JPH07133302A - Preparation of vinyl chloride polymer - Google Patents
Preparation of vinyl chloride polymerInfo
- Publication number
- JPH07133302A JPH07133302A JP30588593A JP30588593A JPH07133302A JP H07133302 A JPH07133302 A JP H07133302A JP 30588593 A JP30588593 A JP 30588593A JP 30588593 A JP30588593 A JP 30588593A JP H07133302 A JPH07133302 A JP H07133302A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- monomer
- polymerization
- wall surface
- scale
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塩化ビニル系単量体の
重合過程における重合器内壁面等へのスケール付着防止
を改良した塩化ビニル系重合体の製法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a vinyl chloride polymer which has improved prevention of scale adhesion to the inner wall surface of a polymerization vessel during the polymerization of vinyl chloride monomer.
【０００２】[0002]
【従来の技術】水性媒体中で塩化ビニルを重合する懸濁
重合および乳化重合において、一般的にスケールと称さ
れる塩化ビニル重合体が重合器内壁面あるいは撹拌翼等
に付着する問題がある。このスケール付着は、重合器の
伝熱効率の低下および剥離スケールの製品重合体への混
入を引き起こし、得られる製品の品質低下の原因とな
る。従来スケールが発生した場合には、重合の前に、そ
れを取り除く清掃作業が行われていたが、そのために重
合器の稼動率を向上させることが困難であった。2. Description of the Related Art In suspension polymerization and emulsion polymerization in which vinyl chloride is polymerized in an aqueous medium, there is a problem that a vinyl chloride polymer, which is generally called scale, adheres to the inner wall surface of a polymerization vessel or a stirring blade. This scale deposition causes a decrease in heat transfer efficiency of the polymerization vessel and contamination of the exfoliation scale with the product polymer, which causes deterioration of the quality of the obtained product. Conventionally, when scale is generated, a cleaning operation for removing it is performed before the polymerization, but it is difficult to improve the operating rate of the polymerization vessel because of this.
【０００３】上記問題の解決のために、塩化ビニルの重
合過程においてスケール付着の発生しない重合方法に関
する検討が種々なされており、例えば染料および／また
は顔料をスケール付着防止剤として用い、それを重合器
内壁面等の塩化ビニル単量体が接触する箇所に予め塗布
しておく方法（特公昭４５ー３０８３５公報）、または
フェノール性化合物と芳香族アルデヒドの反応生成物を
スケール付着防止剤として用いる方法（特開昭５５ー５
４３１７公報）等が提案されている。In order to solve the above-mentioned problems, various studies have been made on a polymerization method in which scale deposition does not occur in the vinyl chloride polymerization process. For example, a dye and / or a pigment is used as a scale deposition inhibitor, which is used as a polymerization reactor. A method in which it is applied in advance to a portion where vinyl chloride monomer contacts such as an inner wall surface (Japanese Patent Publication No. Sho 45-30835), or a method in which a reaction product of a phenolic compound and an aromatic aldehyde is used as a scale adhesion preventive agent ( JP 55-5
4317) and the like have been proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記方
法もあらゆる場合に有効かつ確実にスケール付着を防止
できるのではなく、例えばスケール付着防止剤としてフ
ェノール性化合物と芳香族アルデヒドの反応生成物を用
いた場合には、重合回数が多くなるとスケール防止性能
が劣るという問題があった。また、染料の塗布によるス
ケール防止効果は、その塗布量に大きく依存し、塗布量
が多くなるほど効果は優れるが、塗布量を多くすると、
懸濁重合が不安定になり粗大な重合体粒子の生成比率が
高まるという問題があった。However, the above method cannot effectively and surely prevent scale adhesion in all cases. For example, a reaction product of a phenolic compound and an aromatic aldehyde is used as a scale adhesion inhibitor. In this case, there is a problem that the scale prevention performance is deteriorated as the number of polymerizations increases. Further, the scale prevention effect by application of the dye largely depends on the application amount, and the larger the application amount is, the more excellent the effect is, but when the application amount is increased,
There has been a problem that suspension polymerization becomes unstable and the ratio of formation of coarse polymer particles increases.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、特定の構造を有す
るスルホン酸またはその塩からなるスケール防止剤を、
塩化ビニル単量体等が接触する部分すなわち重合器内壁
等に塗布することにより、優れたスケール防止効果が得
られることを見出し、本発明を完成するに至った。すな
わち、本発明は、塩化ビニル単量体または該単量体を主
成分とするラジカル重合性単量体混合物を水性媒体中で
懸濁重合または乳化重合するにあたり、重合器内壁面お
よび重合器付属設備の単量体が接触する部分に、下記化
２で表されるアミド基を有するスルホン酸（以下アミド
スルホン酸という）またはその塩を予め塗布しておくこ
とを特徴とする塩化ビニル系重合体の製造方法である。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a scale inhibitor comprising a sulfonic acid or a salt thereof having a specific structure,
It has been found that an excellent scale-preventing effect can be obtained by applying it to a portion in contact with a vinyl chloride monomer or the like, that is, the inner wall of a polymerization vessel or the like, and completed the present invention. That is, the present invention provides a method of suspension polymerization or emulsion polymerization of a vinyl chloride monomer or a radical-polymerizable monomer mixture containing the monomer as a main component in suspension polymerization or emulsion polymerization. A vinyl chloride polymer characterized in that a sulfonic acid having an amide group represented by the following chemical formula 2 (hereinafter referred to as amidosulfonic acid) or a salt thereof is applied in advance to a portion of a facility where a monomer contacts. Is a manufacturing method.
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】以下、本発明についてさらに詳しく説明す
る。前記化２におけるＲとしては、炭素数が１〜４個
のアルキル基、炭素数が２〜４個のアルケニル基およ
びフェニル基等が挙げられ、本発明においては、Ｒと
して上記アルケニル基を有するアミドスルホン酸または
その塩（以下これらをアミドスルホン酸等と総称する）
が好ましい。好ましいＲ1〜Ｒ4は、水素原子、メチル基
およびエチル基である。塩を形成する塩基イオンとして
は、ナトリウムイオン、カリウムイオンまたはアンモニ
ウムイオンが好ましい。The present invention will be described in more detail below. Examples of R in the above Chemical Formula 2 include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a phenyl group, and the like, and in the present invention, an amide having the above alkenyl group as R. Sulfonic acid or its salt (hereinafter collectively referred to as amidosulfonic acid, etc.)
Is preferred. Preferred R 1 to R 4 are a hydrogen atom, a methyl group and an ethyl group. The base ion forming a salt is preferably sodium ion, potassium ion or ammonium ion.
【０００８】上記のＲすなわち炭素数が１〜４個のア
ルキル基を有するアミドスルホン酸等の具体例として
は、２−アセトアミドプロパンスルホン酸、２−アセト
アミド−２−メチルプロパンスルホン酸および２−プロ
ピオンアミドプロパンスルホン酸等とそれらの塩が挙げ
られ、また上記のＲすなわちフェニル基を有するアミ
ドスルホン酸等の具体例としては、２−ベンズアミド−
２−メチルプロパンスルホン酸等とそれらの塩が挙げら
れる。Specific examples of the above R, that is, amidosulfonic acid having an alkyl group having 1 to 4 carbon atoms, include 2-acetamidopropanesulfonic acid, 2-acetamido-2-methylpropanesulfonic acid and 2-propion. Examples thereof include amide propane sulfonic acid and salts thereof, and specific examples of the above R, that is, amide sulfonic acid having a phenyl group, include 2-benzamide-
Examples thereof include 2-methylpropanesulfonic acid and salts thereof.
【０００９】本発明において好ましいアミドスルホン酸
等は、前記のとおり、前記化２におけるＲとして炭素数
が２〜４個のアルケニル基を有するものであり、さらに
好ましくは、２−アクリルアミド−２−メチルプロパン
スルホン酸、２−メタクリルアミド−２−メチルプロパ
ンスルホン酸、２−アクリルアミドプロパンスルホン
酸、２−アクリルアミドブタンスルホン酸および３−ア
クリルアミド−２，３−ジメチルブタン−２−スルホン
酸等のアクリル基またはメタクリル基を有するアミドス
ルホン酸またはその塩である。特に好ましくは、２−ア
クリルアミド−２−メチルプロパンスルホン酸およびそ
のナトリウム塩またはカリウム塩である。The amidosulfonic acid and the like preferable in the present invention are those having an alkenyl group having 2 to 4 carbon atoms as R in the above Chemical Formula 2, as described above, and more preferably 2-acrylamido-2-methyl. Acrylic groups such as propanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-acrylamidobutanesulfonic acid and 3-acrylamido-2,3-dimethylbutane-2-sulfonic acid, or It is an amidosulfonic acid having a methacryl group or a salt thereof. Particularly preferred is 2-acrylamido-2-methylpropanesulfonic acid and its sodium salt or potassium salt.
【００１０】アクリル基またはメタクリル基を有するア
ミドスルホン酸等が、本発明においてより優れたスケー
ル防止効果を奏する理由は定かではないが、重合器壁面
で起こる塩化ビニル単量体等の重合が、ラジカル重合性
が高い反面、塩化ビニル単量体との共重合反応比が低い
アクリルアミドまたはメタクリルアミドによって停止す
るのではないかと推定される。Although it is not clear why an amide sulfonic acid having an acrylic group or a methacrylic group has a more excellent scale preventing effect in the present invention, the polymerization of vinyl chloride monomer or the like which occurs on the wall surface of the polymerization vessel is a radical. Although it has high polymerizability, it is presumed that it may be terminated by acrylamide or methacrylamide having a low copolymerization reaction ratio with the vinyl chloride monomer.
【００１１】上記アミドスルホン酸等は、以下の方法に
より重合器内壁面ならびにバッフルおよび攪拌ペラ等の
重合器付属設備に塗布できる。すなわち、上記アミドス
ルホン酸等を水、メタノールまたはエタノール等の溶剤
に0.１〜5.０重量％程度の濃度に溶解した溶液を、刷毛
塗りまたはスプレー塗装等によって塗布できる。塗布
後、４０〜８０℃程度の熱風で一旦乾燥させることが好
ましい。乾燥させることにより、スケール防止効果が長
期間持続する。溶剤としては、メタノールおよびエタノ
ール等の低級アルコールが好ましく、低級アルコールに
不溶なアミドスルホン酸のアルカリ金属塩等は、水と低
級アルコールの混合溶剤が好ましい。アミドスルホン酸
等の好ましい塗布量は、0.００１〜１０ｇ／ｍ2であ
る。The above-mentioned amide sulfonic acid and the like can be applied to the inner wall surface of the polymerization vessel and equipment attached to the polymerization vessel such as baffles and stirring propellers by the following method. That is, a solution prepared by dissolving the above amide sulfonic acid or the like in a solvent such as water, methanol or ethanol to a concentration of about 0.1 to 5.0% by weight can be applied by brush coating or spray coating. After coating, it is preferable to once dry with hot air of about 40 to 80 ° C. By drying, the scale prevention effect lasts for a long time. The solvent is preferably a lower alcohol such as methanol and ethanol, and the alkali metal salt of amidosulfonic acid insoluble in the lower alcohol is preferably a mixed solvent of water and the lower alcohol. The preferable coating amount of amide sulfonic acid or the like is 0.001 to 10 g / m 2 .
【００１２】本発明においては、アミドスルホン酸等の
塗布面への付着性を高めるために、例えばロジン等の天
然高分子またはノニオン型のフッ素系界面活性剤のよう
な公知の定着剤を併用できる。また、本発明におけるア
ミドスルホン酸等と共に、スケール防止剤の一種である
ピロガロールとアセトンの縮合物（特開平５−１２５１
１３号公報）を併用してもよく、併用が好ましいピロガ
ロールとアセトンの縮合物は、ピロガロール１モル当た
りアセトンを0.７５〜１モル使用して、水性媒体中また
はアルコール性媒体中で酸性条件で両者を縮合させて得
られる、融点が１００〜３００℃の縮合物である。In the present invention, a known fixing agent such as a natural polymer such as rosin or a nonionic fluorine-containing surfactant can be used in combination in order to improve the adhesion of amide sulfonic acid or the like to the coated surface. . In addition to the amide sulfonic acid and the like in the present invention, a condensate of pyrogallol, which is a kind of scale inhibitor, and acetone (Japanese Patent Application Laid-Open No. 5-1251).
13) may be used in combination, and the condensate of pyrogallol and acetone, which is preferably used in combination, contains 0.75 to 1 mol of acetone per mol of pyrogallol under acidic conditions in an aqueous medium or an alcoholic medium. It is a condensate having a melting point of 100 to 300 ° C. obtained by condensing both.
【００１３】上記アミドスルホン酸等が塗布された重合
器に水性媒体を仕込み、攪拌下に塩化ビニル単量体また
は該単量体を主成分とするラジカル重合単量体混合物
を、常法に従い懸濁重合または乳化重合することによ
り、スケール付着が起こらない状態で多数回の重合を繰
り返して、塩化ビニル系重合体を製造すことができる。
塩化ビニル単量体等の分散安定剤としては、部分ケン化
ビニルアルコールおよびセルロース誘導体等が使用で
き、重合開始剤としては、イソブチリルパーオキサイ
ド、ラウリルパーオキサイド、ジイソプロピルパーオキ
シジカーボネート、２−エチルヘキシルパーオキシジカ
ーボネートおよびｔ−ブチルパーオキシピバレート等が
使用できる。An aqueous medium is charged into a polymerization vessel coated with the above-mentioned amide sulfonic acid and the vinyl chloride monomer or a radical-polymerized monomer mixture containing the monomer as a main component is suspended under stirring according to a conventional method. By carrying out turbid polymerization or emulsion polymerization, it is possible to produce a vinyl chloride polymer by repeating the polymerization a number of times in a state where scale adhesion does not occur.
As the dispersion stabilizer of vinyl chloride monomer and the like, partially saponified vinyl alcohol and cellulose derivative can be used, and as the polymerization initiator, isobutyryl peroxide, lauryl peroxide, diisopropyl peroxydicarbonate, 2-ethylhexyl are used. Peroxydicarbonate and t-butyl peroxypivalate can be used.
【００１４】また、塩化ビニル単量体と共に使用できる
ラジカル重合性単量体としては、酢酸ビニル、プロピル
ビニルエーテル、ブチルビニルエーテル、アクリル酸メ
チル、塩化ビニリデン、プロピレンおよびアルキルマレ
イミド等が挙げられる。Further, the radical-polymerizable monomer which can be used together with the vinyl chloride monomer includes vinyl acetate, propyl vinyl ether, butyl vinyl ether, methyl acrylate, vinylidene chloride, propylene and alkylmaleimide.
【００１５】[0015]
【実施例】以下、実施例および比較例を挙げて、本発明
を更に具体的に説明する。 ＜実施例１＞メタノール１００ｇに２−アクリルアミド
−２−メチルプロパンスルホン酸１ｇを溶解し塗布液を
調製した。この塗布液を刷毛塗りにより、攪拌機を有す
る５Ｌオートクレーブの内壁面に薄く塗布し、さらに塗
布面を４０℃程度に加温して１０分乾燥させた。その後
内壁面を室温まで冷却し、以下の原料を仕込んだ。すな
わち、純水2,７００ｇ、部分ケン化ポリビニルアルコー
ル２ｇおよび２−エチルヘキシルパーオキシジカーボネ
ート1.２ｇをオートクレーブに仕込み、真空ポンプによ
り−６００ｍｍＨｇまで脱気し、さらに塩化ビニル単量
体を2,０００ｇ仕込んだ。次いで内部温度を５８℃に昇
温し、その温度に７時間維持した後、重合を停止させ
た。得られたポリ塩化ビニル粒子の粒径は、目的どお
り、平均で１２０〜１５０μｍであった。EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. <Example 1> 1 g of 2-acrylamido-2-methylpropanesulfonic acid was dissolved in 100 g of methanol to prepare a coating solution. This coating solution was thinly applied to the inner wall surface of a 5 L autoclave having a stirrer by brush coating, and the coated surface was heated to about 40 ° C. and dried for 10 minutes. After that, the inner wall surface was cooled to room temperature, and the following raw materials were charged. That is, 2,700 g of pure water, 2 g of partially saponified polyvinyl alcohol and 1.2 g of 2-ethylhexyl peroxydicarbonate were charged into an autoclave, degassed by a vacuum pump to -600 mmHg, and further 2000 g of vinyl chloride monomer. I prepared it. Then, the internal temperature was raised to 58 ° C., the temperature was maintained for 7 hours, and then the polymerization was stopped. The particle size of the obtained polyvinyl chloride particles was 120 to 150 μm on average as intended.
【００１６】重合後、重合器内壁面を純水で洗浄し、同
一の重合器を使用して、上記と同様な重合を行うという
操作を１０回繰り返した。各回の重合後に、内壁面のス
ケール付着状態を目視で観測した。その結果、重合回数
１０回の時点でもなおスケールの付着は認められなかっ
た。After the polymerization, the inner wall surface of the polymerization vessel was washed with pure water, and the same polymerization was carried out using the same polymerization vessel, which was repeated 10 times. After each polymerization, the scale adhesion state on the inner wall surface was visually observed. As a result, no scale adhesion was observed even after 10 polymerizations.
【００１７】＜実施例２＞スケール防止剤として２−ア
セトアミド−２−メチルプロパンスルホン酸を使用する
以外は、すべて実施例１と同様な条件を採用して塩化ビ
ニルの重合を行った。この場合は、重合回数７回までは
スケールの付着は認められなかった。なお、得られたポ
リ塩化ビニルは平均粒径１２０〜１５０μｍの粒子であ
り、品質的に問題はなかった。Example 2 Vinyl chloride was polymerized under the same conditions as in Example 1 except that 2-acetamido-2-methylpropanesulfonic acid was used as the scale inhibitor. In this case, no scale adhesion was observed up to the number of polymerizations of 7. The obtained polyvinyl chloride was particles having an average particle size of 120 to 150 μm, and there was no problem in quality.
【００１８】＜比較例１＞重合器内壁面等に塗布する塗
布液として、メタノール５００ｇにニグロシンブラック
２ｇを溶解した塗布液を使用した以外は、実施例１と同
様にして塩化ビニルの重合を行なった。この場合は、重
合回数８回まではスケールの付着は認められなかった
が、重合自体が不安定であり、得られたポリ塩化ビニル
には、粒径が３５０μｍ程度の粗大粒子が多く含まれて
いた。<Comparative Example 1> Polymerization of vinyl chloride is carried out in the same manner as in Example 1 except that a coating solution prepared by dissolving 2 g of nigrosine black in 500 g of methanol is used as a coating solution for coating the inner wall surface of the polymerization vessel. It was In this case, no scale adhesion was observed up to 8 times of polymerization, but the polymerization itself was unstable, and the obtained polyvinyl chloride contained a lot of coarse particles having a particle size of about 350 μm. It was
【００１９】[0019]
【発明の効果】本発明によれば、多数回重合を繰り返し
ても重合体スケールの付着を効果的に防止でき、かつ重
合が安定に進行するので、スケール除去作業を頻繁に行
うことなく、目的とする粒径を有する高品質の塩化ビニ
ル系重合体を効率的に製造できる。EFFECTS OF THE INVENTION According to the present invention, even if the polymerization is repeated many times, the adhesion of polymer scale can be effectively prevented, and the polymerization proceeds stably. It is possible to efficiently produce a high-quality vinyl chloride polymer having a particle size of
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浅田 直則 愛知県名古屋市港区船見町１番地の１ 東 亞合成化学工業株式会社名古屋総合研究所 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naonori Asada 1-1 Funami-cho, Minato-ku, Nagoya, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute
Claims (1)
分とするラジカル重合性単量体混合物を水性媒体中で懸
濁重合または乳化重合するにあたり、重合器内壁面およ
び重合器付属設備の単量体が接触する部分に、下記化１
で表されるアミド基を有するスルホン酸またはその塩を
予め塗布しておくことを特徴とする塩化ビニル系重合体
の製造方法。 【化１】 1. An inner wall surface of a polymerization vessel and equipment attached to the polymerization vessel when suspension-polymerizing or emulsion-polymerizing a vinyl chloride monomer or a radical-polymerizable monomer mixture containing the monomer as a main component in an aqueous medium. The following chemical formula 1
A method for producing a vinyl chloride polymer, characterized in that a sulfonic acid having an amide group represented by or its salt is applied in advance. [Chemical 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30588593A JP3418926B2 (en) | 1993-11-11 | 1993-11-11 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30588593A JP3418926B2 (en) | 1993-11-11 | 1993-11-11 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07133302A true JPH07133302A (en) | 1995-05-23 |
| JP3418926B2 JP3418926B2 (en) | 2003-06-23 |
Family
ID=17950489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30588593A Expired - Fee Related JP3418926B2 (en) | 1993-11-11 | 1993-11-11 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3418926B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9434844B2 (en) | 2011-10-12 | 2016-09-06 | Ineos Europe Ag | Additive, composition comprising it and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5794342U (en) * | 1980-11-29 | 1982-06-10 | ||
| JPS6049739U (en) * | 1983-09-16 | 1985-04-08 | 株式会社クボタ | Combine waste straw processing equipment |
| JPS60171144U (en) * | 1984-04-19 | 1985-11-13 | セイレイ工業株式会社 | Sorting device in combine harvester |
| JPS6125418A (en) * | 1984-07-16 | 1986-02-04 | 井関農機株式会社 | Dust discharge part and cutter part in automatic feed-in type threshing apparatus |
-
1993
- 1993-11-11 JP JP30588593A patent/JP3418926B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5794342U (en) * | 1980-11-29 | 1982-06-10 | ||
| JPS6049739U (en) * | 1983-09-16 | 1985-04-08 | 株式会社クボタ | Combine waste straw processing equipment |
| JPS60171144U (en) * | 1984-04-19 | 1985-11-13 | セイレイ工業株式会社 | Sorting device in combine harvester |
| JPS6125418A (en) * | 1984-07-16 | 1986-02-04 | 井関農機株式会社 | Dust discharge part and cutter part in automatic feed-in type threshing apparatus |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9434844B2 (en) | 2011-10-12 | 2016-09-06 | Ineos Europe Ag | Additive, composition comprising it and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3418926B2 (en) | 2003-06-23 |
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