravity. In addition, the obtained vinyl polymer particles are excellent in various points, such as a large particle size, a sharp distribution, small scattering of powder during handling, and good penetration into molding machines. It is. The low amount of residual vinyl chloride monomer (carcinogenic substance) in the obtained vinyl chloride polymer particles means that the worker who handles the vinyl chloride polymer particles has a reduced exposure to the vinyl chloride monomer, and from the viewpoint of work environment and work hygiene. Important from. Further, the faster plasticizer absorption rate of the obtained vinyl chloride polymer particles means that the kneading time with the plasticizer during molding may be shorter, and from the viewpoint of the molding efficiency of the vinyl chloride resin. is important. Furthermore, the high filling specific gravity of the obtained vinyl chloride polymer particles means that the charging efficiency to the molding machine is high, and is important from the viewpoint of the molding efficiency of the vinyl chloride resin.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 寺田 和俊 岡山県倉敷市酒津1621番地 株式会社ク ラレ内 (56)参考文献 特開 平4−85303(JP,A) 特開 平1−198606(JP,A) 特表 昭57−500245(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08F 2/00 - 2/60 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazutoshi Terada 1621 Sazu, Kurashiki City, Okayama Pref. Kuraray Co., Ltd. (56) References JP-A-4-85303 (JP, A) JP-A-1-198606 (JP) , A) Special Table 57-500245 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 2/00-2/60

Claims (5)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 けん化度60モル%以下および平均重合
度4000以上であり、かつ平均粒子径が100μm以
下のポリビニルエステル系重合体を分散質とする水性分
散液からなるビニル系化合物の懸濁重合用分散助剤。
1. A suspension polymerization of a vinyl compound comprising an aqueous dispersion containing a polyvinyl ester polymer having a degree of saponification of 60 mol% or less and an average degree of polymerization of 4000 or more and an average particle diameter of 100 μm or less as a dispersoid. Dispersing aid.
【請求項2】 けん化度が0モル%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助剤。
2. The dispersion aid for suspension polymerization of a vinyl compound according to claim 1, wherein the saponification degree is 0 mol%.
【請求項3】 請求項1または2記載の分散助剤(A)
および重合度500以上の水溶性高分子(B)からな
り、固形分換算の配合割合が成分(A)5〜70重量%
および成分(B)30〜95重量%であるビニル系化合
物の懸濁重合用分散安定剤(C)。
3. A dispersing aid (A) according to claim 1 or 2.
And a water-soluble polymer (B) having a polymerization degree of 500 or more, and the compounding ratio in terms of solid content is 5 to 70% by weight of the component (A).
And a dispersion stabilizer (C) for suspension polymerization of a vinyl compound which is 30 to 95% by weight of the component (B).
【請求項4】 請求項3記載の分散安定剤(C)並びに
けん化度60モル%以下および平均重合度1000以下
のポリビニルエステル系重合体(D)からなり、固形分
換算の配合割合が成分(C)100重量部に対して成分
(D)5〜100重量部であるビニル系化合物の懸濁重
合用分散安定剤。
4. The dispersion stabilizer (C) according to claim 3, and a polyvinyl ester polymer (D) having a degree of saponification of 60 mol% or less and an average degree of polymerization of 1000 or less. C) A dispersion stabilizer for suspension polymerization of a vinyl compound, wherein the component (D) is 5 to 100 parts by weight per 100 parts by weight.
【請求項5】 請求項3記載の分散安定剤(C)を用い
てビニル系化合物を懸濁重合することを特徴とするビニ
ル系重合体の製造方法。
5. A method for producing a vinyl polymer, comprising subjecting a vinyl compound to suspension polymerization using the dispersion stabilizer (C) according to claim 3.
JP03539693A 1992-03-10 1993-02-24 Dispersion aid for suspension polymerization of vinyl compounds Expired - Fee Related JP3340492B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP03539693A JP3340492B2 (en) 1992-03-10 1993-02-24 Dispersion aid for suspension polymerization of vinyl compounds

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP4-51939 1992-03-10
JP5193992 1992-03-10
JP03539693A JP3340492B2 (en) 1992-03-10 1993-02-24 Dispersion aid for suspension polymerization of vinyl compounds

Publications (2)

Publication Number Publication Date
JPH05345805A JPH05345805A (en) 1993-12-27
JP3340492B2 true JP3340492B2 (en) 2002-11-05

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Country Link
JP (1) JP3340492B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4781622B2 (en) * 2003-09-08 2011-09-28 株式会社クラレ Dispersion stabilizer
CN101663330B (en) 2007-04-16 2012-06-06 可乐丽股份有限公司 Dispersion stabilizer for suspension polymerization
EP3130611B1 (en) * 2014-04-09 2021-09-22 Kuraray Co., Ltd. Dispersion stabilizer for suspension polymerization, and method for producing vinyl resin
TW202005988A (en) * 2018-06-21 2020-02-01 日商可樂麗股份有限公司 Method for producing vinyl-based polymer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH072369Y2 (en) * 1989-09-05 1995-01-25 日野自動車工業株式会社 Truck bed structure
JP2548708Y2 (en) * 1991-10-03 1997-09-24 日本軽金属株式会社 Truck bed

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