JP2938635B2 - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymerInfo
- Publication number
- JP2938635B2 JP2938635B2 JP26900291A JP26900291A JP2938635B2 JP 2938635 B2 JP2938635 B2 JP 2938635B2 JP 26900291 A JP26900291 A JP 26900291A JP 26900291 A JP26900291 A JP 26900291A JP 2938635 B2 JP2938635 B2 JP 2938635B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- weight
- vinyl chloride
- amount
- degree
- 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
Links
Landscapes
- Polymerisation Methods In General (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は塩化ビニル系重合体の製
造方法、とくには嵩比重が高くフィシュアイの少ない成
形品を得ることができる塩化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 method for producing a vinyl chloride polymer, and more particularly to a method for producing a vinyl chloride polymer capable of obtaining a molded article having a high bulk specific gravity and a small fisheye.
【０００２】[0002]
【従来の技術】塩化ビニル系重合体は物理的性質に優れ
た有用な樹脂で、硬質および軟質の材料として広く利用
されている。この塩化ビニル系重合体の成形法として
は、カレンダー成形、押出成形、射出成形などの方法が
一般に採用されているが、とくに近年、硬質押出成形に
おいて成形機の押出量を増大させるために、嵩比重の高
い塩化ビニル系重合体の開発が要望されてきている。2. Description of the Related Art Vinyl chloride polymers are useful resins having excellent physical properties and are widely used as hard and soft materials. As a method for molding the vinyl chloride polymer, methods such as calender molding, extrusion molding, and injection molding are generally employed. In particular, in recent years, in order to increase the extrusion amount of a molding machine in hard extrusion molding, bulk molding is performed. Development of a vinyl chloride polymer having a high specific gravity has been demanded.
【０００３】これまでに提案された水性媒体中での懸濁
重合による嵩比重の高い塩化ビニル系重合体の製造法に
は、単量体を重合の途中で追加する方法（特開昭59 -16
8008号公報）、高ケン化度ポリビニルアルコールを使用
する方法（特開昭57 -7600号公報）、懸濁剤を重合途中
で追加する方法（特願平1-207624号公報）等が知られて
いる。A method for producing a vinyl chloride polymer having a high bulk specific gravity by suspension polymerization in an aqueous medium has been proposed so far, in which a monomer is added during the polymerization (JP-A-59-5959). 16
No. 8008), a method using polyvinyl alcohol having a high degree of saponification (Japanese Patent Laid-Open No. 57-7600), a method of adding a suspending agent during polymerization (Japanese Patent Application No. 1-207624), and the like. ing.
【０００４】しかし、上記特開昭59 -168008号または同
57 -7600号公報に記載の方法によれば、ある程度嵩比重
の高い重合体が得られるものの、成形時にフィシュアイ
の生じない重合体とするのに必要なポロシティをも向上
させることは困難であった。However, Japanese Patent Laid-Open No. Sho 59-168008 or
According to the method described in JP-A-57-7600, although a polymer having a relatively high bulk specific gravity can be obtained, it is difficult to improve the porosity necessary for obtaining a polymer that does not generate fish eyes during molding. Was.
【０００５】この問題を解決するため、分散剤としてカ
ルボキシル基を含む水不溶性の架橋重合体と非イオン系
界面活性剤とを使用する方法が提案され（公表特許昭57
-500614 号、同57-500650 号、特開昭61-91205号、同61
-14204号各公報など）、実際に特開昭61-91205号および
同61-14204号公報に記載の方法では嵩比重が高く、ポロ
シティの向上した重合体が得られているが、これらの方
法において生産性向上のために単量体の仕込み量を増加
させたり重合時間を短縮したりすると、重合反応が不安
定となり、塊状の重合体が生成して嵩比重、粒度分布、
成形時のフィシュアイなどの点で十分満足できる高品質
の塩化ビニル系重合体が得られなくなっていた。In order to solve this problem, a method has been proposed in which a water-insoluble crosslinked polymer containing a carboxyl group and a nonionic surfactant are used as a dispersant (Japanese Patent Application Laid-Open No. SHO 57-57).
-500614, 57-500650, JP-A-61-91205, 61
-14204), and in fact, in the methods described in JP-A-61-91205 and JP-A-61-14204, polymers having high bulk specific gravity and improved porosity have been obtained. In the case of increasing the amount of charged monomers or shortening the polymerization time in order to improve productivity, the polymerization reaction becomes unstable, a bulk polymer is formed and the bulk specific gravity, the particle size distribution,
A high-quality vinyl chloride polymer which is sufficiently satisfactory in terms of fisheye during molding cannot be obtained.
【０００６】[0006]
【発明が解決しようとする課題】したがって、本発明の
目的は嵩比重が高く成形品のフィシュアイを有効に抑制
することのできるポロシティの高い、高品質の塩化ビニ
ル系重合体を、高い生産効率のもとで得ることのできる
製造方法を提供するにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-porosity, high-quality vinyl chloride-based polymer having a high bulk specific gravity and capable of effectively suppressing fisheye of a molded article, with a high production efficiency. To provide a production method that can be obtained under the following conditions.
【０００７】[0007]
【課題を解決するための手段】本発明は、特定の部分ケ
ン化ポリビニルアルコールとヒドロキシプロピルメチル
セルロースとからなる分散安定剤を用いて塩化ビニル系
単量体を水性媒体中に懸濁分散させると共に、重合開始
後、一定のタイミングで一定量の塩化ビニル系単量体を
追加添加すると共に、一定の段階まで重合反応を継続さ
せるという手段を採用することによって上記課題を解決
したものである。According to the present invention, a vinyl chloride monomer is suspended and dispersed in an aqueous medium using a dispersion stabilizer comprising a specific partially saponified polyvinyl alcohol and hydroxypropylmethylcellulose. This problem has been solved by adding a certain amount of a vinyl chloride-based monomer at a certain timing after the start of the polymerization and by employing means for continuing the polymerization reaction to a certain stage.
【０００８】すなわち本発明の塩化ビニル系重合体の製
造方法は、塩化ビニル系単量体と油溶性重合開始剤とを
分散安定剤の存在下に水性媒体中で懸濁重合するに際
し、前記分散安定剤として（Ａ）平均重合度が1500〜27
00、ケン化度が75〜99モル％の部分ケン化ポリビニルア
ルコールと（Ｂ）メトキシ置換度が26〜30重量％、ヒド
ロキシプロポキシ置換度が４〜15重量％で、その２重量
％水溶液の20℃における粘度が５〜 4000cpsであるヒド
ロキシプロピルメチルセルロースとを、合わせて塩化ビ
ニル系単量体の全仕込み量 100重量部当り0.03〜0.15重
量部用いると共に、さらに（Ｃ）平均重合度が 150〜 6
00、ケン化度が20〜55モル％の部分ケン化ポリビニルア
ルコールを、塩化ビニル系単量体の全仕込み量 100重量
部当り0.03〜0.15重量部で、（Ａ）、（Ｂ）両成分の１
〜５重量倍使用し、重合温度を54℃以上に保って重合を
開始した後、重合転化率が10〜60％に達した時点で、さ
らに当初の仕込み単量体の10〜20重量％に相当する量の
単量体を添加し、当初の仕込み単量体量の90％が重合転
化する段階まで重合反応を続けることを特徴とするもの
である。That is, the method for producing a vinyl chloride polymer according to the present invention is characterized in that when the vinyl chloride monomer and an oil-soluble polymerization initiator are subjected to suspension polymerization in an aqueous medium in the presence of a dispersion stabilizer, (A) As a stabilizer, the average degree of polymerization is 1500 to 27
A partially saponified polyvinyl alcohol having a degree of saponification of 75 to 99 mol% and (B) a methoxy substitution degree of 26 to 30% by weight, a hydroxypropoxy substitution degree of 4 to 15% by weight, and a 2% by weight aqueous solution of 20% Hydroxypropyl methylcellulose having a viscosity at 5 ° C. of 5 to 4000 cps is used in an amount of 0.03 to 0.15 part by weight per 100 parts by weight of the total amount of the vinyl chloride monomer, and (C) the average degree of polymerization is 150 to 6
A partially saponified polyvinyl alcohol having a degree of saponification of 20 to 55 mol% is used in an amount of 0.03 to 0.15 parts by weight per 100 parts by weight of the total charged amount of the vinyl chloride monomer. 1
After starting polymerization by maintaining the polymerization temperature at 54 ° C. or more, when the polymerization conversion reaches 10 to 60%, it is further reduced to 10 to 20% by weight of the initially charged monomer. It is characterized in that a corresponding amount of monomer is added, and the polymerization reaction is continued until a stage at which 90% of the initially charged monomer amount undergoes polymerization conversion.
【０００９】以下、本発明をさらに詳細に説明する。本
発明において塩化ビニル系単量体を水性媒体中に懸濁分
散させるために使用される分散安定剤は、上述した
（Ａ）、（Ｃ）２種の部分ケン化ポリビニルアルコール
と（Ｂ）のヒドロキシプロピルメチルセルロースとから
なる。Hereinafter, the present invention will be described in more detail. In the present invention, the dispersion stabilizer used for suspending and dispersing the vinyl chloride-based monomer in an aqueous medium includes the above-mentioned (A) and (C) two kinds of partially saponified polyvinyl alcohols and (B). And hydroxypropyl methylcellulose.
【００１０】この分散安定剤は（Ａ）部分ケン化ポリビ
ニルアルコールと（Ｂ）ヒドロキシプロピルメチルセル
ロースとの合計量として、塩化ビニル系単量体の全仕込
み量100重量部当り0.03〜0.15重量部の割合で使用され
る。この（Ａ）、（Ｂ）両成分の使用割合は、重量基準
でＡ／Ｂ＝９／１〜１／10の範囲とするのが好適であ
る。（Ａ）成分の使用量が上記範囲よりも多いとフィシ
ュアイが多くなり、また上記範囲よりも少ないと嵩比重
向上の効果が得られず、得られる重合体の粒度分布が広
くなるので好ましくない。This dispersion stabilizer has a ratio of 0.03 to 0.15 parts by weight per 100 parts by weight of the total charged amount of the vinyl chloride monomer, as the total amount of (A) partially saponified polyvinyl alcohol and (B) hydroxypropylmethylcellulose. Used in. It is preferable that the use ratio of both components (A) and (B) is in the range of A / B = 9/1 to 1/10 on a weight basis. When the amount of the component (A) is more than the above range, fish eyes are increased, and when the amount is less than the above range, the effect of improving the bulk specific gravity is not obtained, and the particle size distribution of the obtained polymer is unpreferably wide. .
【００１１】（Ｃ）の部分ケン化ポリビニルアルコール
は（Ａ）、（Ｂ）両成分の使用量に対し重量基準で１〜
５倍の範囲内で、また塩化ビニル系単量体の全仕込み量
100重量部当り0.03〜0.15重量部の割合で使用される。The partially saponified polyvinyl alcohol (C) is used in an amount of 1 to 3 based on the weight of both components (A) and (B).
Within 5 times the total amount of vinyl chloride monomer charged
It is used at a ratio of 0.03 to 0.15 parts by weight per 100 parts by weight.
【００１２】（Ａ）成分としての部分ケン化ポリビニル
アルコールは、平均重合度が1500〜2700、ケン化度が75
〜99モル％のものであることが必要とされ、その平均重
合度が1500より低いかケン化度が75モル％より低いと、
嵩比重向上の効果が得られず、得られる重合体の粒度分
布が広くなって、粗粒化したりフィシュアイが増大した
りするようになる。また平均重合度が2700よりも高いか
ケン化度が99モル％を超えると、同様にフィシュアイが
増大する。The partially saponified polyvinyl alcohol as the component (A) has an average degree of polymerization of 1500 to 2700 and a degree of saponification of 75.
~ 99 mol%, if its average degree of polymerization is lower than 1500 or the degree of saponification is lower than 75 mol%,
The effect of improving the bulk specific gravity cannot be obtained, and the particle size distribution of the obtained polymer is widened, resulting in coarsening and an increase in fish eyes. When the average degree of polymerization is higher than 2700 or the degree of saponification exceeds 99 mol%, fish eyes similarly increase.
【００１３】（Ｂ）成分としてのヒドロキシプロピルメ
チルセルロースは、メトキシ置換度が26〜30重量％、ヒ
ドロキシプロポキシ置換度が４〜15重量％で、その２重
量％水溶液の20℃における粘度が５〜 4000cps、好まし
くは５〜100cpsのものであることが必要とされ、このメ
トキシ置換度が26重量％より低いかヒドロキシプロポキ
シ置換度が４重量％より低いと、同様にフィッシュアイ
が増大し、またメトキシ置換度が30重量％より高いかヒ
ドロキシブロポキシ置換度が15重量％を超えると、得ら
れる重合体粒子の粒度分布が広くなる。The hydroxypropylmethylcellulose as the component (B) has a degree of methoxy substitution of 26 to 30% by weight, a degree of hydroxypropoxy substitution of 4 to 15% by weight, and a 2% by weight aqueous solution having a viscosity at 20 ° C. of 5 to 4000 cps. If the degree of methoxy substitution is lower than 26% by weight or the degree of hydroxypropoxy substitution is lower than 4% by weight, the fish eye is increased and the methoxy substitution is also required. If the degree is higher than 30% by weight or the degree of hydroxypropoxy substitution exceeds 15% by weight, the particle size distribution of the obtained polymer particles becomes broad.
【００１４】（Ｃ）成分としての部分ケン化ポリビニル
アルコールは、平均重合度が 150〜600、ケン化度が20
〜55モル％のものであることが必要とされ、この平均重
合度が150 よりも低いかケン化度が20モル％より小さい
と、得られる重合体粒子の粒度分布が広くなって粗粒化
したり重合器内にスケールが付着したりする。また平均
重合度が 600を超えるかケン化度が55モル％より高くな
ると、重合体成形品のフィッシュアイが増加する。The partially saponified polyvinyl alcohol as the component (C) has an average degree of polymerization of 150 to 600 and a degree of saponification of 20.
If the average degree of polymerization is less than 150 or the degree of saponification is less than 20% by mole, the resulting polymer particles have a broad particle size distribution and coarse particles. Or scale adheres in the polymerization vessel. On the other hand, when the average degree of polymerization exceeds 600 or the degree of saponification is higher than 55 mol%, fish eyes of the polymer molded article increase.
【００１５】これら分散安定剤の重合系への仕込み方法
は、（Ａ）、（Ｂ）両成分のように水溶性のものでは水
に溶かして添加するのが好ましく、（Ｃ）成分のような
低ケン化度の部分ケン化ポリビニルアルコールでは、そ
のまま直接添加する方法、メタノール、アセトン、酢酸
メチル、酢酸エチル等の溶剤または水／メタノール等の
混合溶媒に溶解して添加する方法、水性エマルジョンと
して添加する方法など任意に選択することができる。As for the method of charging these dispersion stabilizers into the polymerization system, it is preferable to add them by dissolving them in water if they are water-soluble such as the components (A) and (B). In the case of partially saponified polyvinyl alcohol with a low degree of saponification, a method of directly adding it, a method of dissolving it in a solvent such as methanol, acetone, methyl acetate, ethyl acetate or a mixed solvent such as water / methanol, and adding it as an aqueous emulsion The method can be arbitrarily selected.
【００１６】本発明の方法ではまた、重合温度を54℃以
上に保って重合を開始した後、重合転化率が10〜60％、
好ましくは30〜60％に達した時点で、さらに当初の仕込
み単量体の10〜20重量％に相当する量の単量体を添加す
るのであるが、このとき重合転化率が上記範囲外では嵩
比重向上の効果が得られず、重合体成形品のフィッシュ
アイが増大する傾向となる。Further, in the method of the present invention, after the polymerization is started while maintaining the polymerization temperature at 54 ° C. or higher, the polymerization conversion is 10 to 60%,
Preferably, when the amount reaches 30 to 60%, a monomer equivalent to 10 to 20% by weight of the initially charged monomer is further added. The effect of improving the bulk specific gravity cannot be obtained, and the fish eye of the polymer molded article tends to increase.
【００１７】また、添加量が仕込み単量体の10重量％未
満のときも同様に嵩比重向上の効果が得られず、これが
20重量％を超えると可塑剤吸収性が低下するので好まし
くない。この単量体の添加方法は上記重合転化率の間に
連続的あるいは間けつ的に添加しても、また一括して添
加してもよい。なお、重合転化率は重合を開始してから
の経過時間によって、ほぼ正確に推定することができ
る。Also, when the added amount is less than 10% by weight of the charged monomer, the effect of improving the bulk specific gravity cannot be obtained similarly.
If it exceeds 20% by weight, the plasticizer absorbability decreases, which is not preferable. Regarding the method of adding the monomer, the monomer may be added continuously or intermittently during the polymerization conversion rate, or may be added all at once. The polymerization conversion can be estimated almost exactly by the elapsed time from the start of the polymerization.
【００１８】なお、本発明の重合系で使用される水性媒
体の量としては、当初の仕込み単量体 100重量部に対し
100〜 150重量部であることが好ましく、これが 100重
量部未満では懸濁系が不安定となって粗粒が発生し易く
なり、 150重量部を超えると重合器中に仕込める単量体
の量が相対的に減少して生産性が向上せず経済性が失わ
れる。The amount of the aqueous medium used in the polymerization system of the present invention is based on 100 parts by weight of the initially charged monomer.
When the amount is less than 100 parts by weight, the suspension system becomes unstable and coarse particles are easily generated.When the amount exceeds 150 parts by weight, the amount of the monomer charged in the polymerization vessel is increased. The volume is relatively reduced, productivity is not improved and economics are lost.
【００１９】前述したように、反応系の重合温度は54℃
以上、好ましくは54〜65℃、さらに好ましくは57〜63℃
であることが必要で、54℃未満では同様に嵩比重向上の
効果が得にくくなる。As described above, the polymerization temperature of the reaction system is 54 ° C.
Above, preferably 54-65 ° C, more preferably 57-63 ° C
When the temperature is lower than 54 ° C., the effect of improving the bulk specific gravity similarly becomes difficult to obtain.
【００２０】本発明の方法による重合反応は、当初の仕
込み単量体量の90％、好ましくは90〜 115％が重合転化
する段階まで続ける必要があり、これを90％未満で停止
させると嵩比重向上の効果が得られない。The polymerization reaction according to the method of the present invention needs to be continued until the stage of polymerization conversion of 90%, preferably 90 to 115%, of the initially charged monomer amount. The effect of improving specific gravity cannot be obtained.
【００２１】本発明の方法で重合される塩化ビニル系単
量体としては、塩化ビニル単独のほか、塩化ビニルを主
体とするこれと共重合可能なビニル系単量体の混合物
（通常塩化ビニルが50重量％以上）が包含される。この
塩化ビニルと共重合されるコモノマーとしては、エチレ
ン、プロピレン、１−ブテン、１−ペンテン、１−ヘキ
セン、１−ヘプテン、１−オクテン、１−ノネン、１−
デセン、１−ウンデセン、１−ドデセン、１−トリデセ
ン、１−テトラデセンなどのα−オレフィン；アクリル
酸、アクリル酸メチル、アクリル酸エチルなどのアクリ
ル酸またはそのエステル；メタクリル酸、メタクリル酸
メチルなどのメタクリル酸またはそのエステル；マレイ
ン酸またはそのエステル；酢酸ビニル、プロピオン酸ビ
ニルなどのビニルエステル；ラウリルビニルエーテル、
イソブチルビニルエーテルなどのビニルエーテル；無水
マレイン酸；アクリロニトリル；スチレン；塩化ビニリ
デン；その他塩化ビニルと共重合可能な単量体などが挙
げられ、これらは単独または２種以上の組合せで用いら
れる。Examples of the vinyl chloride monomer polymerized by the method of the present invention include not only vinyl chloride alone but also a mixture of a vinyl monomer mainly composed of vinyl chloride and copolymerizable therewith (usually vinyl chloride is used). 50% by weight or more). Comonomers copolymerized with this vinyl chloride include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
Α-olefins such as decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene; acrylic acid such as acrylic acid, methyl acrylate, and ethyl acrylate or esters thereof; methacrylic acid such as methacrylic acid and methyl methacrylate Acids or esters thereof; maleic acid or esters thereof; vinyl esters such as vinyl acetate and vinyl propionate; lauryl vinyl ether;
Vinyl ethers such as isobutyl vinyl ether; maleic anhydride; acrylonitrile; styrene; vinylidene chloride; and other monomers copolymerizable with vinyl chloride. These may be used alone or in combination of two or more.
【００２２】本発明において用いられる重合開始剤は従
来塩化ビニル系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、ｔ−ブチルパーオキシピバレート、ｔ−ヘキ
シルパーオキシピバレ−ト、α−クミルパーオキシネオ
デカネート、２, ４, ４−トリメチルペンチル−２−パ
ーオキシ−２−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、３, ５, ５−トリメチルヘキサノイ
ルパーオキシド、ラウロイルパーオキシドなどの過酸化
物；アゾビス−２, ４−ジメチルバレロニトリル、アゾ
ビス（４−メトキシ−２, ４−ジメチルバレロニトリ
ル）などのアゾ化合物等を、単独または２種以上の組み
合わせで使用することができる。また、これらの油溶性
触媒には過硫酸カリウム、過硫酸アンモニウム、過酸化
水素、キュメンハイドロパーオキシド等の水溶性触媒
を、単独または２種以上の組み合わせで併用することも
できる。The polymerization initiator used in the present invention may be any of those conventionally used for vinyl chloride polymerization, such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxy. Percarbonate compounds such as ethyl peroxydicarbonate; t-butylperoxyneodecanate, t-butylperoxypivalate, t-hexylperoxypivalate, α-cumylperoxyneodecanate, 2,4 Perester compounds such as, 4-trimethylpentyl-2-peroxy-2-neodecanate; acetylcyclohexylsulfonyl peroxide;
Peroxides such as 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, 3,5,5-trimethylhexanoyl peroxide and lauroyl peroxide; azobis-2,4-dimethylvaleronitrile, azobis (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile) and the like can be used alone or in combination of two or more. Water-soluble catalysts such as potassium persulfate, ammonium persulfate, hydrogen peroxide and cumene hydroperoxide can be used alone or in combination of two or more of these oil-soluble catalysts.
【００２３】これら重合開始剤の添加量は塩化ビニル系
単量体の全仕込み量 100重量部に対して0.01〜 0.3重量
部が好ましい。この添加方法は通常実施されている方法
でよく、そのまま直接重合器内に投入するか、分散剤を
用いてエマルジョンにして投入するなど、とくに制限さ
れるものではない。The amount of the polymerization initiator to be added is preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the total charged amount of the vinyl chloride monomer. This addition method may be a commonly used method, and is not particularly limited, for example, it may be directly charged into the polymerization vessel as it is, or may be charged as an emulsion using a dispersant.
【００２４】本発明の塩化ビニル系重合体の製造方法
は、前述したように（Ａ）、（Ｂ）、（Ｃ）３種類の分
散安定剤を使用すると共に、一定量の単量体を一定のタ
イミングで添加し、一定の重合転化率のときに反応を終
了させることを除けば、従来公知の方法で行われる。す
なわち、重合器への水性媒体、塩化ビニル単量体、場合
によっては他のコモノマー、分散助剤、重合開始剤など
の仕込み方法などは従来と同様に行えばよい。The process for producing a vinyl chloride polymer of the present invention uses the three types of dispersion stabilizers (A), (B) and (C) as described above, The reaction is carried out by a conventionally known method except that the reaction is terminated at a certain polymerization conversion rate. That is, the method of charging the polymerization vessel with the aqueous medium, the vinyl chloride monomer, and optionally other comonomers, dispersing aids, polymerization initiators, and the like may be performed in the same manner as in the related art.
【００２５】さらにこの重合系には、必要に応じて、塩
化ビニル系の重合に適宜使用される重合調整剤、連鎖移
動剤、ｐＨ調整剤、ゲル化改良剤、帯電防止剤、架橋
剤、安定剤、充てん剤、酸化防止剤、緩衝剤、スケール
防止剤などを添加することも任意である。The polymerization system may further include, if necessary, a polymerization regulator, a chain transfer agent, a pH regulator, a gelling improver, an antistatic agent, a crosslinking agent, and a stabilizer which are appropriately used in vinyl chloride polymerization. It is also optional to add agents, fillers, antioxidants, buffers, scale inhibitors and the like.
【００２６】[0026]
【実施例】以下、本発明の具体的態様を実施例により説
明するが、本発明はこれらの記載に限定されるものでは
ない。EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to examples, but the present invention is not limited to these descriptions.
【００２７】実験 No.１ 撹拌器およびジャッケット付きの内容積2000Ｌのステン
レス製重合器に、脱イオン水 900kg、ジ−２−エチルヘ
キシルパーオキシジカーボネート 400ｇ、分散安定剤と
して（Ａ）平均重合度2600、ケン化度80.2モル％の部分
ケン化ポリビニルアルコール 105ｇ、（Ｂ）メトキシ置
換度29.2重量％、ヒドロキシプロポキシ置換度 8.9重量
％で、その２重量％水溶液の20℃における粘度が49.5cp
sのヒドロキシプロピルメチルセルロース 245ｇおよび
（Ｃ）平均重合度 235、ケン化度48モル％の部分ケン化
ポリビニルアルコール350ｇを、（Ａ）、（Ｂ）は６％
水溶液として、（Ｃ）は水／メタノール＝１／１の30重
量％溶液として、それぞれ仕込んだ。次いで重合器内圧
が50mmHgになるまで脱気した後、塩化ビニル 700kgを仕
込んだ。Experiment No. 1 900 kg of deionized water, 400 g of di-2-ethylhexyl peroxydicarbonate, and a dispersion stabilizer (A) having an average degree of polymerization of 2600 were placed in a 2000 L stainless steel polymerization vessel equipped with a stirrer and a jacket. 105 g of partially saponified polyvinyl alcohol having a saponification degree of 80.2 mol%, (B) a degree of methoxy substitution of 29.2% by weight, a degree of hydroxypropoxy substitution of 8.9% by weight, and a 2% by weight aqueous solution having a viscosity at 20 ° C. of 49.5 cp.
245 g of hydroxypropyl methylcellulose and 350 g of partially saponified polyvinyl alcohol (C) having an average degree of polymerization of 235 and a degree of saponification of 48 mol%, (A) and (B) being 6%
As an aqueous solution, (C) was charged as a 30% by weight solution of water / methanol = 1/1. Next, after degassing until the internal pressure of the polymerization reactor became 50 mmHg, 700 kg of vinyl chloride was charged.
【００２８】撹拌しながらジャッケットに熱水を通じて
57℃まで昇温させた後、この温度を保ちながら重合させ
た。その後、重合転化率が40％に達した時点で、塩化ビ
ニル単量体 105kgを追加・圧入して重合を続けた。重合
器内圧が 6.0kg/cm2・Gに低下した時点で未反応単量体を
回収した後、反応混合物であるスラリーを重合器内から
取り出し、脱水・乾燥して重合体を得た。Pass hot water into the jacket while stirring
After the temperature was raised to 57 ° C., polymerization was carried out while maintaining this temperature. Thereafter, when the polymerization conversion reached 40%, 105 kg of a vinyl chloride monomer was added and injected, and the polymerization was continued. After the unreacted monomer was recovered when the internal pressure of the polymerization reactor dropped to 6.0 kg / cm 2 · G, the slurry as the reaction mixture was taken out of the polymerization reactor, dehydrated and dried to obtain a polymer.
【００２９】実験 No.２ 実験 No.１において、重合温度を49℃に変えたほかは同
様にして重合体を得た。Experiment No. 2 A polymer was obtained in the same manner as in Experiment No. 1, except that the polymerization temperature was changed to 49 ° C.
【００３０】実験 No.３ 実験 No.１において、塩化ビニル単量体の重合中での追
加を行わなかったほかは同様にして重合体を得た。Experiment No. 3 A polymer was obtained in the same manner as in Experiment No. 1 except that the vinyl chloride monomer was not added during the polymerization.
【００３１】実験 No.４ 実験 No.１において、塩化ビニル単量体の重合中での追
加量を 210kgとしたほかは同様にして重合体を得た。Experiment No. 4 A polymer was obtained in the same manner as in Experiment No. 1 except that the additional amount during the polymerization of the vinyl chloride monomer was changed to 210 kg.
【００３２】実験 No.５ 実験 No.１において、塩化ビニル単量体の重合中での追
加時期を重合転化率が70％に達したときとしたほかは同
様にして重合体を得た。Experiment No. 5 A polymer was obtained in the same manner as in Experiment No. 1, except that the vinyl chloride monomer was added during the polymerization when the polymerization conversion reached 70%.
【００３３】実験 No.６ 実験 No.１において、重合器内圧が8.2kg/cm2Gに低下し
た時点で未反応単量体の回収を行ったほかは同様にして
重合体を得た。Experiment No. 6 A polymer was obtained in the same manner as in Experiment No. 1, except that the unreacted monomer was recovered when the internal pressure of the polymerization reactor dropped to 8.2 kg / cm 2 G.
【００３４】実験 No.７ 実験 No.１において、（Ａ）成分の部分ケン化ポリビニ
ルアルコールを添加せず、（Ｂ）成分のヒドロキシプロ
ピルメチルセルロースの添加量を 350ｇに変えたほかは
同様にして重合体を得た。Experiment No. 7 In Experiment No. 1, the weight was changed in the same manner as in Experiment No. 1 except that the partially saponified polyvinyl alcohol of the component (A) was not added and the amount of the hydroxypropyl methylcellulose of the component (B) was changed to 350 g. A coalescence was obtained.
【００３５】実験 No.８ 実験 No.１において、（Ａ）成分の部分ケン化ポリビニ
ルアルコールの添加量を 350ｇとし、（Ｂ）成分のヒド
ロキシプロピルメチルセルロースを添加しなかったほか
は同様にして重合体を得た。Experiment No. 8 The same procedure as in Experiment No. 1 was carried out except that the amount of the partially saponified polyvinyl alcohol of the component (A) was 350 g and the hydroxypropylmethylcellulose of the component (B) was not added. I got
【００３６】実験 No.９ 実験 No.１において、（Ｃ）成分の部分ケン化ポリビニ
ルアルコールを添加しなかったほかは同様にして重合体
を得た。Experiment No. 9 A polymer was obtained in the same manner as in Experiment No. 1 except that the partially saponified polyvinyl alcohol as the component (C) was not added.
【００３７】実験 No.10 実験 No.１において、（Ｃ）成分の部分ケン化ポリビニ
ルアルコールの添加量を2450ｇに変えたほかは同様にし
て重合体を得た。Experiment No. 10 A polymer was obtained in the same manner as in Experiment No. 1 except that the amount of the partially saponified polyvinyl alcohol (C) was changed to 2450 g.
【００３８】実験 No.11 実験 No.１において、仕込み当初の脱イオン水の添加量
を 700kgに変えたほかは同様にして重合体を得た。Experiment No. 11 A polymer was obtained in the same manner as in Experiment No. 1, except that the amount of deionized water added at the beginning of the preparation was changed to 700 kg.
【００３９】実験 No.12 実験 No.１において、（Ａ）成分として平均重合度170
0、ケン化度99.0モル％の部分ケン化ポリビニルアルコ
ール 105ｇを用いたほかは同様にして重合体を得た。Experiment No. 12 In Experiment No. 1, the average degree of polymerization was 170 as the component (A).
A polymer was obtained in the same manner except that 105 g of partially saponified polyvinyl alcohol having a saponification degree of 99.0 mol% was used.
【００４０】実験 No.13 実験 No.１において、（Ａ）成分として平均重合度400
0、ケン化度99.5モル％の部分ケン化ポリビニルアルコ
ール 105ｇを用いたほかは同様にして重合体を得た。Experiment No. 13 In Experiment No. 1, the average degree of polymerization was 400 as the component (A).
A polymer was obtained in the same manner except that 105 g of partially saponified polyvinyl alcohol having a saponification degree of 99.5 mol% was used.
【００４１】実験 No.14 実験 No.１において、（Ａ）成分として平均重合度100
0、ケン化度88.0モル％の部分ケン化ポリビニルアルコ
ール 105ｇを用いたほかは同様にして重合体を得た。Experiment No. 14 In Experiment No. 1, the average degree of polymerization was 100 as the component (A).
A polymer was obtained in the same manner except that 105 g of partially saponified polyvinyl alcohol having a saponification degree of 88.0 mol% was used.
【００４２】実験 No.14 実験 No.１において、（Ａ）成分として平均重合度 78
0、ケン化度72.9モル％の部分ケン化ポリビニルアルコ
ール 180ｇを用いたほかは同様にして重合体を得た。Experiment No. 14 In Experiment No. 1, the average degree of polymerization was 78 as the component (A).
A polymer was obtained in the same manner except that 180 g of partially saponified polyvinyl alcohol having a saponification degree of 72.9 mol% was used.
【００４３】実験 No.15 実験 No.１において、（Ｂ）成分としてメトキシ置換度
21.5重量％、ヒドロキシプロポキシ置換度 8.2重量％
で、その２重量％水溶液の20℃における粘度が100cpsの
ヒドロキシプロピルメチルセルロース 245ｇを用いたほ
かは同様にして重合体を得た。Experiment No. 15 In Experiment No. 1, the degree of methoxy substitution was determined as the component (B).
21.5% by weight, degree of hydroxypropoxy substitution 8.2% by weight
A polymer was obtained in the same manner except that 245 g of hydroxypropylmethylcellulose having a viscosity of 100 cps at 20 ° C. of the 2% by weight aqueous solution was used.
【００４４】実験 No.16 実験 No.１において、（Ｂ）成分としてメトキシ置換度
29.0重量％、ヒドロキシプロポキシ置換度10.0重量％
で、その２重量％水溶液の20℃における粘度が400cpsの
ヒドロキシプロピルメチルセルロース 245ｇを用いたほ
かは同様にして重合体を得た。Experiment No. 16 In Experiment No. 1, the methoxy substitution degree was used as the component (B).
29.0% by weight, degree of hydroxypropoxy substitution 10.0% by weight
A polymer was obtained in the same manner except that 245 g of hydroxypropyl methylcellulose having a viscosity of 400 cps at 20 ° C. of the 2% by weight aqueous solution was used.
【００４５】実験 No.17 実験 No.１において、（Ｃ）成分として平均重合度100
0、ケン化度45.0モル％の部分ケン化ポリビニルアルコ
ール 350ｇを用いたほかは同様にして重合体を得た。Experiment No. 17 In Experiment No. 1, the average degree of polymerization was 100 as the component (C).
A polymer was obtained in the same manner except that 350 g of partially saponified polyvinyl alcohol having a saponification degree of 45.0 mol% was used.
【００４６】実験 No.18 実験 No.１において、（Ｃ）成分として平均重合度 50
0、ケン化度81.0モル％の部分ケン化ポリビニルアルコ
ール 350ｇを用いたほかは同様にして重合体を得た。Experiment No. 18 In Experiment No. 1, the average degree of polymerization was 50 as the component (C).
A polymer was obtained in the same manner except that 350 g of partially saponified polyvinyl alcohol having a saponification degree of 81.0 mol% was used.
【００４７】得られた各重合体について、下記の方法に
より嵩比重、粒度分布および可塑剤吸収量を測定すると
共に、成形品のフィシュアイ量を測定し、それらの結果
を、表１（実験 No.１〜９）および表２（実験 No.10〜
18）に示した。なお、実験 No.１、11〜12および16が本
発明、他は対照例である。For each of the obtained polymers, the bulk specific gravity, the particle size distribution and the amount of the plasticizer absorbed were measured by the following method, and the fisheye amount of the molded article was measured. The results are shown in Table 1 (Experiment No. .1-9) and Table 2 (Experiment No.10-
18). Experiment Nos. 1, 11 to 12 and 16 are the present invention, and others are control examples.
【００４８】・嵩比重：JIS K-6721にしたがって測定し
た。 ・粒度分布：JIS Z-8801に準じた #60、#100、#200の各
篩を用いて篩分けし、通過量（重量％）を計量した。Bulk specific gravity: Measured according to JIS K-6721. Particle size distribution: Sieved using each of # 60, # 100, and # 200 sieves according to JIS Z-8801, and the passing amount (% by weight) was measured.
【００４９】・可塑剤吸収量：内径25mm、深さ85mmのア
ルミニウム合金製容器の底にグラスファイバ−を詰め、
得られた重合体10ｇを採取して投入する。これにジオク
チルフタレ−ト（ＤＯＰ）15ccを加え、30分放置してＤ
ＯＰを樹脂に充分浸透させる。その後1500Ｇの加速度下
に過剰のＤＯＰを遠心分離し、樹脂に吸収されたＤＯＰ
の量を樹脂 100重量部当りの値で表した。A plasticizer absorption amount: A glass fiber is packed in the bottom of an aluminum alloy container having an inner diameter of 25 mm and a depth of 85 mm.
10 g of the obtained polymer is sampled and charged. Add 15 cc of dioctyl phthalate (DOP) to this and leave for 30 minutes to add D
Allow OP to fully penetrate the resin. Then, the excess DOP was centrifuged under an acceleration of 1500 G, and the DOP absorbed by the resin was removed.
Was expressed as a value per 100 parts by weight of the resin.
【００５０】・成形品のフィシュアイ量： 得られた重合体 100重量部 ＤＯＰ（フタル酸ジオクチル） 50 〃 三塩基性硫酸鉛 0.5 〃 ステアリン酸鉛 1.5 〃 酸化チタン 0.1 〃 カーボンブラック 0.05 〃 からなる配合物25ｇを、６”ロールを用いて 140℃で７
分間混練した後、幅10cm×厚さ 0.2mmのシートに成形し
た。得られたシートの面積100cm2当りの透明粒子数を計
数し、これをフィシュアイ量とした。Amount of fisheye in molded article: 100 parts by weight of obtained polymer DOP (dioctyl phthalate) 50 〃 Tribasic lead sulfate 0.5 鉛 Lead stearate 1.5 チ タ ン Titanium oxide 0.1 カ ー ボ ン Carbon black 0.05 配合25 g of the product at 140 ° C. using a 6 ″ roll for 7 g
After kneading for minutes, it was formed into a sheet having a width of 10 cm and a thickness of 0.2 mm. The number of transparent particles per 100 cm 2 of the area of the obtained sheet was counted, and this was defined as a fisheye amount.
【００５１】[0051]
【表１】 [Table 1]
【００５２】[0052]
【表２】 [Table 2]
【００５３】[0053]
【発明の効果】本発明によれば、嵩比重が高く成形品の
フィシュアイを有効に抑制することのできるポロシティ
の高い、高品質の塩化ビニル系重合体を、高い生産効率
のもとで製造することができる。According to the present invention, a high-porosity, high-quality vinyl chloride polymer having a high bulk specific gravity and capable of effectively suppressing fisheye of a molded article can be produced with high production efficiency. can do.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C08F 2/18 - 2/20 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C08F 2/18-2/20
Claims (1)
を分散安定剤の存在下に水性媒体中で懸濁重合するに際
し、前記分散安定剤として（Ａ）平均重合度が1500〜27
00、ケン化度が75〜99モル％の部分ケン化ポリビニルア
ルコールと（Ｂ）メトキシ置換度が26〜30重量％、ヒド
ロキシプロポキシ置換度が４〜15重量％で、その２重量
％水溶液の20℃における粘度が５〜 4000cpsであるヒド
ロキシプロピルメチルセルロースとを、合わせて塩化ビ
ニル系単量体の全仕込み量 100重量部当り0.03〜0.15重
量部用いると共に、さらに（Ｃ）平均重合度が 150〜 6
00、ケン化度が20〜55モル％の部分ケン化ポリビニルア
ルコールを、塩化ビニル系単量体の全仕込み量 100重量
部当り0.03〜0.15重量部で、（Ａ）、（Ｂ）両成分の１
〜５重量倍使用し、重合温度を54℃以上に保って重合を
開始した後、重合転化率が10〜60％に達した時点で、さ
らに当初の仕込み単量体の10〜20重量％に相当する量の
単量体を添加し、当初の仕込み単量体量の90％が重合転
化する段階まで重合反応を続けることを特徴とする塩化
ビニル系重合体の製造方法。When a vinyl chloride monomer and an oil-soluble polymerization initiator are subjected to suspension polymerization in an aqueous medium in the presence of a dispersion stabilizer, the dispersion stabilizer (A) has an average degree of polymerization of from 1500 to less. 27
A partially saponified polyvinyl alcohol having a degree of saponification of 75 to 99 mol% and (B) a methoxy substitution degree of 26 to 30% by weight, a hydroxypropoxy substitution degree of 4 to 15% by weight, and a 2% by weight aqueous solution of 20% Hydroxypropyl methylcellulose having a viscosity at 5 ° C. of 5 to 4000 cps is used in an amount of 0.03 to 0.15 part by weight per 100 parts by weight of the total amount of the vinyl chloride monomer, and (C) the average degree of polymerization is 150 to 6
A partially saponified polyvinyl alcohol having a degree of saponification of 20 to 55 mol% is used in an amount of 0.03 to 0.15 parts by weight per 100 parts by weight of the total charged amount of the vinyl chloride monomer. 1
After starting polymerization by maintaining the polymerization temperature at 54 ° C. or more, when the polymerization conversion reaches 10 to 60%, it is further reduced to 10 to 20% by weight of the initially charged monomer. A method for producing a vinyl chloride polymer, comprising adding a corresponding amount of a monomer and continuing the polymerization reaction until a stage in which 90% of the initially charged monomer amount undergoes polymerization conversion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26900291A JP2938635B2 (en) | 1991-09-20 | 1991-09-20 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26900291A JP2938635B2 (en) | 1991-09-20 | 1991-09-20 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0578405A JPH0578405A (en) | 1993-03-30 |
| JP2938635B2 true JP2938635B2 (en) | 1999-08-23 |
Family
ID=17466309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26900291A Expired - Fee Related JP2938635B2 (en) | 1991-09-20 | 1991-09-20 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2938635B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101168400B1 (en) * | 2008-07-07 | 2012-07-25 | 주식회사 엘지화학 | Suspension polymerization method for polyvinylchloride and polyvinylchloride produced thereby |
| KR101808048B1 (en) | 2010-09-22 | 2017-12-12 | 비놀리트 게엠베하 운트 콤파니 카게 | Process for producing a polyvinyl chloride(PVC) resin |
-
1991
- 1991-09-20 JP JP26900291A patent/JP2938635B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101168400B1 (en) * | 2008-07-07 | 2012-07-25 | 주식회사 엘지화학 | Suspension polymerization method for polyvinylchloride and polyvinylchloride produced thereby |
| KR101808048B1 (en) | 2010-09-22 | 2017-12-12 | 비놀리트 게엠베하 운트 콤파니 카게 | Process for producing a polyvinyl chloride(PVC) resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0578405A (en) | 1993-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2583453B2 (en) | Method for producing vinyl chloride polymer with improved plasticizer absorption | |
| JP2938635B2 (en) | Method for producing vinyl chloride polymer | |
| JP3169673B2 (en) | Method for producing vinyl chloride polymer | |
| JP3257174B2 (en) | Method for producing vinyl chloride polymer | |
| JP3115919B2 (en) | Method for producing vinyl chloride polymer | |
| JP3317830B2 (en) | Method for producing vinyl chloride polymer | |
| JP2986276B2 (en) | Method for producing vinyl chloride polymer | |
| JP2878874B2 (en) | Method for producing vinyl chloride polymer | |
| JP3317798B2 (en) | Method for producing vinyl chloride polymer | |
| JP2986258B2 (en) | Method for producing vinyl chloride polymer | |
| JP2823681B2 (en) | Method for producing vinyl chloride polymer | |
| JP2851453B2 (en) | Method for producing vinyl chloride polymer | |
| JP3210388B2 (en) | Method for producing vinyl chloride polymer | |
| JP2962615B2 (en) | Method for producing vinyl chloride polymer | |
| JP3284723B2 (en) | Method for producing vinyl chloride polymer | |
| JP3071239B2 (en) | Suspension polymerization of vinyl chloride monomer | |
| JPH0778084B2 (en) | Method for producing vinyl chloride polymer | |
| JPH0539309A (en) | Production of vinyl chloride polymer | |
| JP3210504B2 (en) | Method for producing vinyl chloride polymer | |
| JPH06166704A (en) | Production of vinyl chloride-based polymer | |
| JP2531570B2 (en) | Method for producing vinyl chloride polymer | |
| JP3437018B2 (en) | Method for producing vinyl chloride polymer | |
| JP3239619B2 (en) | Method for producing vinyl chloride polymer | |
| JP3139840B2 (en) | Method for producing vinyl chloride polymer | |
| JPH06340714A (en) | Production of vinyl chloride polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 10 Free format text: PAYMENT UNTIL: 20090611 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 10 Free format text: PAYMENT UNTIL: 20090611 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 11 Free format text: PAYMENT UNTIL: 20100611 |
|
| LAPS | Cancellation because of no payment of annual fees |