JP3619926B2 - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymer Download PDFInfo
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- JP3619926B2 JP3619926B2 JP15161397A JP15161397A JP3619926B2 JP 3619926 B2 JP3619926 B2 JP 3619926B2 JP 15161397 A JP15161397 A JP 15161397A JP 15161397 A JP15161397 A JP 15161397A JP 3619926 B2 JP3619926 B2 JP 3619926B2
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- vinyl chloride
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Description
【0001】
【発明の属する技術分野】
本発明は、成形体におけるフィッシュアイの発生が少ない、塩化ビニル系重合体の製造方法に関するものである。
【0002】
【従来の技術】
塩化ビニル系重合体は、その優れた物理的および機械的性質により広範な分野に使用されているが、最近、その軟質成形において、成形体の耐候性を向上させるために、成形温度を低くすることが要求されている。
【0003】
軟質用の塩化ビニル系重合体としては、通常懸濁重合法により得られた重合体が用いられるが、該重合体中には、成形体におけるフィッシュアイの原因となる難溶融性の重合体粒子(以下、「難溶融性粒子」という)が含まれるため、該難溶融性粒子が溶融する温度条件を用いることにより、成形体におけるフィッシュアイの発生を抑制している。
そのため、難溶融性粒子の含有量の多い塩化ビニル系重合体を使用する場合には、成形温度が高くなるため、その結果、成形体の耐候性が劣るという問題が発生する。従って、軟質塩化ビニル系樹脂用の材料として、低い成形温度での成形が可能な、難溶融性粒子の含有量の少ない塩化ビニル系重合体が求められている。
【0004】
上記難溶融性粒子の含有量の少ない塩化ビニル系重合体の製造方法として、ケン化度が65〜75モル%の高部分ケン化ポリビニルアルコール、ケン化度が35〜45モル%の低部分ケン化ポリビニルアルコールおよびメトキシ基含有率が28〜30モル%でヒドロキシ基の含有量が7〜12モル%のヒドロキシプロピルメチルセルロースの3種類の分散剤を併用する方法(特開昭61−152703号公報)が提案されているが、フィッシュアイの発生を無くするためには、5分間程度の混練時間を必要とするなど、成形体におけるフィッシュアイの改良は十分とはいえない。
また、未反応モノマーを除去する目的で、ケン化度が60モル%以下の油溶性の特殊な部分ケン化ポリビニルアルコールを重合用助剤として使用する方法(特開昭53−43792号公報)が提案されているが、本発明者らが確認した結果、ケン化度が60モル%以下の部分ケン化ポリビニルアルコールを1種類使用しただけでは、成形体におけるフィッシュアイの抑制には十分な効果は見られなかった。
【0005】
【発明が解決しようとする課題】
本発明は、難溶融性粒子の含有量が極めて少なく、そのため短時間の混練時間で、成形体におけるフィッシュアイが極めて少ない塩化ビニル系重合体の製造方法を提供することを目的とする。
【0006】
【課題を解決するための手段】
本発明者らは、鋭意研究を重ねた結果、塩化ビニル系重合体の水性懸濁重合方法において、ケン化度が異なる2種類の低部分ケン化ポリビニルアルコールを分散剤として用いることにより、前記課題が解決できることを見出し、本発明を完成させるに至った。
【0007】
すなわち、本発明は、
塩化ビニル単量体または塩化ビニル単量体およびこれと共重合可能な単量体からなる混合物を分散剤の存在下に水性媒体中で懸濁重合させる塩化ビニル系重合体の製造方法において、
分散剤として
(A)ケン化度が20〜50モル%であり、かつ、水:メチルアルコールが容量比で1:1である混合溶媒に4重量 % となる量溶解した溶液の温度20℃における粘度が2〜7cpsである部分ケン化ポリビニルアルコールと、
(B)ケン化度が前記(A)に比較して10〜20モル%高く、かつ60モル%以下である部分ケン化ポリビニルアルコールを併用すること
を特徴とする塩化ビニル系重合体の製造方法である。
【0008】
【発明の実施の形態】
以下、本発明を詳細に説明する。なお、本発明におけるケン化度および粘度は、いずれも、JIS K 6726(ポリビニルアルコール試験方法)に記載の方法で測定したものである。
【0009】
本発明における塩化ビニル系重合体は、塩化ビニル単量体または塩化ビニル単量体及びこれと共重合可能な単量体からなる混合物(以下、「塩化ビニル系単量体」という)を水性媒体中で懸濁重合させて得られるものであり、塩化ビニル単量体と共重合可能な単量体としては、エチレン、プロピレン、酢酸ビニル、アルキルビニルエーテル、アクリル酸もしくはメタクリル酸およびそのエステル類、マレイン酸もしくはフマール酸およびそのエステル類が挙げられ、これらの単量体は、塩化ビニル単量体100重量部に対して20重量部を超えない範囲で用いることが好ましい。
【0010】
本発明における製造方法は、(A)ケン化度が20〜50モル%、かつ、水:メチルアルコールが容量比で1:1である混合溶媒に4重量 % となる量溶解した溶液の温度20℃における粘度が2〜7cpsの部分ケン化ポリビニルアルコール(以下、単に「PVA」という)と、(B)ケン化度が前記(A)より10〜20モル%高く、かつ60モル%以下であるPVAの2種類を分散剤に用いることを特徴とする。
【0011】
本発明における製造方法において、使用するPVAの合計量は、塩化ビニル系単量体100重量部当たり、0.02〜0.50重量部であることが好ましく、更に好ましくは、0.05〜0.40重量部である。PVAの合計量が0.02重量部未満であるとフィッシュアイの発生が多くなり易く、一方、0.50重量部を越えると得られる重合体粒子が細かくなり易い。
【0012】
さらに、本発明における製造方法において、上記以外の分散剤を併用しても差し支えない。併用できる分散剤としては、例えば、ケン化度60%以上のポリビニルアルコール、メチルセルロース、ヒドロキシプロピルセルロースおよびメチルヒドロキシプロピルセルロース等の水溶性セルロースエーテル類、アクリル酸共重合体、無水マレイン酸共重合体、ゼラチンおよびデン粉等の保護コロイド性の薬剤、天然高分子化合物、高級脂肪酸と多価アルコールとのエステル類、ポリオキシエチレン誘導体等のノニオン界面活性剤、高級脂肪酸の金属塩ならびに高級アルコール硫酸エルテルのアルカリ塩等のアニオン界面活性剤等が挙げられ、上記その他の分散剤は、全分散剤量の80重量%以下であることが好ましい。
【0013】
本発明の製造方法において、全分散剤の使用量は、塩化ビニル系単量体100重量部に対して、0.03〜0.5重量部であることが好適である。分散剤の使用量が0.03重量部未満であると重合体粒子が粗大化し、成形体においてフィッシュアイが発生し易くなり、0.5重量部を超えると得られる重合体粒子が細かくなり、粒子の取扱が困難となる恐れがある。
【0014】
さらに、本発明の製造方法においては、水が媒体として使用されるが、水と塩化ビニル系単量体との割合は、重量比で、水/塩化ビニル系単量体=0.8〜4.0の範囲であることが好ましい。
【0015】
また、本発明において、重合開始剤として、各種のラジカル重合触媒を用いることができる。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、カプロイルパーオキサイド、ターシャリーブチルパーオキシネオデカノエート、ジ(2−エトキシエチル)パーオキシジカーボネート、ターシャリーヘキシルパーオキシネオヘキサノエート、イソブチリルパーオキサイドおよびクミルパーオキシネオデカノエート等の有機過酸化物、2,2’−アゾビスイソブチロニトリルおよび2,2’−アゾビス−ジメチルバレロニトリル等のアゾ化合物あるいはそれらを組み合わせて使用することも可能である。
前記重合開始剤の使用量は、塩化ビニル系単量体100重量部当たり0.02〜0.20重量部が好ましく、より好ましくは0.03〜0.15重量部である。
【0016】
本発明の製造方法においては、重合反応温度は30〜90℃の範囲が好ましく、また、重合時間は2〜15時間が適当である。
【0017】
また、本発明における製造方法において、本発明の目的を損なわない範囲において、他の添加剤を任意に併用することができる。
これらの添加剤として、例えば、アルコール類、脂肪酸塩類、エステル類、緩衝剤、ハイドロタルサイトおよびゼオライト等の塩化水素補足剤等が挙げられる。また、上記添加剤の添加方法については、特に限定されない。
【0018】
【実施例】
以下、実施例によって本発明を更に具体的に説明する。なお、重合体の粒度分布およびフィッシュアイは以下の方法で測定した。
1)粒度分布:ふるい振とう法により測定した。
2)フィッシュアイ:塩化ビニル系重合体100重量部、トリメリット系可塑剤50重量部、2塩基性鉛5重量部およびステアリン酸鉛1重量部を混合後、直径8インチ回転数19/21rpmの2本ロールを、温度170℃に加熱して、0.3mmのロール間隙で4分間混練し、シートを作成し、10cm×10cmの面積中に認められるフィッシュアイの数を数えた。
【0019】
実施例1
内容積5リットルのオートクレーブに、脱イオン水2700g、分散剤として
(A)ケン化度34モル%、かつ容量比で1:1の水−メタノールの混合溶媒に4重量%となる量溶解した溶液の温度20℃における粘度が5cpsのポリビニルアルコール0.3g、
(B)ケン化度52モル%、かつ容量比で1:1の水−メタノールの混合溶媒に4重量%となる量溶解した溶液の温度20℃における粘度が5cpsのポリビニルアルコール0.3g、
(C)ケン化度80モル%、かつ4重量%水溶液の温度20℃における粘度が34cpsのポリビニルアルコール1.2g、クミルパーオキシネオデカノエート0.3gおよびジ(2−エトキシエチル)パーオキシジカーボネート1.0gを仕込み、オートクレーブ内の空気を真空ポンプで除去した。
その後、塩化ビニル単量体1900gを挿入し、攪拌下、温度57℃の条件で重合を8時間行った。
【0020】
実施例2
(A)の代わりに、ケン化度40モル%、かつ容量比で1:1の水−メタノールの混合溶媒に4重量%となる量溶解した溶液の温度20℃における粘度が3cpsのポリビニルアルコール0.3gを用いた以外は実施例1と同様に重合を行った。
【0021】
実施例3
(A)の代わりに、ケン化度40モル%、かつ容量比で1:1の水−メタノールの混合溶媒に4重量%となる量溶解した溶液の温度20℃における粘度が3cpsのポリビニルアルコール0.4g、(B)の代わりに、ケン化度52モル%、かつ容量比で1:1の水−メタノールの混合溶媒に4重量%となる量溶解した溶液の温度20℃における粘度が3cpsのポリビニルアルコール0.2gを用いた以外は、実施例1と同様に重合を行った。
【0022】
比較例1
(A)の代わりに、ケン化度40モル%、かつ容量比で1:1の水−メタノールの混合溶媒に4重量%となる量溶解した溶液の温度20℃における粘度が3cpsのポリビニルアルコール0.6gを添加し、(B)は使用しなかった以外は実施例1と同様に重合を行った。
【0023】
実施例1〜3および比較例の評価
上記実施例1〜3および比較例で得られた重合生成物について、前記の方法により、粒度分布およびフィッシュアイの個数の測定を行った。その結果を後記表1に示す。
【0024】
【表1】
【0025】
【発明の効果】
本発明の製造方法によれば、短時間の混練時間でも、成形体におけるフィッシュアイが極めて少ない塩化ビニル系重合体を得ることができ、得られた塩化ビニル系重合体は軟質塩化ビニル樹脂用に極めて好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a vinyl chloride polymer with less generation of fish eyes in a molded product.
[0002]
[Prior art]
Vinyl chloride polymers have been used in a wide range of fields due to their excellent physical and mechanical properties. Recently, in the soft molding, the molding temperature is lowered to improve the weather resistance of the molded body. It is requested.
[0003]
As the vinyl chloride polymer for softness, a polymer obtained by a suspension polymerization method is usually used, and in the polymer, hardly fusible polymer particles that cause fish eyes in a molded product are used. (Hereinafter referred to as “hardly fusible particles”), the generation of fish eyes in the molded body is suppressed by using the temperature condition at which the hardly fusible particles melt.
For this reason, when a vinyl chloride polymer having a high content of hardly fusible particles is used, the molding temperature becomes high. As a result, there arises a problem that the weather resistance of the molded body is inferior. Therefore, a vinyl chloride polymer having a low content of hardly fusible particles that can be molded at a low molding temperature is demanded as a material for a soft vinyl chloride resin.
[0004]
As a method for producing the vinyl chloride polymer having a low content of hardly fusible particles, a highly partially saponified polyvinyl alcohol having a saponification degree of 65 to 75 mol% and a low partially saponification having a saponification degree of 35 to 45 mol% are used. Of using three types of dispersants, chloropolyvinyl alcohol and hydroxypropyl methylcellulose having a methoxy group content of 28-30 mol% and a hydroxy group content of 7-12 mol% (Japanese Patent Laid-Open No. 61-152703) However, in order to eliminate the generation of fish eyes, improvement of fish eyes in a molded article is not sufficient, for example, a kneading time of about 5 minutes is required.
In addition, for the purpose of removing unreacted monomers, there is a method (JP-A-53-43792) using an oil-soluble specially saponified polyvinyl alcohol having a saponification degree of 60 mol% or less as a polymerization aid. Although it has been proposed, as a result of confirmation by the present inventors, only using one kind of partially saponified polyvinyl alcohol having a saponification degree of 60 mol% or less has a sufficient effect for suppressing fish eyes in a molded article. I couldn't see it.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a vinyl chloride polymer that has a very low content of hardly fusible particles, and therefore, has a short kneading time and extremely little fish eye in a molded product.
[0006]
[Means for Solving the Problems]
As a result of intensive research, the present inventors have used the above-mentioned problems by using two types of low partially saponified polyvinyl alcohols having different saponification degrees as dispersants in an aqueous suspension polymerization method of a vinyl chloride polymer. As a result, the present invention has been completed.
[0007]
That is, the present invention
In a method for producing a vinyl chloride polymer, a suspension comprising a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith in an aqueous medium in the presence of a dispersant,
As a dispersant
(A) The viscosity at a temperature of 20 ° C. of a solution in which a saponification degree is 20 to 50 mol% and water: methyl alcohol is dissolved in an amount of 4 % by weight in a mixed solvent having a volume ratio of 1: 1 is 2 Partially saponified polyvinyl alcohol which is ˜7 cps;
(B) A method for producing a vinyl chloride polymer characterized by using a partially saponified polyvinyl alcohol having a saponification degree of 10 to 20 mol% higher than that of (A) and 60 mol% or less. It is.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. The saponification degree and the viscosity in the present invention are both measured by the method described in JIS K 6726 (Test method for polyvinyl alcohol).
[0009]
The vinyl chloride polymer in the present invention is a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith (hereinafter referred to as “vinyl chloride monomer”) in an aqueous medium. Monomers that can be copolymerized with vinyl chloride monomer include ethylene, propylene, vinyl acetate, alkyl vinyl ether, acrylic acid or methacrylic acid and esters thereof, maleic Examples thereof include acid or fumaric acid and esters thereof, and these monomers are preferably used in an amount not exceeding 20 parts by weight with respect to 100 parts by weight of the vinyl chloride monomer.
[0010]
The production method according to the present invention is as follows: (A) The temperature of a solution in which a saponification degree is 20 to 50 mol% and dissolved in an amount of 4 % by weight in a mixed solvent in which water: methyl alcohol has a volume ratio of 1: 1 is 20 Partially saponified polyvinyl alcohol (hereinafter simply referred to as “PVA”) having a viscosity at 2 ° C. of 2 to 7 cps, and (B) the saponification degree is 10 to 20 mol% higher than (A) and 60 mol% or less. Two types of PVA are used as a dispersant.
[0011]
In the production method of the present invention, the total amount of PVA to be used is preferably 0.02 to 0.50 parts by weight, more preferably 0.05 to 0 parts per 100 parts by weight of the vinyl chloride monomer. 40 parts by weight. If the total amount of PVA is less than 0.02 parts by weight, the generation of fish eyes tends to increase, whereas if it exceeds 0.50 parts by weight, the resulting polymer particles tend to be fine.
[0012]
Furthermore, in the production method of the present invention, a dispersant other than the above may be used in combination. Examples of the dispersant that can be used in combination include polyvinyl alcohol having a saponification degree of 60% or more, water-soluble cellulose ethers such as methyl cellulose, hydroxypropyl cellulose, and methylhydroxypropyl cellulose, acrylic acid copolymers, maleic anhydride copolymers, Protective colloidal drugs such as gelatin and den powder, natural polymer compounds, esters of higher fatty acids and polyhydric alcohols, nonionic surfactants such as polyoxyethylene derivatives, metal salts of higher fatty acids and higher alcohol sulfates Examples thereof include an anionic surfactant such as an alkali salt, and the other dispersant is preferably 80% by weight or less of the total amount of the dispersant.
[0013]
In the production method of the present invention, the amount of the total dispersant used is preferably 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the vinyl chloride monomer. When the amount of the dispersant used is less than 0.03 parts by weight, the polymer particles are coarsened, and fish eyes are easily generated in the molded body. When the amount exceeds 0.5 parts by weight, the polymer particles obtained are fine, Particle handling may be difficult.
[0014]
Furthermore, in the production method of the present invention, water is used as a medium, but the ratio of water to the vinyl chloride monomer is, by weight, water / vinyl chloride monomer = 0.8-4. A range of 0.0 is preferable.
[0015]
In the present invention, various radical polymerization catalysts can be used as the polymerization initiator. For example, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, tertiary butyl peroxyneodecanoate, di (2-ethoxyethyl) peroxydicarbonate, tertiary hexyl peroxyneohexanoate, isobutyryl per Use organic peroxides such as oxide and cumylperoxyneodecanoate, azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-dimethylvaleronitrile, or combinations thereof. Is also possible.
The amount of the polymerization initiator used is preferably 0.02 to 0.20 parts by weight, more preferably 0.03 to 0.15 parts by weight, per 100 parts by weight of the vinyl chloride monomer.
[0016]
In the production method of the present invention, the polymerization reaction temperature is preferably in the range of 30 to 90 ° C., and the polymerization time is suitably 2 to 15 hours.
[0017]
Moreover, in the manufacturing method in this invention, in the range which does not impair the objective of this invention, another additive can be used together arbitrarily.
Examples of these additives include alcohols, fatty acid salts, esters, buffering agents, hydrogen chloride scavengers such as hydrotalcite and zeolite, and the like. Moreover, it does not specifically limit about the addition method of the said additive.
[0018]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. The particle size distribution and fish eye of the polymer were measured by the following methods.
1) Particle size distribution: measured by a sieve shaking method.
2) Fisheye: After mixing 100 parts by weight of vinyl chloride polymer, 50 parts by weight of trimellitic plasticizer, 5 parts by weight of basic lead and 1 part by weight of lead stearate, the diameter is 8 inches and the rotational speed is 19/21 rpm. The two rolls were heated to a temperature of 170 ° C. and kneaded for 4 minutes with a roll gap of 0.3 mm to prepare a sheet, and the number of fish eyes found in an area of 10 cm × 10 cm was counted.
[0019]
Example 1
The content volume of 5 liter autoclave, deionized water 2700 g, (A) a saponification degree 34 mol% as a dispersing agent, and a volume ratio of 1: 1 water - solution amount dissolved as a 4% by weight in a mixed solvent of methanol 0.3 g of polyvinyl alcohol having a viscosity of 5 cps at a temperature of 20 ° C.
(B) Polyvinyl alcohol 0.3 g having a viscosity of 5 cps at a temperature of 20 ° C. of a solution dissolved in an amount of 4% by weight in a water-methanol mixed solvent having a saponification degree of 52 mol% and a volume ratio of 1: 1,
(C) a saponification degree 80 mol%, and 4 wt% Temperature 20 viscosity at ℃ is 34cps polyvinyl alcohol 1.2g of an aqueous solution, cumyl peroxyneodecanoate 0.3g and di (2-ethoxyethyl) peroxy 1.0 g of dicarbonate was charged, and the air in the autoclave was removed with a vacuum pump.
Thereafter, 1900 g of vinyl chloride monomer was inserted, and polymerization was carried out for 8 hours under stirring at a temperature of 57 ° C.
[0020]
Example 2
Instead of (A), a polyvinyl alcohol having a viscosity of 3 cps at a temperature of 20 ° C. in a solution of 4 mol% in a water-methanol mixed solvent having a saponification degree of 40 mol% and a volume ratio of 1: 1 was obtained. Polymerization was carried out in the same manner as in Example 1 except that 3 g was used.
[0021]
Example 3
Instead of (A), 1 in saponification degree 40 mol%, and volume ratio: 1 water - Polyvinyl alcohol 0 viscosity of 3cps at mixing temperature 20 ° C. of the solvent to 4% by weight and comprising an amount dissolved solution of methanol .4 g, instead of (B), a viscosity of 3 cps at a temperature of 20 ° C. of a solution dissolved in an amount of 4% by weight in a water-methanol mixed solvent having a saponification degree of 52 mol% and a volume ratio of 1: 1 Polymerization was performed in the same manner as in Example 1 except that 0.2 g of polyvinyl alcohol was used.
[0022]
Comparative Example 1
Instead of (A), a polyvinyl alcohol having a viscosity of 3 cps at a temperature of 20 ° C. in a solution of 4 mol% in a water-methanol mixed solvent having a saponification degree of 40 mol% and a volume ratio of 1: 1 was obtained. Polymerization was carried out in the same manner as in Example 1 except that .6 g was added and (B) was not used.
[0023]
Evaluation of Examples 1 to 3 and Comparative Examples For the polymerization products obtained in Examples 1 to 3 and Comparative Examples, the particle size distribution and the number of fish eyes were measured by the methods described above. The results are shown in Table 1 below.
[0024]
[Table 1]
[0025]
【The invention's effect】
According to the production method of the present invention, it is possible to obtain a vinyl chloride polymer having very little fish eye in a molded product even in a short kneading time, and the obtained vinyl chloride polymer is used for a soft vinyl chloride resin. Very suitable.
Claims (1)
分散剤として
(A)ケン化度が20〜50モル%であり、かつ、水:メチルアルコールが容量比で1:1である混合溶媒に4重量 % となる量溶解した溶液の温度20℃における粘度が2〜7cpsである部分ケン化ポリビニルアルコールと、
(B)ケン化度が前記(A)に比較して10〜20モル%高く、かつ60モル%以下である部分ケン化ポリビニルアルコールを併用すること
を特徴とする塩化ビニル系重合体の製造方法。In a method for producing a vinyl chloride polymer, a suspension comprising a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith in an aqueous medium in the presence of a dispersant,
As a dispersant
(A) The viscosity at a temperature of 20 ° C. of a solution in which a saponification degree is 20 to 50 mol% and water: methyl alcohol is dissolved in an amount of 4 % by weight in a mixed solvent having a volume ratio of 1: 1 is 2 Partially saponified polyvinyl alcohol which is ˜7 cps;
(B) a degree of saponification of the (A) 10 to 20 mol% higher than that, and is partially saponified be used together polyvinyl alcohol you wherein the vinyl chloride polymer is 60 mol% or less Production method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15161397A JP3619926B2 (en) | 1997-05-26 | 1997-05-26 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP15161397A JP3619926B2 (en) | 1997-05-26 | 1997-05-26 | Method for producing vinyl chloride polymer |
Publications (2)
Publication Number | Publication Date |
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JPH10324705A JPH10324705A (en) | 1998-12-08 |
JP3619926B2 true JP3619926B2 (en) | 2005-02-16 |
Family
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Application Number | Title | Priority Date | Filing Date |
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JP15161397A Expired - Lifetime JP3619926B2 (en) | 1997-05-26 | 1997-05-26 | Method for producing vinyl chloride polymer |
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JP (1) | JP3619926B2 (en) |
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1997
- 1997-05-26 JP JP15161397A patent/JP3619926B2/en not_active Expired - Lifetime
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JPH10324705A (en) | 1998-12-08 |
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