JPH0114241B2 - - Google Patents
Info
- Publication number
- JPH0114241B2 JPH0114241B2 JP7729479A JP7729479A JPH0114241B2 JP H0114241 B2 JPH0114241 B2 JP H0114241B2 JP 7729479 A JP7729479 A JP 7729479A JP 7729479 A JP7729479 A JP 7729479A JP H0114241 B2 JPH0114241 B2 JP H0114241B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- mercaptan
- gas phase
- parts
- vinyl monomers
- 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
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
Description
【発明の詳細な説明】
本発明はビニル単量体の重合方法に関し、より
詳しくはビニル単量体の重合に際し、重合器の内
壁に重合ポリマーの付着を防止するビニル単量体
の重合方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing vinyl monomers, and more particularly to a method for polymerizing vinyl monomers that prevents the polymer from adhering to the inner wall of a polymerization vessel during polymerization of vinyl monomers. .
従来、ビニル単量体を撹拌機付重合器内で塊状
重合、溶液重合、懸濁重合又は乳化重合する方法
が知られている。これらの重合法においては、反
応熱の除去、安全及び操作上の問題、あるいは重
合装置の構造上の制限等の理由により重合器内の
全空間を重合反応液で満して行うことは少なく、
通常気相部分が存在した状態で重合が行われる。
この重合においては気相中に存在するガス状の単
量体が重合器気相部で重合し、重合器の気相部内
壁に多量の重合体スケールが付着する。このよう
な重合体が付着するとノズルが閉そくしたり、撹
拌機の機能に障害が起るなどの機械的異常の発生
原因となり、あるいは重合体スケールの剥離スケ
ールが製品中に混入して異常製品を発生したりす
ると共に、この付着ポリマーの除去に多大の労力
と時間を要し、工業規模で生産を行う場合大きな
問題となる。 Conventionally, methods are known in which vinyl monomers are subjected to bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization in a polymerization vessel equipped with a stirrer. In these polymerization methods, the entire space in the polymerization vessel is rarely filled with the polymerization reaction liquid for reasons such as removal of reaction heat, safety and operational issues, or structural limitations of the polymerization equipment.
Polymerization is usually carried out in the presence of a gas phase.
In this polymerization, gaseous monomers present in the gas phase are polymerized in the gas phase portion of the polymerization vessel, and a large amount of polymer scale adheres to the inner wall of the gas phase portion of the polymerization vessel. If this kind of polymer adheres, it may cause mechanical abnormalities such as blocking the nozzle or disrupting the function of the stirrer, or the flaking scale of the polymer may be mixed into the product, resulting in abnormal products. At the same time, it takes a great deal of effort and time to remove this adhered polymer, which becomes a big problem when producing on an industrial scale.
このような重合器の気相部内壁への重合体スケ
ールの付着防止法として、重合器内の気相部壁に
水又は増粘した水を散布する方法が知られている
（特公昭48−42470号）。 As a method for preventing the adhesion of polymer scale to the inner wall of the gas phase section of a polymerization vessel, a method is known in which water or thickened water is sprayed onto the wall of the gas phase section of the polymerization vessel (Japanese Patent Publication No. 1973- No. 42470).
しかし、この方法はビニル単量体を水性媒体中
で重合を行う方法に限られており、これ以外の方
法、例えば塊状重合及び溶液重合には使用できな
いという欠点を有している。 However, this method is limited to polymerizing vinyl monomers in an aqueous medium, and has the disadvantage that it cannot be used for other methods, such as bulk polymerization and solution polymerization.
したがつて、ビニル単量体のすべての重合方法
に対して、重合器内の気相部壁への重合体スケー
ルを防止することはできなかつた。 Therefore, in all methods of polymerizing vinyl monomers, it has not been possible to prevent polymer scale from forming on the walls of the gas phase in the polymerization vessel.
本発明者はこのような状況に鑑み種々検討を行
つた結果、特殊な重合方法を採用することによ
り、前記の問題点が一挙に解決できることを見い
出し本発明を完成した。 In view of this situation, the present inventor conducted various studies, and as a result, discovered that the above-mentioned problems could be solved at once by employing a special polymerization method, and completed the present invention.
すなわち、本発明の要旨とするところはビニル
単量体を液相で撹拌しつつ重合を行うビニル単量
体の重合方法において、該重合を行う反応装置内
の反応液上の気相部に沸点が常圧で100℃以下で
あるメルカプタンを存在させて重合を行うことを
特徴とするビニル単量体の重合方法にある。 That is, the gist of the present invention is to provide a method for polymerizing vinyl monomers in which vinyl monomers are polymerized while being stirred in a liquid phase. A method for polymerizing vinyl monomers, characterized in that the polymerization is carried out in the presence of a mercaptan whose temperature is 100° C. or less at normal pressure.
本発明の実施において、反応装置内の気相部に
存在させるメルカプタンとしては、例えばメチル
メルカプタン、エチルメルカプタン、プロピルメ
ルカプタン、イソプロピルメルカプタン、Ｎ−ブ
チルメルカプタン、イソブチルメルカプタン等の
メルカプタン類で常圧における沸点が100℃以下
のものである。 In carrying out the present invention, examples of mercaptans to be present in the gas phase in the reaction apparatus include mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, N-butyl mercaptan, and isobutyl mercaptan, which have a boiling point at normal pressure. The temperature is below 100℃.
本発明の場合には、特に沸点が40℃以下のメチ
ルメルカプタン、エチルメルカプタンが好まし
い。 In the case of the present invention, methyl mercaptan and ethyl mercaptan having a boiling point of 40° C. or lower are particularly preferred.
沸点が100℃以上の場合には沸点があまり高い
ため、重合温度条件においてガス状になりにくく
て、単量体中に混入し、重合体の分子量を低下さ
せるので好ましくない。 If the boiling point is 100°C or higher, the boiling point is so high that it is difficult to become gaseous under the polymerization temperature conditions, and it is undesirable because it mixes into the monomer and lowers the molecular weight of the polymer.
また気相部に存在させる上記メルカプタンの量
は気相部の空間において１〜1000ppm、好ましく
は10〜500ppm存在させることがよい。気相部の
メルカプタン量が1ppm以下の場合には、重合器
内の気相部壁に重合体スケールが付着しやすくな
り、また一方気相部のメルカプタン量が1000ppm
以上の場合には、メルカプタン濃度が高くなるた
め、液相中へ溶解量が多くなり、生成する重合体
の重合度に支障を起すので好ましくない。 The amount of the mercaptan present in the gas phase is preferably 1 to 1000 ppm, preferably 10 to 500 ppm. When the amount of mercaptan in the gas phase is less than 1 ppm, polymer scale tends to adhere to the walls of the gas phase in the polymerization vessel, and on the other hand, when the amount of mercaptan in the gas phase is 1000 ppm or less,
In the above case, since the mercaptan concentration becomes high, the amount dissolved in the liquid phase increases, which causes a problem in the degree of polymerization of the produced polymer, which is not preferable.
なお、本発明の実施においては、上記した沸点
及びメルカプタン量を考慮して行えば十分その所
期の目的を達成しうるが、更に好ましくは前記し
たメタルカプタン類の中でも単量体に対する溶解
度の小さいものほどよい。 In carrying out the present invention, the intended purpose can be sufficiently achieved by taking into consideration the boiling point and amount of mercaptan described above, but it is more preferable to use metal captans that have low solubility in the monomer among the metal captans mentioned above. Moderate.
本発明の実施に際して用いられるビニル単量体
としては、例えばアルキル（メタ）アクリレー
ト、スチレン、アクリロニトリル等があげられ
る。また本発明の方法において使用できる重合方
法としては、前記ビニル単量体を液相で重合でき
る塊状重合、溶液重合、懸濁重合又は乳化重合が
あげられる。 Examples of vinyl monomers used in the practice of the present invention include alkyl (meth)acrylates, styrene, acrylonitrile, and the like. Polymerization methods that can be used in the method of the present invention include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization in which the vinyl monomer can be polymerized in a liquid phase.
また本発明の方法において使用される重合反応
器としては公知の重合器、例えば撹拌機を有する
種々の重合器が用いられる。本発明の実施におけ
る重合温度及び反応圧力はそれぞれ50〜250℃及
び０〜50Kg／cm2Ｇである。 Further, as the polymerization reactor used in the method of the present invention, known polymerization reactors such as various polymerization reactors having a stirrer can be used. The polymerization temperature and reaction pressure in the practice of the present invention are 50-250°C and 0-50 Kg/cm 2 G, respectively.
本発明によれば、従来ビニル単量体の重合にお
いて問題の多かつた重合器内の気相部壁への重合
体スケールの付着を完全に防止し、しかも生産性
良く物性の優れた製品を歩留りよくうることがで
きる。 According to the present invention, it is possible to completely prevent polymer scale from adhering to the walls of the gas phase in a polymerization vessel, which has been a problem in the conventional polymerization of vinyl monomers, and to produce products with good productivity and excellent physical properties. It can be produced with good yield.
以下、例により本発明を更に詳しく説明する
が、例中における部及び％はそれぞれ重量部及び
重量％を示す。 Hereinafter, the present invention will be explained in more detail with reference to examples, in which parts and % indicate parts by weight and % by weight, respectively.
例 １
撹拌機、温度計、窒素吹込管を有する内容積２
のステンレス製の反応器中に下記の単量体混合
物、及び分散媒組成からなる混合物を仕込んだ。Example 1 Internal volume 2 with stirrer, thermometer and nitrogen blowing tube
A mixture consisting of the following monomer mixture and dispersion medium composition was charged into a stainless steel reactor.
単量体組成；
アクリル酸ブチル 395.0ｇ（79部）
スチレン 100.0ｇ（20部）
メタクリル酸アリル 5.0ｇ（1.0部）
分散媒組成；
脱イオン水 1000ｇ（200部）
ホウ酸 5.0ｇ（1.0部）
炭酸ナトリウム 0.3ｇ（0.06部）
オレイン酸カリ 15ｇ（３部）
過硫酸カリ 1.5ｇ（0.3部）
内容物を撹拌しながら室温で、ｎ−エチルメル
カプタンを100ppm含有する窒素ガスを15分間吹
込んで系内の酸素を追い出した後、ジヤケツトで
内温を60℃に加熱して３時間重合させた。次いで
反応器の内容物を冷却して反応物を取り出した
後、反応器の蓋を開き、反応器の気相部壁を観察
したところ、重合体スケールの付着は見られなか
つた。Monomer composition: Butyl acrylate 395.0g (79 parts) Styrene 100.0g (20 parts) Allyl methacrylate 5.0g (1.0 parts) Dispersion medium composition: Deionized water 1000g (200 parts) Boric acid 5.0g (1.0 parts) Sodium carbonate 0.3 g (0.06 parts) Potassium oleate 15 g (3 parts) Potassium persulfate 1.5 g (0.3 parts) While stirring the contents, nitrogen gas containing 100 ppm of n-ethyl mercaptan was blown into the system at room temperature for 15 minutes. After expelling the oxygen inside the reactor, the inner temperature was heated to 60°C using a jacket and polymerization was carried out for 3 hours. Next, after the contents of the reactor were cooled and the reactants were taken out, the lid of the reactor was opened and the wall of the gas phase section of the reactor was observed, and no polymer scale was found to be attached.
一方、上記重合条件において、ｎ−エチルメル
カプタンを含有しない窒素ガスのみを用いた場合
には反応器の気相部分には単量体供給パイプ及び
反応器壁に重合の付着が生じていた。 On the other hand, under the above polymerization conditions, when only nitrogen gas not containing n-ethyl mercaptan was used, polymerization occurred in the gas phase portion of the reactor, on the monomer supply pipe and on the walls of the reactor.
例 ２
メタクリル酸メチル63部、メタクリル酸メチル
７部、トルエン30部、アゾビスイソブチロニトリ
ル0.01部、ｎ−ドデシルメルカプタン0.03部より
なる混合物を100の撹拌機付オートクレーブに
入れ、メチルメルカプタンを150ppm含有する窒
素ガスで10分間置換して20Kg／cm2に加圧して110
℃で６時間反応させた。Example 2 A mixture consisting of 63 parts of methyl methacrylate, 7 parts of methyl methacrylate, 30 parts of toluene, 0.01 part of azobisisobutyronitrile, and 0.03 part of n-dodecyl mercaptan was placed in a 100 autoclave equipped with a stirrer, and 150 ppm of methyl mercaptan was added. Purge with nitrogen gas for 10 minutes and pressurize to 20Kg/cm 2 to 110
The reaction was carried out at ℃ for 6 hours.
冷却後、内容物を取り出し、オートクレーブ内
の気相部壁を調べたところ重合体スケールの付着
はみられなかつた。 After cooling, the contents were taken out and the walls of the gas phase section inside the autoclave were examined, and no polymer scale was observed.
例 ３
メタクリル酸メチル99部、アクリル酸メチル１
部に対し、Ｎ−ドデシルメルカプタン0.03部、ジ
−tert−ブチルパーオキサイド0.0017部からなる
単量体混合物を窒素下で調合し25／Hrで連続
的に300の反応槽に供給した。反応槽内をメチ
ルメルカプタンを50ppm含有する窒素ガスで加圧
して内圧を8.2Kg／cm2ゲージ圧とし、重合温度は
160℃に調整した。撹拌回転数を60rpmとして十
分な混合を行なわせ、平均滞留時間を4.5時間と
して、1000時間連続運転して重合率62％のシロツ
プを製造した。該反応器の気相部を観察したが重
合体スケールの付着個所はなかつた。Example 3 99 parts of methyl methacrylate, 1 part of methyl acrylate
A monomer mixture consisting of 0.03 parts of N-dodecyl mercaptan and 0.0017 parts of di-tert-butyl peroxide was prepared under nitrogen and continuously fed to 300 reactors at a rate of 25/hr. The inside of the reaction tank was pressurized with nitrogen gas containing 50 ppm of methyl mercaptan to give an internal pressure of 8.2 kg/cm 2 gauge pressure, and the polymerization temperature was
The temperature was adjusted to 160℃. Sufficient mixing was performed by setting the stirring rotation speed to 60 rpm, and the average residence time was set to 4.5 hours, and continuous operation was performed for 1000 hours to produce syrup with a polymerization rate of 62%. The gas phase of the reactor was observed, but no polymer scale was observed.
Claims (1)
ビニル単量体の重合方法において、該重合を行う
反応装置内の反応液上の気相部に沸点が常圧で
100℃以下であるメルカプタンを存在させて重合
を行うことを特徴とするビニル単量体の重合方
法。 ２ 反応装置内の反応液上の気相部に存在させる
メルカプタンの沸点が常圧で40℃以下であること
を特徴とする特許請求の範囲第１項記載のビニル
単量体の重合方法。[Scope of Claims] 1. In a vinyl monomer polymerization method in which vinyl monomer is polymerized while being stirred in a liquid phase, the boiling point of the gas phase above the reaction liquid in the reaction apparatus for the polymerization is at normal pressure. in
A method for polymerizing vinyl monomers, characterized in that polymerization is carried out in the presence of mercaptan at a temperature of 100°C or less. 2. The method for polymerizing vinyl monomers according to claim 1, wherein the boiling point of the mercaptan present in the gas phase above the reaction liquid in the reaction apparatus is 40° C. or lower at normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7729479A JPS56806A (en) | 1979-06-18 | 1979-06-18 | Polymerization of vinyl monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7729479A JPS56806A (en) | 1979-06-18 | 1979-06-18 | Polymerization of vinyl monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56806A JPS56806A (en) | 1981-01-07 |
| JPH0114241B2 true JPH0114241B2 (en) | 1989-03-10 |
Family
ID=13629855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7729479A Granted JPS56806A (en) | 1979-06-18 | 1979-06-18 | Polymerization of vinyl monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56806A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62201902A (en) * | 1986-02-28 | 1987-09-05 | Sekisui Plastics Co Ltd | Prevention of deposition of scale |
| US4803251A (en) * | 1987-11-04 | 1989-02-07 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
-
1979
- 1979-06-18 JP JP7729479A patent/JPS56806A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56806A (en) | 1981-01-07 |
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