JPS61134343A - Photo-chlorination of acrylic acid or acrylic acid ester - Google Patents
Photo-chlorination of acrylic acid or acrylic acid esterInfo
- Publication number
- JPS61134343A JPS61134343A JP25572884A JP25572884A JPS61134343A JP S61134343 A JPS61134343 A JP S61134343A JP 25572884 A JP25572884 A JP 25572884A JP 25572884 A JP25572884 A JP 25572884A JP S61134343 A JPS61134343 A JP S61134343A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- ester
- acrylic
- chlorine
- photo
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、アクリル酸あるいはアクリル酸エステルの光
塩素化方法に関する。アクリル酸及びアクリル酸エステ
々の塩素化によって得られる１、２−ジクロルプロピオ
ン酸及びそのエステルは、各種工業薬品の中間体として
重要であり、特に金属封鎖剤、洗剤用とルダーとしての
用途を持つポリ−α−ヒドロキシアクリル酸ソーダの中
間原料として重要である。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for photochlorination of acrylic acid or acrylic ester. 1,2-dichloropropionic acid and its esters obtained by chlorination of acrylic acid and acrylic acid esters are important as intermediates for various industrial chemicals, and are particularly useful as sequestering agents, detergents, and lubricants. It is important as an intermediate raw material for sodium poly-α-hydroxyacrylate.
（従来の技術）
アクリル酸及びアクリル酸エステルへの塩素付加反応が
光によって促進される事は既に知られている。しかし、
単にアクリル酸あるいはアクリル酸エステルを含む反応
系に、光照射下塩素を吹き込んだ場合には、アクリル酸
あるいはアクリル酸エステルの重合反応が同時に進行す
るため収率良く１，２−ジクロルプロピオン酸あるいは
そのエステルを得る事が出来ない。これを解決する方法
として、公開特許昭４９−１３３３１９号明細書におい
て、アンチモン、ビスマスなどの金属化合物を共存させ
ておき、アクリル酸あるいはアクリル酸エステルを含む
反応系に、光照射下塩素を吹き込む方法が提案されてい
る。(Prior Art) It is already known that the chlorine addition reaction to acrylic acid and acrylic esters is promoted by light. but,
If chlorine is simply blown into a reaction system containing acrylic acid or acrylic ester under light irradiation, the polymerization reaction of acrylic acid or acrylic ester proceeds simultaneously, resulting in 1,2-dichloropropionic acid or 1,2-dichloropropionic acid or acrylic ester in high yield. I can't get that ester. As a method to solve this problem, as disclosed in Japanese Patent Publication No. 133319/1984, a method is proposed in which metal compounds such as antimony and bismuth are allowed to coexist, and chlorine is blown into the reaction system containing acrylic acid or acrylic acid ester under light irradiation. is proposed.
（発明が解決しようとする問題点）
しかしながら、アンチモン、ビスマス等の金属化合物を
共存させておく方法においては、生成物に対する重金属
汚染、排水の重金属汚染、オペレーターの重金属被毒等
、重金属を使用する事から発生ぼる種々の問題を持って
いる。(Problems to be solved by the invention) However, in the method of coexisting metal compounds such as antimony and bismuth, heavy metals are used, such as heavy metal contamination of products, heavy metal contamination of wastewater, and heavy metal poisoning of operators. There are various problems that arise from this.
本発明の目的は、金属化合物等の触媒を°使用せず、し
かもアクリル酸あるいはアクリル酸エステルの重合反応
を抑制し、高収率で１．２−ジクロルプロピオン酸ある
いは１．２−ジクロルプロピオン酸エステルを製造する
事にある。The object of the present invention is to suppress the polymerization reaction of acrylic acid or acrylic ester without using catalysts such as metal compounds, and to produce 1,2-dichloropropionic acid or 1,2-dichloropropionic acid in high yield. The purpose is to produce propionate ester.
（問題点を解決するための手段）
本発明者らは、アクリル酸あるいはアクリル酸エステル
の光塩素化反応について長年にわたり研究を続け、その
結果、ある一時点において反応系に存在するアクリル酸
あるいはアクリル酸エステルと塩素とのモル比率が収率
に対して極めて重要な因子である事を知見し、本発明を
完成するに至った。(Means for Solving the Problem) The present inventors have continued research on the photochlorination reaction of acrylic acid or acrylic acid ester for many years, and as a result, they have discovered that acrylic acid or acrylic acid present in the reaction system at a certain point in time The inventors discovered that the molar ratio of acid ester and chlorine is an extremely important factor for yield, and completed the present invention.
すなわち本発明は、アクリル酸あるいはアクリル酸エス
テルの光塩素化反応を行うに際し、アクリル酸あるいは
アクリル酸エステルと塩素を、光照射下、１ ： ０．
６〜１．８のアクリル酸あるいはアクリル酸エステル対
塩素の供給モル比で反応させることｔ−特徴とするアク
リル酸あるいはアクリル酸エステルの光塩素化方法であ
る。That is, in the present invention, when performing a photochlorination reaction of acrylic acid or acrylic ester, acrylic acid or acrylic ester and chlorine are mixed under light irradiation in a ratio of 1:0.
This is a method for photochlorination of acrylic acid or acrylic ester, characterized in that the reaction is carried out at a molar ratio of acrylic acid or acrylic ester to chlorine supplied of 6 to 1.8.
本発明の方法におけるアクリル酸あるいはアクリル酸エ
ステル及び塩素の供給方法は連続的であっても間欠的で
あっても良く、途中で供給速度を変化させる事も可能で
あるが、一定の速度で連続的に供給するのが一般的であ
る。その際、アクリル酸あるいはアクリル酸エステルの
供給速度に対する塩素の供給速度をモル比率で０．６〜
１．８倍モルに保つ必要があるが、ある瞬間においてこ
の値から逸脱しても、数分間単位でそれぞれの全供給量
をとらえた場合、その全供給モル比が前記比率の範囲に
あればよく、これも本発明の範囲に含まれる。The method of supplying acrylic acid or acrylic ester and chlorine in the method of the present invention may be continuous or intermittent, and it is possible to change the supply rate midway through, but it is possible to supply acrylic acid or acrylic ester and chlorine continuously at a constant rate. It is common to supply At that time, the molar ratio of chlorine supply rate to acrylic acid or acrylic acid ester supply rate is 0.6~
It is necessary to maintain the ratio to 1.8 times the molar ratio, but even if it deviates from this value at a certain moment, if the total supply amount of each is captured in units of several minutes, as long as the total supply molar ratio is within the above ratio range. Well, this is also within the scope of the invention.
本発明の方法におけるアクリル酸あるいはアクリル酸エ
ステルに対する塩素のモル比率は、０．６〜１．８倍モ
ルの範囲で可能であり、特に０．９〜１．１倍モルの範
囲が好ましい。０．６倍モル以下の塩素量の場合には重
合系の副反応が多く起り、１．８倍モル以上の塩素量の
場合には、トリクロルプロピオン酸等の副生物が多く出
現し、また塩素の歩留りを悪くする。The molar ratio of chlorine to acrylic acid or acrylic ester in the method of the present invention can range from 0.6 to 1.8 times by mole, and is particularly preferably from 0.9 to 1.1 times by mole. When the amount of chlorine is less than 0.6 times the mole, many side reactions occur in the polymerization system, and when the amount of chlorine is more than 1.8 times the mole, many by-products such as trichloropropionic acid appear, and chlorine This results in poor yield.
本発明を実施する際の反応方式としては、回分式と連続
式の二方法が可能である。回分式においては、例えば、
まず溶剤だけを反応器中に入れておき、光照射下、一定
流量でアクリル酸あるいはアクリル酸エステルを供給し
、同時にそのアクリル酸あるいはアクリル酸エステルの
供給量に対して０．６〜１．８倍モルの供給速度で塩素
を吹き込み、所定量のアクリル酸を投入した時点で反応
終了とするような方法が可能である。As a reaction method when carrying out the present invention, two methods are possible: a batch method and a continuous method. In the batch method, for example,
First, only a solvent is placed in a reactor, and acrylic acid or acrylic ester is supplied at a constant flow rate under light irradiation, and at the same time, 0.6 to 1.8% of the amount of acrylic acid or acrylic ester supplied is A method is possible in which chlorine is blown in at twice the molar supply rate and the reaction is terminated when a predetermined amount of acrylic acid is added.
連続方式においては、例えば溶剤、アクリル酸あるいは
アクリル酸エステル、塩素を同時に反応器の下部から供
給し、その際、アクリル酸あるいはアクリル酸エステル
量に対して０．６〜１．８倍モルとなるように塩素供給
速度を調節し、反応器上部より反応終了液をオーバフロ
ーさせて取り出すような形態が可能である。In a continuous system, for example, a solvent, acrylic acid or acrylic ester, and chlorine are simultaneously supplied from the bottom of the reactor, and at this time, the amount is 0.6 to 1.8 times the amount of acrylic acid or acrylic ester by mole. It is possible to adjust the chlorine supply rate so that the reaction-completed liquid is overflowed and taken out from the upper part of the reactor.
本発明において使用される溶剤は、ハロゲン化炭化水素
であれば何でも使用可能であるが、特に四塩化炭素等、
完全にハロゲン元素で置換されたハロゲン化炭化水素が
好ましい。The solvent used in the present invention can be any halogenated hydrocarbon, but in particular, carbon tetrachloride, etc.
Preference is given to halogenated hydrocarbons which are completely substituted with halogen elements.
本発明で使用される光源としては、特に限定されるもの
ではなく、日光、白熱灯、水銀灯、等この糧の反応で用
いられる光源でよい。The light source used in the present invention is not particularly limited, and may be any light source used in the reaction of this food, such as sunlight, an incandescent lamp, or a mercury lamp.
本発明での温度条件は、特に限定的ではなく、使用する
溶剤の凝固点以上、沸点以下であれば良いが一般には、
１０℃〜６０℃の範囲が好適である。The temperature conditions in the present invention are not particularly limited, and may be above the freezing point and below the boiling point of the solvent used, but in general,
A range of 10°C to 60°C is suitable.
本発明における溶剤とアクリル酸等の重量比率は、−概
に限定されないが、通常、溶剤に対して０．２〜０．５
重量比のアクリル酸おるいはアクリル酸エステルとする
のが好ましい。The weight ratio of the solvent to acrylic acid, etc. in the present invention is generally not limited, but is usually 0.2 to 0.5 to the solvent.
The weight ratio of acrylic acid or acrylic acid ester is preferably used.
（作 用）
アクリル酸おるいはアクリル酸エステルの光塩素化反応
は、ラジカル連鎖機構で進むものと考えられる。(Function) The photochlorination reaction of acrylic acid or acrylic ester is thought to proceed by a radical chain mechanism.
一方、一般にアクリル酸あるいはアクリル酸エステルは
、ラジカル化学樵によって連鎖的に重合する事が知られ
ている。従ってアクリル酸濃度が塩素濃度に比べて高い
状態で光を照射する場合には、光によって発生したラジ
カルによって、過剰に存在するアクリル酸が連鎖的に重
合してしまうものと考えられる。本発明によれば、発生
′してくる塩素ラジカルに対応する分量のアクリル！！
あるいはアクリル酸エステルを反応系に送シ込む事によ
り、塩素濃度とアクリル酸あるいはアクリル酸エステル
濃度との均衡を保ち、それによって重０合系の副反応を
抑制する事が可能である。On the other hand, it is generally known that acrylic acid or acrylic esters undergo chain polymerization using radical chemistry. Therefore, when light is irradiated in a state where the acrylic acid concentration is higher than the chlorine concentration, it is thought that the radicals generated by the light cause chain polymerization of the acrylic acid present in excess. According to the present invention, the amount of acrylic that corresponds to the generated chlorine radicals! !
Alternatively, by injecting acrylic ester into the reaction system, it is possible to maintain a balance between the chlorine concentration and the acrylic acid or acrylic ester concentration, thereby suppressing side reactions in the polymerization system.
（発明の効果）
本発明によれば、金属化合物等の触媒は一切使用する事
なく目的とする塩素化物を高収率で得る事が出来るため
、製品の重金属に！る汚染、排水の重金、属汚染、オペ
レーターの被毒等の心配が全くなく、塩素化後の処理、
精製工程、排水処理等に多くの利点金与える事が可能で
ある。(Effects of the Invention) According to the present invention, it is possible to obtain the desired chlorinated product in high yield without using any catalyst such as a metal compound, so it is possible to eliminate heavy metals in products! There is no need to worry about contamination, heavy metal or metal contamination of wastewater, poisoning of operators, etc., and the treatment after chlorination,
It can bring many benefits to purification processes, wastewater treatment, etc.
（実施例） 以下に本発明の実施例を示す。(Example) Examples of the present invention are shown below.
実施例１〜９
内径５０ｍ、高さ７０５１のジャケット付ガラス反応器
に、四塩化炭素５００ｆを入れ、反応の外側に光源をお
いて光を照射しながら、攪拌下アクリル酸あるいはアク
リル酸エステルを一定流量で供給し、同時に塩素ガスを
一定流量で吹き込み４０℃に液温を保った。所定量のア
クリル酸あるいはアクリル酸エステルを供給し終った時
点で供給を停止し、反応を終了とした。反応液をガスク
ロマトグラフィーにて分析した。結果を表−１に示す。Examples 1 to 9 500 f of carbon tetrachloride was placed in a jacketed glass reactor with an inner diameter of 50 m and a height of 7051 mm, and while a light source was placed outside the reaction chamber and irradiated with light, acrylic acid or acrylic acid ester was constantly heated under stirring. At the same time, chlorine gas was blown in at a constant flow rate to maintain the liquid temperature at 40°C. When a predetermined amount of acrylic acid or acrylic ester had been supplied, the supply was stopped and the reaction was terminated. The reaction solution was analyzed by gas chromatography. The results are shown in Table-1.
比較例１〜５
実施例１と同様に反応を行い、Ｃ１ｔ／原料の供給モル
比を変えたものおよび実施例１と同一の装置を用い、四
塩化炭素５００ｆと、所定量のアクリル酸あるいはアク
リル酸エステルの全量を仕込み、攪拌しながら、光照射
下塩素を吹き込んだものを実施例１と同様に分析を行な
った。結果を表−１に合せて示す。Comparative Examples 1 to 5 A reaction was carried out in the same manner as in Example 1, except that the molar ratio of C1t/raw material was changed, and using the same equipment as in Example 1, 500f of carbon tetrachloride and a predetermined amount of acrylic acid or acrylic acid were used. Analysis was conducted in the same manner as in Example 1 after charging the entire amount of acid ester and blowing chlorine under light irradiation while stirring. The results are also shown in Table-1.
実施例１０〜１５
内径４０ ｍ 、高さ１ｍのジャケット付ガラス反応器
の外側に、２０Ｗの螢光ケミカルラング（東芝ＦＬ２０
ＢＬ ） ４本を設置し、温度を４０℃に保ちながら、
光照射下、四塩化炭素、アクリル酸あるいはアクリル酸
エステル、及び塩素を一定流量で供給し、反応系が定常
状ｉとなった後、反応器上部よりオーバーフローしてく
る反応液をガスクロマトグラフィーにて分析した。結果
を表−２に示す。Examples 10 to 15 A 20W fluorescent chemical rung (Toshiba FL20
BL) 4 were installed, and while keeping the temperature at 40℃,
Under light irradiation, carbon tetrachloride, acrylic acid or acrylic ester, and chlorine are supplied at a constant flow rate, and after the reaction system reaches a steady state i, the reaction liquid overflowing from the top of the reactor is subjected to gas chromatography. It was analyzed. The results are shown in Table-2.
Claims (1)
を行うに際し、アクリル酸あるいはアクリル酸エステル
と塩素を、光照射下、１：０．６〜１．８のアクリル酸
あるいはアクリル酸エステル対塩素の供給モル比で反応
させることを特徴とするアクリル酸あるいはアクリル酸
エステルの光塩素化方法。When performing a photochlorination reaction of acrylic acid or acrylic ester, acrylic acid or acrylic ester and chlorine are mixed under light irradiation at a ratio of 1:0.6 to 1.8 molar ratio of acrylic acid or acrylic ester to chlorine. A method for photochlorinating acrylic acid or acrylic ester, which is characterized by reacting at a specific ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25572884A JPS61134343A (en) | 1984-12-05 | 1984-12-05 | Photo-chlorination of acrylic acid or acrylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25572884A JPS61134343A (en) | 1984-12-05 | 1984-12-05 | Photo-chlorination of acrylic acid or acrylic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61134343A true JPS61134343A (en) | 1986-06-21 |
Family
ID=17282806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25572884A Pending JPS61134343A (en) | 1984-12-05 | 1984-12-05 | Photo-chlorination of acrylic acid or acrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61134343A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484956A (en) * | 1990-01-22 | 1996-01-16 | Dekalb Genetics Corporation | Fertile transgenic Zea mays plant comprising heterologous DNA encoding Bacillus thuringiensis endotoxin |
| US5780708A (en) * | 1990-01-22 | 1998-07-14 | Dekalb Genetics Corporation | Fertile transgenic corn plants |
| US5780709A (en) * | 1993-08-25 | 1998-07-14 | Dekalb Genetics Corporation | Transgenic maize with increased mannitol content |
| US5969213A (en) * | 1990-04-17 | 1999-10-19 | Dekalb Genetics Corporation | Methods and compositions for the production of stably transformed fertile monocot plants and cells thereof |
| CN111056937A (en) * | 2020-01-02 | 2020-04-24 | 大连凯飞化学股份有限公司 | Synthetic method of 2, 3-dichloro-2-methylpropanoic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49133319A (en) * | 1972-11-10 | 1974-12-21 |
-
1984
- 1984-12-05 JP JP25572884A patent/JPS61134343A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49133319A (en) * | 1972-11-10 | 1974-12-21 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484956A (en) * | 1990-01-22 | 1996-01-16 | Dekalb Genetics Corporation | Fertile transgenic Zea mays plant comprising heterologous DNA encoding Bacillus thuringiensis endotoxin |
| US5554798A (en) * | 1990-01-22 | 1996-09-10 | Dekalb Genetics Corporation | Fertile glyphosate-resistant transgenic corn plants |
| US5780708A (en) * | 1990-01-22 | 1998-07-14 | Dekalb Genetics Corporation | Fertile transgenic corn plants |
| US5969213A (en) * | 1990-04-17 | 1999-10-19 | Dekalb Genetics Corporation | Methods and compositions for the production of stably transformed fertile monocot plants and cells thereof |
| US5780709A (en) * | 1993-08-25 | 1998-07-14 | Dekalb Genetics Corporation | Transgenic maize with increased mannitol content |
| CN111056937A (en) * | 2020-01-02 | 2020-04-24 | 大连凯飞化学股份有限公司 | Synthetic method of 2, 3-dichloro-2-methylpropanoic acid |
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