JPS6025442B2 - Suspension polymerization method of vinyl chloride - Google Patents
Suspension polymerization method of vinyl chlorideInfo
- Publication number
- JPS6025442B2 JPS6025442B2 JP12163874A JP12163874A JPS6025442B2 JP S6025442 B2 JPS6025442 B2 JP S6025442B2 JP 12163874 A JP12163874 A JP 12163874A JP 12163874 A JP12163874 A JP 12163874A JP S6025442 B2 JPS6025442 B2 JP S6025442B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- melting point
- suspension polymerization
- point compound
- 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
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 10
- 238000010558 suspension polymerization method Methods 0.000 title description 3
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000000499 gel Substances 0.000 description 6
- 241000251468 Actinopterygii Species 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000010005 Catalpa ovata Nutrition 0.000 description 1
- 240000004528 Catalpa ovata Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- -1 acetylcyclohexylsulfonyl Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 本発明は、塩化ビニルの水性媒体中の懸濁重合に係る。[Detailed description of the invention] The present invention relates to the suspension polymerization of vinyl chloride in an aqueous medium.
更に詳記すれば、ゲル効果を惹き起すことなく、重合器
壁における重合体スケールの生成付着を防止し、優れた
熱安定性をもつ着色の少ないポリ塩化ビニルを、容易に
且つ効率よく製造する方法に関する。懸濁重合により製
せられるポリ塩化ビニルは、汎用樹脂として近年ますま
すその需要が拡大しているが、技術的には、‘１｝重合
器壁にスケールが付着して冷却効果が低下し、更にこれ
が剥落して製品中に混入した場合には、フィッシュアイ
の原因になる等の悪影響を与える。More specifically, it prevents the formation and adhesion of polymer scale on the walls of a polymerization vessel without causing a gel effect, and easily and efficiently produces polyvinyl chloride with excellent thermal stability and little coloring. Regarding the method. Demand for polyvinyl chloride, which is produced by suspension polymerization, has been increasing in recent years as a general-purpose resin, but technically, there are two problems: 1) Scale adheres to the walls of the polymerization vessel, reducing the cooling effect. Furthermore, if this flakes off and mixes into the product, it will cause adverse effects such as causing fish eyes.
（２｝重合物が単量体に不溶である為、通常ゲル効果と
呼ばれるのであるが、所要の高重合率に到る時に重合速
度が急激に上昇し、この為製品の不・均一化やフィッシ
ュアィ等の問題が生じる。糊重合効率の増大をはかる為
にジイソピロピルパーオキシジカーポネート、アセチル
シクロヘキシルスルホニル／ぐーオキサイド等の重合開
始剤を使用すると、反応が爆発的に起って制御が困難に
なり、生成するポリ塩化ピニルの物性が低下し、開始剤
量を減ずると、高い重合率に達する以前に実質的に重合
が停止する等種々の問題が有り、その為更に優れた重合
方法が求められつづけている。本発明者等は、上記した
如き従釆法の欠点を克服する為鋭意検討し、塩化ビニル
又はこれを主体とするビニル系単量体を含む水性媒体中
に、低融点の異性体を９０％以上有する２，２−アゾビ
ス（２，４ージメチルワレロニトリル）の低融点化合物
を加えて、重合することにより、上述した従来法の欠点
を一挙に解決し、効率よく優れた製品が得られる、新規
な塩化ピニルの懸濁重合法を見出し、本発明を完成した
。(2) Since the polymer is insoluble in the monomer, it is usually called the gel effect, but when the required high polymerization rate is reached, the polymerization rate increases rapidly, resulting in non-uniformity and non-uniformity of the product. Problems such as fish eyes occur.If a polymerization initiator such as diisopropyl peroxydicarbonate or acetylcyclohexylsulfonyl/gu oxide is used to increase the glue polymerization efficiency, the reaction will occur explosively and be difficult to control. However, if the amount of initiator is reduced, the polymerization will substantially stop before reaching a high polymerization rate. The inventors of the present invention have made extensive studies to overcome the drawbacks of the conventional method as described above, and have found that the present inventors have carried out intensive studies to overcome the drawbacks of the conventional method as described above, and have found that they By adding a low melting point compound such as 2,2-azobis(2,4-dimethylvaleronitrile) having 90% or more of low melting point isomers and polymerizing it, the drawbacks of the conventional method described above are solved at once, We have discovered a new suspension polymerization method for pinyl chloride that can efficiently produce excellent products, and have completed the present invention.
２，２ーアゾピス（２，４−ジメチルワレロニトリル）
は、オーバーバーガーらのＪｏｕｍａｌｏｆｍｅＡｍｅ
ｒｉｃａｎＣｈｅｍｉｃａｌＳ比ｉｅｔｙ、第７鏡篭、
２６１８−２６２１頁（１９５１）の報告に、「２，２
ーアゾピス（２，４−ジメチルワレロニトリル）が融点
５６℃〜５７０、若しくは７４ｑｏ〜７７０のメソ体若
しくはｄ‘体なる立体異性に起因する２種の異性体から
成る。2,2-azopis (2,4-dimethylvaleronitrile)
The JoumalofmeAme of Oberberger et al.
ricanChemicalS ratio, 7th kyogo,
In the report on pages 2618-2621 (1951), “2,2
-Azopis (2,4-dimethylvaleronitrile) consists of two stereoisomers, the meso form and the d' form, with a melting point of 56° C. to 570°C or 74qo to 770°.
」の記載があるとおり、低融点化合物と高融点化合物の
２種の異性体からなり、通常公知の製法によっては、こ
れら分子内の２つの不整炭素原子に起因して生ずる２種
の異性体の混合物として提供される。その為、従来の塩
化ビニルの懸濁重合方法では、重合開始剤としてこれら
異性体の混合物を使用して行なわれていたが、吾々はこ
れら異性体の内で、低融点化合物が高融点化合物と比べ
、重合活性が高く、ゲル効果の点でも非常に改善された
重合反応を提供することを見出し本発明を完成した。As stated in ``, it consists of two isomers, a low melting point compound and a high melting point compound, and depending on the commonly known manufacturing method, the two isomers resulting from the two asymmetric carbon atoms in these molecules can be separated. Supplied as a mixture. Therefore, in the conventional suspension polymerization method of vinyl chloride, a mixture of these isomers was used as a polymerization initiator, but we found that among these isomers, the low melting point compound is the high melting point compound. The present invention was completed based on the discovery that the present invention provides a polymerization reaction with higher polymerization activity and significantly improved gel effect.
従来、２，２−アゾビス（２，４ージメチルワレロニト
リル）は、低融点化合物と高融点化合物とがほぼ等量混
合された形で生産されていたが、本発明で用いる場合は
低融点化合物が約９０％以上含有されている必要があり
、これ未満であっては本発明の効果を十分発揮しない。Conventionally, 2,2-azobis(2,4-dimethylvaleronitrile) was produced in the form of a mixture of approximately equal amounts of a low melting point compound and a high melting point compound, but when used in the present invention, a low melting point compound and a high melting point compound are mixed together in approximately equal amounts. The content of the compound must be about 90% or more, and if it is less than this, the effects of the present invention will not be sufficiently exhibited.
低融点化合物の使用量は、単量体に対し、０．００１〜
０．５重量％であるのが好ましく、これ以下の量である
と効果が減少し、これ以上であると、製品の物性の低下
をきたすと共に経済的でない。重合温度は汎用の重合度
のものを得るには、３０〜７０ｑ○で行うのが好ましい
。本発明方法におけるその他の重合条件は、従来公知の
懸濁重合と全く同様でよい。The amount of the low melting point compound used is 0.001 to 0.001 to the monomer.
The amount is preferably 0.5% by weight; if the amount is less than this, the effect will be reduced, and if it is more than this, the physical properties of the product will deteriorate and it will be uneconomical. The polymerization temperature is preferably 30 to 70 q○ in order to obtain a general-purpose polymerization degree. Other polymerization conditions in the method of the present invention may be exactly the same as those for conventionally known suspension polymerization.
従って、これには懸濁剤としてポリビニルアルコール、
各種の水熔性セルロース誘導体、酢酸ビニルー無水マレ
ィン酸共重合体、ゼラチン、デンプンなどの合成又は天
然の水落性高分子物質を使用し、更に必要に応じ各種分
子量調節剤を添加して、縄梓下に重合を行なえばよい。
なお、上記においては主として塩化ビニルの単一重合体
について記載したが、この発明の方法は塩化ビニルを主
体とするその共重合体にも同様に適用され、この塩化ビ
ニルと共重合し得る単量体としては各種ビニルヱステル
、ビニルェーテル、芳香族ビニル化合物アクリル酸また
はメタクリル酸またはそれらのェステル、マレイン酸ま
たはフマール酸あるいはそれらの無水物およびェステル
−オレフィン類等が挙げられる。Therefore, this includes polyvinyl alcohol as a suspending agent,
Various water-soluble cellulose derivatives, vinyl acetate-maleic anhydride copolymers, gelatin, starch, and other synthetic or natural water-soluble polymeric substances are used, and if necessary, various molecular weight regulators are added to make rope Azusa. Polymerization may be performed at the bottom.
In addition, although the above description mainly concerns a homopolymer of vinyl chloride, the method of the present invention is similarly applicable to its copolymer mainly composed of vinyl chloride, and monomers copolymerizable with vinyl chloride can be used. Examples include various vinyl esters, vinyl ethers, aromatic vinyl compounds acrylic acid or methacrylic acid or their esters, maleic acid or fumaric acid or their anhydrides, and ester-olefins.
更に本発明方法の効果を述べると、従来ゲル効果を抑え
る為に、低温活性と高温活性の双方を組み合わせた開始
剤系を採用したりしていたが、この系の欠点は、主に低
温活性開始剤から高温活性開始剤へ開始効果が移行する
重合中期に重合速度の中だるみ現象がみられ、この為重
合時間の延長、製品の不均一化、フィッシュアィの生成
等好ましくない現象を生じたが、本発明方法を適用する
ことにより、上記の如き中だるみ現象がなく、ゲル効果
も解消し、その為初期着色やフィッシュアィ等の問題の
解決された製品が得られる。Furthermore, to describe the effect of the method of the present invention, in order to suppress the gel effect, an initiator system that combines both low-temperature activity and high-temperature activity has been used, but the drawback of this system is that it mainly has low-temperature activity. A sagging phenomenon was observed in the polymerization rate during the middle stage of polymerization when the initiation effect was transferred from the initiator to the high temperature active initiator, and this caused undesirable phenomena such as prolongation of polymerization time, non-uniformity of the product, and formation of fish eyes. By applying the method of the present invention, there is no sagging phenomenon as described above, the gel effect is also eliminated, and therefore a product can be obtained in which problems such as initial discoloration and fish eyes are solved.
以下に実施例を挙げ、本発明を更に説瀕する。実施例中
数量を表わす部は重量部である。実施例
封管中に各々水１碇部、塩化ビニル５３部、ポリブニル
アルコール（ゴーセノールＧＨ−２０，日本合成化学工
業製）０．０６部と、低融点物含量９８％の２，２′ー
アゾビス（２，４−ジメチルワレロニトリル）０．００
４群部加え、５０℃で重合させ、重合時間と重合率との
関係をプロットし、別紙図面に示す結果を得た。Examples are given below to further explain the present invention. In the examples, parts expressed are parts by weight. Example: In a sealed tube, 1 part of water, 53 parts of vinyl chloride, 0.06 part of polyvinyl alcohol (Gohsenol GH-20, manufactured by Nippon Gosei Kagaku Kogyo), and 2,2' with a low melting point content of 98% were added. -Azobis(2,4-dimethylvaleronitrile) 0.00
Group 4 was added and polymerized at 50°C, and the relationship between polymerization time and polymerization rate was plotted, and the results shown in the attached drawings were obtained.
比較の為、高融点化合物（含量９６％）単独及び高融点
化合物と低融点化合物との等量混合物を重合開始剤とし
て行った結果も併記した。図から明らかな如く、低融点
化合物は、高融点化合物を使用した場合と比べ、活性が
高く、ゲル効果も改善された重合速度が得られる。For comparison, the results of using a high melting point compound (96% content) alone and a mixture of equal amounts of a high melting point compound and a low melting point compound as a polymerization initiator are also shown. As is clear from the figure, a low melting point compound has higher activity and a polymerization rate with improved gel effect compared to the case where a high melting point compound is used.
図面は、実施例の重合時間と重合率との関係を示す。 The drawing shows the relationship between polymerization time and polymerization rate in Examples.
Claims (1)
含む水性媒体中に、低融点の異性体を９０％以上含有す
る２，２′−アゾビス（２，４−ジメチルワレロニトリ
ル）を加えて、重合させることを特徴とする、塩化ビニ
ルの懸濁重合方法。1. Adding 2,2'-azobis(2,4-dimethylvaleronitrile) containing 90% or more of a low melting point isomer to an aqueous medium containing vinyl chloride or a vinyl-based simple substance mainly composed of vinyl chloride, A method for suspension polymerization of vinyl chloride, characterized by polymerizing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12163874A JPS6025442B2 (en) | 1974-10-21 | 1974-10-21 | Suspension polymerization method of vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12163874A JPS6025442B2 (en) | 1974-10-21 | 1974-10-21 | Suspension polymerization method of vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5147083A JPS5147083A (en) | 1976-04-22 |
| JPS6025442B2 true JPS6025442B2 (en) | 1985-06-18 |
Family
ID=14816200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12163874A Expired JPS6025442B2 (en) | 1974-10-21 | 1974-10-21 | Suspension polymerization method of vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6025442B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337687Y2 (en) * | 1973-03-31 | 1978-09-12 | ||
| JPS59157063A (en) * | 1983-02-26 | 1984-09-06 | Wako Pure Chem Ind Ltd | Preparation of 2,2'-azobis(2,4-dimethylvaleronitrile) having improved solvent solubility |
-
1974
- 1974-10-21 JP JP12163874A patent/JPS6025442B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5147083A (en) | 1976-04-22 |
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