JPH111457A - 2,2'-azobis(2-methylpropionate) excellent in storage stability - Google Patents
2,2'-azobis(2-methylpropionate) excellent in storage stabilityInfo
- Publication number
- JPH111457A JPH111457A JP12419098A JP12419098A JPH111457A JP H111457 A JPH111457 A JP H111457A JP 12419098 A JP12419098 A JP 12419098A JP 12419098 A JP12419098 A JP 12419098A JP H111457 A JPH111457 A JP H111457A
- Authority
- JP
- Japan
- Prior art keywords
- azobis
- methylpropionate
- pieces
- strip
- fine pieces
- 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
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 238000003860 storage Methods 0.000 title abstract description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000007790 scraping Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 9
- 239000002184 metal Substances 0.000 description 6
- 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 5
- 239000007877 V-601 Substances 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- -1 Dimethyl 2,2'-azobis Chemical compound 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の利用分野】本発明は、取扱が容易で保存中にブ
ロック化が生じない、ジメチル ２，２’−アゾビス
（２−メチルプロピオネート）の細片に関する。The present invention relates to strips of dimethyl 2,2'-azobis (2-methylpropionate) which are easy to handle and do not block during storage.
【０００２】[0002]
【発明の背景】ジメチル ２，２’−アゾビス（２−メ
チルプロピオネート）は、２，２’−アゾビスイソブチ
ロニトリル(AIBN)とほぼ同等の分解活性及び重合活性を
有する重合開始剤であるが、ＡＩＢＮに比べ毒性が低く
また溶剤溶解性に優れていることからＡＩＢＮに替わる
開始剤として各種ビニルモノマーの重合反応に使用され
る。BACKGROUND OF THE INVENTION Dimethyl 2,2'-azobis (2-methylpropionate) is a polymerization initiator having almost the same decomposition activity and polymerization activity as 2,2'-azobisisobutyronitrile (AIBN). However, since it is less toxic and has better solvent solubility than AIBN, it is used as an initiator instead of AIBN in the polymerization reaction of various vinyl monomers.
【０００３】現在、この化合物は、ブロック形状として
販売されているが、これには種々の問題点がある。即
ち、例えば、粉末状のものに比較して計量し難い、
大きな固まりを粉砕してブロック形状としているが、こ
の際に機械を使用すると摩擦等によりジメチル ２，
２’−アゾビス（２−メチルプロピオネート）自体が分
解する虞があるため、人手により粉砕しなければなら
ず、ブロック形状のものを調製するのに手間がかかる等
の問題点がそれである。At present, this compound is sold in the form of a block, but this has various problems. That is, for example, it is difficult to measure compared to a powdery one,
Large blocks are crushed to form blocks, but when using a machine at this time, dimethyl 2,2
Since 2'-azobis (2-methylpropionate) itself may be decomposed, it must be pulverized by hand, and it takes time and effort to prepare a block-shaped product.
【０００４】そのため、これを粉末状、フレーク状とし
た販売形態について検討を行ったが、ジメチル ２，
２’−アゾビス（２−メチルプロピオネート）は融点が
室温付近（２２〜３２℃）にあるため、粉末状或いは単
にフレーク状としただけでは保存中に結晶と結晶が付着
してブロック化する現象が認められ、その結果、使用時
の計量が難しくなり作業性を著しく低下させるという問
題点が生ずることが判った。また、作業性を向上させる
ため融点以上の温度で保存すれば、液状となり計量も容
易になるが、液状では保存安定性が悪く含量の低下を招
く等の問題点もあった。[0004] For this reason, a study was made on a sales form in powder or flake form.
Since 2'-azobis (2-methylpropionate) has a melting point near room temperature (22 to 32 [deg.] C.), if it is made into powder or simply flakes, crystals adhere to each other during storage and block. Phenomenon was observed, and as a result, it was found that there was a problem that it became difficult to measure when used and the workability was remarkably reduced. Further, when stored at a temperature equal to or higher than the melting point in order to improve workability, it becomes liquid and the measurement is easy, but there is a problem that the liquid has poor storage stability and lowers the content.
【０００５】[0005]
【発明が解決すべき課題】上記した如き問題点を有さ
ず、取扱が容易なジメチル ２，２’−アゾビス（２−
メチルプロピオネート）の細片の提供をその課題とす
る。DISCLOSURE OF THE INVENTION Dimethyl 2,2'-azobis (2-
It is an object of the present invention to provide a strip of methyl propionate).
【０００６】[0006]
【課題を解決するための手段】本発明は、 （１）厚さが０．５〜５ｍｍで、最小径が２．３８ｍｍ
以上であるものを５０％以上含む、ジメチル ２，２’
−アゾビス（２−メチルプロピオネート）の細片、の発
明である。The present invention provides: (1) a thickness of 0.5 to 5 mm and a minimum diameter of 2.38 mm;
Dimethyl 2,2 'containing at least 50% of the above
Azobis (2-methylpropionate) strips.
【０００７】即ち、本発明者らは、各種用途において、
作業性に優れ、安定に保存できるジメチル ２，２’−
アゾビス（２−メチルプロピオネート）を提供すべく、
その結晶化方法について鋭意研究を重ねた結果、溶融状
態とした本品を薄く伸展しながら冷却し結晶化させた後
掻き取り、一定形状の細片とすることにより、品質的に
も問題なく、強度、経時安定性とも優れ、上記した目的
を充分達成し得るジメチル ２，２’−アゾビス（２−
メチルプロピオネート）の細片が得られることを見いだ
し、本発明を完成するに至った。[0007] That is, the present inventors, in various applications,
Dimethyl 2,2'- which has excellent workability and can be stored stably
To provide azobis (2-methylpropionate)
As a result of intensive research on the crystallization method, this product in the molten state was cooled and crystallized while stretching thinly, scraped off, and made into strips of a certain shape, without any problem in quality, Dimethyl 2,2'-azobis (2-
(Methyl propionate) was obtained, and the present invention was completed.
【０００８】本発明の細片は、例えば以下の方法により
容易に得られる。即ち、先ず、溶融状態としたジメチル
２，２’−アゾビス（２−メチルプロピオネート）を
冷却した板状物表面に薄く伸展させることにより結晶化
させ、これを掻き取り、必要に応じて粉砕機や篩等を用
いて形を整え、一定形状の細片とすればよい。この際に
用いられる板状物としては、本発明の目的を達成し得る
ものであればその材質、形状等は特に限定されないが、
望ましくは熱伝導性の高い金属の板でその表面が滑らか
なものが良く、より具体的には、そのような特性を備え
た例えば金属製ドラム、移動式の金属板（例えばベルト
コンベアを利用したもの等）等が好ましく挙げられる。
板状物として金属製ドラムを用いた場合を例に取り本発
明の細片の調製方法を詳述すると例えば以下の如くであ
る。即ち、冷却した金属製ドラムを回転させながらその
表面に、溶融させたジメチル ２，２’−アゾビス（２
−メチルプロピオネート）を所定の厚さとなるように薄
く流下し、晶析した結晶をスクレーパー等を用いてかき
とれば目的の細片が得られる。尚、細片の厚さを調節す
るために邪魔板を用いて整形したり、プレッシャーロー
ルを用いて圧縮して結晶化させても良く、必要に応じ
て、かきとり後、形を整えるための粉砕機や篩等を用い
ても良い。The strip of the present invention can be easily obtained, for example, by the following method. That is, first, dimethyl 2,2'-azobis (2-methylpropionate) in a molten state is crystallized by thinly spreading it on the surface of a cooled plate-like material, scraped off, and crushed if necessary. What is necessary is just to shape it using a machine, a sieve, etc., and to make a strip of a fixed shape. The material used in this case is not particularly limited as long as it can achieve the object of the present invention.
Desirably, a metal plate having a high thermal conductivity and a smooth surface is better. More specifically, for example, a metal drum or a movable metal plate (for example, using a belt conveyor) having such characteristics is used. And the like).
Taking the case where a metal drum is used as a plate-like material as an example, the method for preparing the strip of the present invention will be described in detail as follows, for example. That is, while rotating a cooled metal drum, the surface of the melted dimethyl 2,2′-azobis (2
-Methyl propionate) is allowed to flow down to a predetermined thickness, and the crystallized crystals are scraped off with a scraper or the like to obtain the desired strip. In addition, it may be shaped using a baffle plate to adjust the thickness of the strip, or may be crystallized by compressing using a pressure roll.If necessary, after scraping, pulverization to adjust the shape A machine or a sieve may be used.
【０００９】上記の方法に於ける、ドラム等の接液表面
温度は通常−３０〜５℃であり、好ましくは−２０〜−
１０℃である。また、その回転速度（移動式の金属板の
場合はその移動速度、また、ベルト式コンベアを用いる
場合はその駆動速度）は、特に限定されず、目的の厚み
の細片が得られるように適宜選択すればよい。In the above method, the surface temperature of the liquid contacting the drum or the like is usually -30 to 5 ° C, preferably -20 to-
10 ° C. The rotation speed (the moving speed in the case of a movable metal plate, and the driving speed in the case of using a belt-type conveyor) is not particularly limited, and is appropriately set so that strips having a desired thickness are obtained. Just choose.
【００１０】本発明の細片の厚さは、通常０．５〜５ｍ
ｍ、好ましくは１〜５ｍｍ、より好ましくは１．５〜４
ｍｍである。厚さが薄すぎると、細片が脆く壊れ易いた
め保存中にブロック化しやすくなる。また、厚すぎる
と、計量し難くなり、また、溶媒への溶解速度が遅くな
る等の問題が生じ作業性が低下する。The thickness of the strip of the present invention is usually 0.5 to 5 m
m, preferably 1-5 mm, more preferably 1.5-4
mm. If the thickness is too small, the strips are brittle and easily broken, so that they tend to be blocked during storage. On the other hand, if it is too thick, it will be difficult to measure, and there will be problems such as a slow rate of dissolution in the solvent, and the workability will be reduced.
【００１１】細片の径（厚みではなく）は、特に限定さ
れないが、取扱のし易さ等を考慮すると、２．３８ｍｍ
以上（即ち、８メッシュの篩を通過し得ないもの）、好
ましくは２．３８〜５０ｍｍ、より好ましくは４．７６
（即ち、４メッシュの篩を通過し得ないもの）〜５０ｍ
ｍ、更に好ましくは４．７６〜２０ｍｍである。[0011] The diameter (not the thickness) of the strip is not particularly limited, but is 2.38 mm in consideration of easy handling.
Above (that is, those which cannot pass through an 8-mesh sieve), preferably 2.38 to 50 mm, more preferably 4.76.
(Ie, those that cannot pass through a 4-mesh sieve)-50 m
m, more preferably 4.76 to 20 mm.
【００１２】本発明の細片は、厚さが０．５〜５ｍｍ
で、最小径が２．３８ｍｍ以上である細片を５０％以
上、好ましくは６０％以上、より好ましくは７０％以上
含有するものであるが、更に最小径が０．４２ｍｍ以下
のもの（即ち、１６メッシュの篩いを通過するもの）の
含量は５％以下であることが望ましい。即ち、微細なも
のの含量が少ない方がブロック化現象を生じがたいから
である。The strip of the present invention has a thickness of 0.5 to 5 mm.
And containing 50% or more, preferably 60% or more, more preferably 70% or more of flakes having a minimum diameter of 2.38 mm or more, and further having a minimum diameter of 0.42 mm or less (ie, It is desirable that the content of the material passing through a 16-mesh sieve is 5% or less. That is, the smaller the content of fine particles, the more difficult it is to cause the blocking phenomenon.
【００１３】[0013]
【実施例】 実施例１．溶融させたジメチル ２，２’−アゾビス
（２−メチルプロピオネート）（以下、Ｖ−６０１と略
記する。和光純薬工業（株）製）を、ドラム表面を−１
５℃に冷却したドラムクーラー（三菱化成エンジニアリ
ング社製）を回転させながらその表面に流下し、プレッ
シャーロールで圧縮しながら結晶化させた後、結晶をド
ラム表面からかきとり、粉砕機を通してＶ−６０１の細
片を得た。細片の厚さは、大部分が１.５ｍｍ以上５ｍ
ｍ未満であった。また、得られた細片の粒度分布は、下
記の通りであった。 ６０メッシュ通過 （０．２５ｍｍ未満） ０．４％ ４０〜６０メッシュ（０．２５〜０．４２ｍｍ） １．６％ １６〜４０メッシュ（０．４２〜１．１９ｍｍ） ６．８％ ８〜１６メッシュ（１．１９〜２．３８ｍｍ） ２０．３％ ８〜４メッシュ （２．３８〜４．７６ｍｍ） ２０．６％ ４メッシュ以下 （４．７６ｍｍ以上） ５０．３％ このようにして得られた細片（即ち、最小径２．３８ｍ
ｍ以上のもの７０．９％からなる細片）１．６Ｋｇをポ
リ袋に入れ、これをダンボール箱（底辺２２×２３ｃ
ｍ）中に均一になるように収容した。この細片の上に６
Ｋｇの重りを乗せ、１０℃で保存した（荷重試験）。経
日的に細片の状態を観察したが、保存後３カ月後でもブ
ロック化現象は認められなかった。Embodiment 1 Melted dimethyl 2,2'-azobis (2-methylpropionate) (hereinafter abbreviated as V-601; manufactured by Wako Pure Chemical Industries, Ltd.)
A drum cooler (manufactured by Mitsubishi Kasei Engineering Co., Ltd.) cooled to 5 ° C. is allowed to flow down onto the surface thereof while rotating, and is crystallized while being compressed by a pressure roll. A strip was obtained. The thickness of the strip is mostly 1.5mm or more and 5m
m. The particle size distribution of the obtained strip was as follows. 60 mesh passage (less than 0.25 mm) 0.4% 40 to 60 mesh (0.25 to 0.42 mm) 1.6% 16 to 40 mesh (0.42 to 1.19 mm) 6.8% 8 to 16 Mesh (1.19 to 2.38 mm) 20.3% 8 to 4 mesh (2.38 to 4.76 mm) 20.6% 4 mesh or less (4.76 mm or more) 50.3% Obtained in this way Strip (ie, minimum diameter 2.38m)
1.6 kg in a plastic bag, which is placed in a cardboard box (base 22 × 23c)
m). 6 on this strip
A Kg weight was placed and stored at 10 ° C. (load test). The state of the strips was observed over time, but no blocking phenomenon was observed even three months after storage.
【００１４】また、得られた細片を８メッシュの篩にか
けた後、８メッシュの篩を通過しない細片含量が５０％
となるように、８メッシュ通過細片と混合した。これを
上記した荷重試験にかけたところ、保存後３カ月後でも
ブロック化現象は認められなかった。Further, after the obtained strips are sieved through an 8 mesh screen, the content of the strips that do not pass through the 8 mesh screen is 50%.
And mixed with 8 mesh passing strips to obtain When this was subjected to the above-mentioned load test, no blocking phenomenon was observed even after 3 months from the storage.
【００１５】比較例１．溶融させたＶ−６０１をドラム
フレーカー（パウレック社製）の供給パンに入れ、−３
℃に冷却したドラム表面をこれに浸漬して、回転させ、
ドラム上で結晶化させた後、結晶をドラム表面から掻き
取り、実施例１で用いた粉砕機を通してＶ−６０１の細
片を得た。尚、細片の厚さは、大部分が０．２ｍｍ以上
０．４ｍｍ未満であった。また、得られた細片の粒度分
布は、下記の通りであった。 ６０メッシュ通過 （０．２５ｍｍ未満） １．４％ ４０〜６０メッシュ（０．２５〜０．４２ｍｍ） ５．６％ １６〜４０メッシュ（０．４２〜１．１９ｍｍ） １５．８％ ８〜１６メッシュ（１．１９〜２．３８ｍｍ） ４０．３％ ８〜４メッシュ （２．３８〜４．７６ｍｍ） ２０．９％ ４メッシュ以下 （４．７６ｍｍ以上） １６．０％ このようにして得られた細片を実施例１と同じ条件で荷
重試験にかけた。その結果、一週間後にはブロック化し
ていることが確認された。Comparative Example 1 The melted V-601 was put into a supply pan of a drum flaker (manufactured by Powrex), and -3 was added.
The drum surface cooled to ℃ is immersed in this and rotated,
After crystallization on the drum, the crystals were scraped off the drum surface and passed through the grinder used in Example 1 to obtain V-601 strips. In addition, the thickness of the strip was mostly 0.2 mm or more and less than 0.4 mm. The particle size distribution of the obtained strip was as follows. 60 mesh passage (less than 0.25 mm) 1.4% 40 to 60 mesh (0.25 to 0.42 mm) 5.6% 16 to 40 mesh (0.42 to 1.19 mm) 15.8% 8 to 16 Mesh (1.19 to 2.38 mm) 40.3% 8 to 4 mesh (2.38 to 4.76 mm) 20.9% 4 mesh or less (4.76 mm or more) 16.0% The strip was subjected to a load test under the same conditions as in Example 1. As a result, it was confirmed that it was blocked one week later.
【００１６】比較例２．比較例１で得られたＶ−６０１
の細片の中から、８メッシュの篩を通過しなかったもの
のみを集め、これを実施例１と同じ条件で荷重試験にか
けた。その結果、１カ月後にはブロック化していること
が確認された。このことから、最小径が２．３８ｍｍ以
上の細片であっても厚さが０．４ｍｍ未満のものでは本
発明の細片の如き効果は得られないことが判る。Comparative Example 2 V-601 obtained in Comparative Example 1
Among the strips, only those that did not pass through the 8-mesh sieve were collected and subjected to a load test under the same conditions as in Example 1. As a result, it was confirmed that it was blocked one month later. From this, it can be seen that even if the minimum diameter is 2.38 mm or more, if the thickness is less than 0.4 mm, the effect of the present invention cannot be obtained.
【００１７】[0017]
【発明の効果】上述した如く、本発明は、ジメチル
２，２’−アゾビス（２−メチルプロピオネート）の細
片及びその製造方法を提供するものであり、本発明の細
片は、取扱が容易で保存中にブロック化が生じない、と
いう効果を奏するので斯業に貢献するところ大なる発明
である。As described above, the present invention relates to dimethyl
An object of the present invention is to provide a strip of 2,2'-azobis (2-methylpropionate) and a method for producing the strip. The strip of the present invention is easy to handle and does not block during storage. Therefore, it is a great invention that contributes to the industry.
Claims (1)
８ｍｍ以上であるものを５０％以上含む、ジメチル
２，２’−アゾビス（２−メチルプロピオネート）の細
片。1. The thickness is 0.5 to 5 mm and the minimum diameter is 2.3.
Dimethyl containing 50% or more of those having a size of 8 mm or more
Strips of 2,2'-azobis (2-methylpropionate).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12419098A JP3932670B2 (en) | 1997-04-18 | 1998-04-17 | Dimethyl 2,2'-azobis (2-methylpropionate) with excellent storage stability |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11616497 | 1997-04-18 | ||
| JP9-116164 | 1997-04-18 | ||
| JP12419098A JP3932670B2 (en) | 1997-04-18 | 1998-04-17 | Dimethyl 2,2'-azobis (2-methylpropionate) with excellent storage stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH111457A true JPH111457A (en) | 1999-01-06 |
| JP3932670B2 JP3932670B2 (en) | 2007-06-20 |
Family
ID=26454542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12419098A Expired - Fee Related JP3932670B2 (en) | 1997-04-18 | 1998-04-17 | Dimethyl 2,2'-azobis (2-methylpropionate) with excellent storage stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3932670B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012062238A (en) * | 2010-09-18 | 2012-03-29 | Sekisui Chem Co Ltd | Gas generating agent and micro-pump |
-
1998
- 1998-04-17 JP JP12419098A patent/JP3932670B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012062238A (en) * | 2010-09-18 | 2012-03-29 | Sekisui Chem Co Ltd | Gas generating agent and micro-pump |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3932670B2 (en) | 2007-06-20 |
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