JPH0288544A - Production of allyldialkylamine - Google Patents
Production of allyldialkylamineInfo
- Publication number
- JPH0288544A JPH0288544A JP63239958A JP23995888A JPH0288544A JP H0288544 A JPH0288544 A JP H0288544A JP 63239958 A JP63239958 A JP 63239958A JP 23995888 A JP23995888 A JP 23995888A JP H0288544 A JPH0288544 A JP H0288544A
- Authority
- JP
- Japan
- Prior art keywords
- allyl
- waste water
- halide
- inorganic alkali
- separated
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 239000002351 wastewater Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- -1 allyl halide Chemical class 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 150000004820 halides Chemical class 0.000 claims abstract description 9
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 30
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 abstract description 26
- 150000003335 secondary amines Chemical class 0.000 abstract description 16
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 2
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- 239000010410 layer Substances 0.000 description 32
- 239000011780 sodium chloride Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000003134 recirculating effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
し産業上の利用分野］
本発明はアリルジアルキルアミンの製造方法に関し、特
に無機アルカリの存在下に水溶媒中で第二級アミンとハ
ロゲン化アリルとを反応させるアリルジアルキルアミン
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a method for producing allyl dialkyl amines, in particular allyl dialkyl amines, which are produced by reacting a secondary amine with an allyl halide in an aqueous solvent in the presence of an inorganic alkali. This invention relates to a method for producing amines.
アリルジアルキルアミン、特にアリルジメチルアミンは
、廃水処理剤、紙力増強剤、農薬等の中間体として有用
な化合物である。Allyl dialkylamine, especially allyl dimethylamine, is a compound useful as an intermediate for wastewater treatment agents, paper strength agents, agricultural chemicals, and the like.
［従来の技術］
アリルジアルキルアミンの製法に関する公知技術は少な
く、特表昭６２−５０１９１３号公報にはトルエン等の
有機溶媒下での反応が、また、ハンガリ公告特許第１８
２２３号にはトルエン溶媒下で臭化力Ｊラム又はヨウ化
カリウムを触媒に用いて反応させる方法が開示されてい
る。[Prior art] There are few known technologies related to the production method of allyl dialkylamine.
No. 223 discloses a method of reacting in a toluene solvent using ram bromide or potassium iodide as a catalyst.
特表昭６２−５０１９１３号の方法によれば、アリルジ
アルキルアミンの収量は９０％以上と記されているが、
多量の有機溶媒を取り扱う煩雑さ、およびその使用量が
アリルジアルキルアミンに対して１〜３倍量（重量）と
多く、必ずしも工業的に有利な方法とはいえない。According to the method of Japanese Patent Publication No. 62-501913, the yield of allyl dialkylamine is said to be 90% or more, but
It is not necessarily an industrially advantageous method because it is complicated to handle a large amount of organic solvent and the amount used is 1 to 3 times the amount (by weight) of allyl dialkylamine.
また、上記ハンガリー公告特許の方法も有機溶媒を使用
しているため、同様の問題があり、更に、本方法でのア
リルジアルキルアミンの収量は４５．８〜５６％（用い
たハロゲン化アリル基２１りと低い。Furthermore, since the method of the Hungarian published patent uses an organic solvent, it has the same problem, and furthermore, the yield of allyl dialkylamine in this method is 45.8 to 56% (21% of the halogenated allyl groups used). Very low.
［発明が解決しようとする課題］
アリルジアルキルアミン、例えばアリルジメチルアミン
は、下記の （０式に示すように、水酸仕ナトリウムの
如き無機アルカリの存在下において、ジメチルアミンと
塩化アリルを反応させることにより得られる。[Problem to be Solved by the Invention] Allyl dialkylamine, for example allyl dimethylamine, can be prepared by reacting dimethylamine and allyl chloride in the presence of an inorganic alkali such as sodium hydroxide as shown in the following formula (0). It can be obtained by
””＞Ｎ］ ＋ Ｃｔ（□８ＣＩＩＣＨｚＣｆｆｉ ＋
Ｎａ０ＩＩ −１ｌｆｆ
本反応は、塩化ナトリウムが副生ずるため、反応液はス
ラリー状態となる。そこで、通常は反応を円滑に進行さ
せるために、水の存在下に行われる。この水は、原料の
ジメチルアミンあるいは水酸化ナトリウムを水溶液で用
いることにより賄われている。””＞N] + Ct(□8CIICHzCffi +
Na0II -1lff Since sodium chloride is produced as a by-product in this reaction, the reaction solution becomes a slurry. Therefore, in order to allow the reaction to proceed smoothly, it is usually carried out in the presence of water. This water is provided by using the raw material dimethylamine or sodium hydroxide as an aqueous solution.
また、副反応として （２）式に示したように、アリル
ジメチルアミンに更に１モルの塩化アリルが反応して、
ジアリルジメチルアンモニウムクロライドが生じる。In addition, as a side reaction, as shown in equation (2), 1 mole of allyl chloride reacts with allyldimethylamine,
Diallyldimethylammonium chloride is produced.
””＞Ｎ−ＣＨ２−Ｃｌｌ＝Ｃ１１，＋ ＣＨ２＝ＣＨ
ＣＨ２Ｃｆｆ１Ｌ
この結果、アリルジメチルアミンの収量は満足いくもの
ではないのが現状である。"">N-CH2-Cll=C11,+ CH2=CH
CH2Cff1L As a result, the yield of allyldimethylamine is currently not satisfactory.
副生じた塩化ナトリウムと、副反応によって生成したジ
アリルジメチルアンモニウムクロライドは、一部塩化ナ
トリウムの析出した水溶液の状態であり、一般に廃水と
して処理される。アリルジメチルアミンの収量が低い場
合は、その分ジアリルジメチルアンモニウムクロライド
が多く生成することになり、廃水のＣＯＯ値は非常に高
く、廃水処理の負荷を高め、コスト的に大きな負担にな
る。従って、アリルジメチルアミンの収量を向上させ、
廃水処理を容易にするためには、（２）式の反応をでき
るだけ抑制することが必要である。The by-produced sodium chloride and the diallyldimethylammonium chloride produced by the side reaction are in the form of an aqueous solution in which sodium chloride is partially precipitated, and are generally treated as wastewater. If the yield of allyldimethylamine is low, a correspondingly large amount of diallyldimethylammonium chloride will be produced, and the COO value of the wastewater will be extremely high, increasing the burden of wastewater treatment and causing a large cost burden. Therefore, improving the yield of allyldimethylamine,
In order to facilitate wastewater treatment, it is necessary to suppress the reaction of formula (2) as much as possible.
本発明の目的は、従来技術に見られるような多量の有機
溶媒を用いる煩雑な工程及び生産性の悪さ等の問題を解
決すると共に、従来、考慮が払われていなかった廃水処
理問題の軽減を図ることにある。The purpose of the present invention is to solve problems such as the complicated process using a large amount of organic solvent and poor productivity, which are seen in the prior art, and to alleviate the problem of wastewater treatment, which has not been considered in the past. It's about trying.
［課題を解決するための手段］
本発明者等は、前記の ＋１１式及び （２）式の反応
について種々の検討を行なった結果、反応によって生じ
たジアリルジメチルアンモニウムクロライドと塩化ナト
リウムを含む廃水を再循環使用することによって前記
（２）式の反応が抑制され、アリルジメチルアミンの収
量が大きく増加することを見出した。[Means for Solving the Problems] As a result of various studies on the reactions of formula +11 and formula (2), the present inventors have determined that the wastewater containing diallyldimethylammonium chloride and sodium chloride produced by the reaction can be Said by using recirculation
It has been found that the reaction of formula (2) is suppressed and the yield of allyldimethylamine is greatly increased.
＋１１式の反応により得られた反応終了液は、主反応生
成物であるアリルジメチルアミンの層と、副生した塩化
ナトリウム及び副反応によって生じたジアリルジメチル
アンモニウムクロライドを含む水層に分液するので、上
層のアリルジメチルアミン層を分離した後、残った水層
から析出している塩化ナトリウムを除去し、得られた廃
水の一部を次回の反応にリサイクル使用した。その結果
、廃水リサイクルの有無により同反応条件下において、
アリルジメチルアミンの収量に大きな差が生じることを
見出し本発明に到達した。The reaction completed liquid obtained by the reaction of formula +11 is separated into a layer of allyldimethylamine, which is the main reaction product, and an aqueous layer containing by-product sodium chloride and diallyldimethylammonium chloride produced by the side reaction. After separating the upper allyldimethylamine layer, precipitated sodium chloride was removed from the remaining aqueous layer, and a portion of the resulting waste water was recycled for use in the next reaction. As a result, under the same reaction conditions with or without wastewater recycling,
The present invention was achieved by discovering that there is a large difference in the yield of allyldimethylamine.
すなわち１本発明は、無機アルカリの存在下に水溶媒中
で第二級アミンとハロゲン化フリルとを反応させるアリ
ルジアルキルアミンの製造方法において、反応液から分
離された廃水を反応系に再循環せしめることを特徴とす
るアリルジアルキルアミンの製造方法である。That is, 1 the present invention is a method for producing allyl dialkylamine in which a secondary amine and a furyl halide are reacted in an aqueous solvent in the presence of an inorganic alkali, in which wastewater separated from the reaction solution is recycled to the reaction system. This is a method for producing allyl dialkylamine.
［発明の詳細な説明］
本発明において用いられるジアルキルアミンは、一般式
（式中、Ｒ７及びＲ２はそれぞれ独立に炭素原子１〜４
個のアルキル基である。）
で表わされる第二級アミンであって、Ｒ＋及びＲ２が各
々独立してメチル基又はエチル基であることが好ましい
。[Detailed Description of the Invention] The dialkylamine used in the present invention has the general formula (wherein R7 and R2 each independently represent 1 to 4 carbon atoms).
number of alkyl groups. ) It is preferable that R+ and R2 are each independently a methyl group or an ethyl group.
ハロゲン化アリルは、アリルハライドの他、メタリルハ
ライド、エタリルハライドが用いることができ、ハライ
ドとしてはクロライド又はブロマイドが好ましい。本発
明に使用するには塩化アリルが最も好ましい。As the allyl halide, in addition to allyl halide, methallyl halide and ethylyl halide can be used, and the halide is preferably chloride or bromide. Allyl chloride is most preferred for use in the present invention.
第二級アミンの使用量は、ハロゲン化アリル１モルに対
して０．８〜２モル、好ましくは０．９〜１．１モルで
ある。０．８モル以下では、アリルジアルキルアミンの
収量が低下し、２モル以上使用しても収量は増加せず、
第二級アミンの回収のため工程が複雑になるだけである
。使用する第二級アミンは、無水物又は水溶液のいずれ
でもよいが、生産効率の面から濃度４０重量％以上の水
溶液が好ましい。The amount of secondary amine used is 0.8 to 2 mol, preferably 0.9 to 1.1 mol, per mol of allyl halide. When the amount is less than 0.8 mol, the yield of allyl dialkylamine decreases, and even when 2 mol or more is used, the yield does not increase.
Recovery of the secondary amine only complicates the process. The secondary amine used may be an anhydride or an aqueous solution, but from the viewpoint of production efficiency, an aqueous solution with a concentration of 40% by weight or more is preferable.
無機アルカリは、アルカリ金属の水酸化物又は炭酸塩で
あり、アルカリ金属水酸化物が好ましい６本発明で使用
するには水酸化ナトリウムが最も好ましい。The inorganic alkali is an alkali metal hydroxide or carbonate, with alkali metal hydroxides being preferred. Sodium hydroxide is most preferred for use in the present invention.
無機アルカリの保圧下に第二級アミンとハロゲン化アリ
ルとを反応させて、アリルジアルキルアミンを得る上に
おいて、無機アルカリの使用量はハロゲン化アリル１モ
ルに対して０．８〜５モル、好ましくは０．９〜１４モ
ルである。０．８モル以下の使用ではアリルジアルキル
アミンの収量が低下し、５モル以上使用しても収量の増
加には効果がない。使用する無機アルカリの水溶液の濃
度は特に限定はしないが、使用にあたり無機アルカリの
結晶の析出を防ぎ、水溶液状態を保って操作するのに比
較的容易な７５重量％以下の水溶液で用いることが好ま
しい。In obtaining allyl dialkylamine by reacting a secondary amine with an allyl halide under the pressure of an inorganic alkali, the amount of inorganic alkali used is preferably 0.8 to 5 moles per mole of allyl halide. is 0.9 to 14 mol. If less than 0.8 mol is used, the yield of allyl dialkylamine will decrease, and if more than 5 mol is used, there will be no effect on increasing the yield. The concentration of the inorganic alkali aqueous solution used is not particularly limited, but it is preferable to use an aqueous solution of 75% by weight or less, which prevents the precipitation of inorganic alkali crystals and is relatively easy to operate while maintaining the aqueous state. .
本発明の実施において１反応系に加える前記の水の量は
、特に規制はしないが、使用する無機アルカリ及び第二
級アミンの合計重量を基準として水の存在量を１０〜６
０重量％の範囲に調整することが、本発明の効果を引き
出す上で好ましい。In carrying out the present invention, the amount of water added to one reaction system is not particularly limited, but the amount of water present is 10 to 6 % based on the total weight of the inorganic alkali and secondary amine used.
It is preferable to adjust the content to a range of 0% by weight in order to bring out the effects of the present invention.
各原料の導入時期は、下記の３方法が好ましい。Regarding the introduction timing of each raw material, the following three methods are preferable.
＋１１ 無１！アルカリと第二級アミンを全量仕込み、
ハロゲン化アリルを滴下する。+11 No 1! Prepare the entire amount of alkali and secondary amine,
Add allyl halide dropwise.
（２）無機アルカリを全量仕込み、第二級アミンとハロ
ゲン化アリルを滴下する。但し、第二級アミンの滴下時
間は、ハロゲン化アリルの滴下時間に等しいか又はそれ
以内にすることが好ましい。(2) Charge the entire amount of inorganic alkali, and dropwise add secondary amine and allyl halide. However, the time for dropping the secondary amine is preferably equal to or shorter than the time for dropping the allyl halide.
（３）第二級アミンを全量仕込み、無機アルカリとハロ
ゲン化アリルを滴下する。(3) Charge the entire amount of secondary amine, and dropwise add inorganic alkali and allyl halide.
以上の３方法のうちでは、（＋１の方法が工程が簡単で
あり、最も好ましい。Among the above three methods, method (+1) is the most preferable because the process is simple.
本発明の方法における再循環液の導入は、上記（１１〜
（３）の各方法共、ハロゲン化アリルの滴下開始以前に
完了していることが好ましい。The introduction of the recirculating liquid in the method of the present invention is as described above (11-
It is preferable that each method (3) is completed before the dropwise addition of allyl halide is started.
第二級アミンとハロゲン化アリルの反応において、その
温度は使用する原料物質の性質に依存するが、一般に１
０〜８０℃の温度で実施するのが好ましく、３０〜６０
℃が更に好ましい。反応混合物はそれらの温度に２〜ｌ
Ｏ時間、好ましくは４〜８時間維持するのが有利である
。In the reaction of secondary amines and allyl halides, the temperature depends on the nature of the raw materials used, but generally 1
It is preferable to carry out at a temperature of 0 to 80 °C, and 30 to 60 °C.
C. is more preferred. The reaction mixture is brought to those temperatures by 2 to 1
It is advantageous to maintain the temperature for 0 hours, preferably from 4 to 8 hours.
なお１反応圧力は、常圧、加圧下のいずれの方法でもよ
いが、加圧下で行なう方が有利である。Note that the reaction pressure may be either normal pressure or increased pressure, but it is more advantageous to carry out the reaction under increased pressure.
以上の方法により得られた反応終了液は、反応生成物で
あるアリルジアルキルアミンの有機層と、副生じた塩及
び副反応によって生成したジアリルジメチルアンモニウ
ムクロライドを含む水層とが上下層に分液されるので、
生成物の分離は容易である。The reaction-completed liquid obtained by the above method is separated into upper and lower layers: an organic layer containing allyl dialkylamine, which is a reaction product, and an aqueous layer containing by-product salt and diallyldimethylammonium chloride produced by the side reaction. Because it is done,
Separation of the products is easy.
反応時において、使用した原料の無機アルカリ及び第二
級アミンの合計重量を基準として、水１０〜６０重１％
の範囲に調整した場合は、生成物を分離した後の水層は
、多量の塩化ナトリウムが析出した状態となっている。During the reaction, 10 to 60% water by weight, based on the total weight of the inorganic alkali and secondary amine used as raw materials.
When the concentration is adjusted to within this range, a large amount of sodium chloride is precipitated in the aqueous layer after the product is separated.
この廃水をそのまま再循環使用しても、アリルジアルキ
ルアミンの収量（使用したハロゲン化アＪルの壜を基準
）の増加に効果はあるが、ｌバッチ当りのアリルジアル
キルアミンの仕上り量の低下等により生産性が悪くなる
ので、通常下記の（ａｌ〜ｌｃ）の３方法のいずれかで
処理することが好ましい。Even if this wastewater is recycled and used as it is, it is effective in increasing the yield of allyl dialkylamine (based on the bottle of halogenated aluminum used), but the amount of finished allyl dialkyl amine per 1 batch is reduced, etc. Since the productivity deteriorates, it is usually preferable to use one of the following three methods (al to lc).
（ａｔ 析出した塩化ナトリウムを濾過又は遠心分離に
よって除き、得られた処理液の一部又は全量を再循環液
とする。(at) Remove precipitated sodium chloride by filtration or centrifugation, and use part or all of the resulting treated liquid as a recirculating liquid.
ｔｂ＋廃水を、単蒸留によって濃縮し、析出した塩化ナ
トリウムを濾過又は遠心分離によって除き、処理液の一
部、或は全量を再循環液とする。The tb+ wastewater is concentrated by simple distillation, the precipitated sodium chloride is removed by filtration or centrifugation, and part or all of the treated liquid is used as a recirculating liquid.
ｌｃｌ上記 ｆａｌ又はｔｂｌの処理を行なった後、重
に無機アルカリを処理液に加えて攪拌した後、静置分離
し、濃厚なジアリルジアルキルアンモニウムハライドを
含む上層と、無機アルカＪ及び塩化ナトリウムを含む下
層のそれぞれの水溶液からなる２層に分液するので、シ
アツルジアルキルアンモニウムハライドを含む上層の一
部、或は全量を再循ｒ＝液とする。After performing the fal or tbl treatment above, an inorganic alkali is added to the treatment solution, stirred, and then separated by standing to separate an upper layer containing concentrated diallyldialkylammonium halide and an upper layer containing inorganic alkali J and sodium chloride. Since the liquid is separated into two layers consisting of the respective aqueous solutions of the lower layer, a part or the entire amount of the upper layer containing the cyazuldialkylammonium halide is recycled r=liquid.
、反応時の原料モル比において、第二級アミンハロゲン
化アリル：無機アルカリ＝０．９〜１．１：１．０・１
．２以上として、無機アルカリを多（した場合、ｆｂｌ
の操作を行なっただけで、（ｃ）の層分離が起こり、再
循環が容易である。, In the raw material molar ratio during reaction, secondary amine allyl halide: inorganic alkali = 0.9 to 1.1: 1.0.1
．． 2 or more, inorganic alkali is added (if fbl
Just by performing the above operation, the layer separation (c) occurs and recycling is easy.
上記各方法では ｆｂｌ及びｆｃｌの方法によった場合
１本発明の効果が顕著に現われる。ここでｆｂｌ及びｆ
ｃｌの処理について、以下に詳細に説明する。Among the above-mentioned methods, the effects of the present invention are particularly apparent when using the fbl and fcl methods. Here fbl and f
The processing of cl will be explained in detail below.
廃水を濃縮する場合の単蒸留は、減圧下、常圧下のいづ
れも可能である。しかし廃水に含まれている物質の熱分
解、或はそれによる着色を防ぐため、減圧下１００℃以
下の温度で行なうことが好ましく、８０°Ｃ以下が更に
好ましい。Simple distillation when concentrating wastewater can be carried out either under reduced pressure or normal pressure. However, in order to prevent thermal decomposition of substances contained in the wastewater or coloration thereof, the reaction is preferably carried out under reduced pressure at a temperature of 100°C or lower, more preferably 80°C or lower.
濃縮の程度は任意であるが、 ｇｌ（２に、より濃縮さ
れて１反応系へ再循環される水の総量が少なくなればア
リルジアルキルアミンの収量はより向上する。しかし、
過度の濃縮は、工程時間が長くなり不利である。一方、
逆に濃縮不足であると、本発明の効果が薄れる。Although the degree of concentration is arbitrary, the yield of allyl dialkylamine will be further improved if the total amount of water that is concentrated to 1 gl (2) and recycled to the reaction system is reduced. However,
Excessive concentration is disadvantageous because it increases the process time. on the other hand,
Conversely, if the concentration is insufficient, the effects of the present invention will be diminished.
そこで通常は、廃水中の水分含有率が６０〜２０重量％
、好ましくは５０〜３０重量％になるまで濃縮される。Therefore, the water content in wastewater is usually 60 to 20% by weight.
, preferably 50 to 30% by weight.
廃水に無機アルカリを加えて濃縮する場合において、用
いる無機アルカリは、アルカリ金属又はアルカリ土類金
属の水酸化物であり、水酸化ナトノウム、水酸化カリウ
ムが好ましい。無機アルカリの添加量は、多い程、ジア
リルジアルキルアンモニウムハライドを含む上層の濃縮
に効果があるが、多すぎると経済的に不利となる。通常
は廃水に対して無機アルカリの濃度が５〜２５重１％、
好ましくは１０〜２０重量％になる様調整する。When an inorganic alkali is added to wastewater for concentration, the inorganic alkali used is an alkali metal or alkaline earth metal hydroxide, and sodium hydroxide and potassium hydroxide are preferable. The larger the amount of inorganic alkali added is, the more effective it is in concentrating the upper layer containing diallyldialkylammonium halide, but if it is too large, it is economically disadvantageous. Usually, the concentration of inorganic alkali in wastewater is 5 to 25% by weight,
The content is preferably adjusted to 10 to 20% by weight.
［実施例］
以下、実施例によって本発明を具体的に説明するが、こ
れは本発明の範囲を限定するものではない。実施例及び
比較例におけるすべての％は重量％である。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but these are not intended to limit the scope of the present invention. All percentages in Examples and Comparative Examples are by weight.
比較例１
５０％水酸化ナトリウム水溶液４４０ｇ ＋５．５モル
）をを２．５ｅの磁気撹拌機付の鋼製オートクｌｚ−ブ
に仕込み、更に、５０％ジメチルアミン水溶液４５０ｇ
（５，０モル）を仕込んで、４０〜４５℃に加温した
。次いでこの混合物を撹拌しながら塩化アリル：１８２
．５ｇ （５，０モル）を５時間かけて添加した。アリ
ルクロライド全量を加えた後、更に同じ温度で３詩間撹
拌を開けた。Comparative Example 1 440 g of 50% aqueous sodium hydroxide solution (+5.5 mol) was charged into a 2.5e steel autoclave equipped with a magnetic stirrer, and then 450 g of 50% aqueous dimethylamine solution was charged.
(5.0 mol) was charged and heated to 40-45°C. Then, while stirring this mixture, allyl chloride: 182
．． 5 g (5.0 mol) were added over 5 hours. After adding the entire amount of allyl chloride, stirring was continued for three more cycles at the same temperature.
反応終了後、混合物を室温まで冷却し、約１時間静置さ
せた後、上層のアリルジメチルアミン層を分離した。得
られたアリルジメチルアミンの層３６６ｇを分析した結
果、アリルジメチルアミンの収用は、使用した４化アリ
ルの量を基準にして７６２％であった。After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for about 1 hour, and then the upper allyldimethylamine layer was separated. Analysis of 366 g of the resulting allyldimethylamine layer showed that the allyldimethylamine expropriation was 762% based on the amount of allyl tetrahydride used.
実施例１
比較例１でアリルジメチルアミン層を分離した残りの塩
化ナトリウムを含む水層をそのままにして、その中へ、
更に比較例１と同じ原料を仕込み、同様の操作を行なっ
た。Example 1 The remaining aqueous layer containing sodium chloride from which the allyldimethylamine layer was separated in Comparative Example 1 was left as is, and into it,
Furthermore, the same raw materials as in Comparative Example 1 were charged, and the same operations were performed.
それにより得られたアリルジメチルアンミン層３７６ｇ
を分析した結果、アリルジメチルアミンの収量は、新た
に仕込んだ塩化アリルの量を基準にして８１．９％であ
った。376 g of allyldimethylammine layer obtained thereby
As a result of analysis, the yield of allyldimethylamine was 81.9% based on the amount of newly charged allyl chloride.
実施例２
比較例１で残存した塩化ナトリウムを含む水層！１０６
．５ｇを遠心分離器にかけて、含水した塩化ナトＪウム
１９３ｇと廃水７０６ｇ （ロス７、５ｇｌ とに分離
した、この廃水７０６ｇのＩ７２の３５３ｇを再循環液
として使用した以外は、比較例１と同じ操作を行なった
。Example 2 Aqueous layer containing sodium chloride remaining in Comparative Example 1! 106
．． 5g of sodium chloride was centrifuged and separated into 193g of water-containing sodium chloride and 706g of wastewater (loss 7, 5gl).The same procedure as Comparative Example 1 was performed, except that 353g of I72 from this 706g of wastewater was used as the recirculating liquid. I did it.
それにより得られたアリルジメチルアミン層３７５ｇを
分析した結果、アリルジメチルアミンの収：ｉは、新た
に仕込んだ塩化アリルの量を基準にして８１６％であっ
た。As a result of analysis of 375 g of the allyldimethylamine layer thus obtained, the yield i of allyldimethylamine was 816% based on the amount of newly charged allyl chloride.
実施例３
比較例１で残イアした塩化ナトリウムを含む水層を減圧
下にて！ｉ′ｉ蒸留を行ない、水３５０ｇ （ロスを含
も）を留出させた。第蒸留後のボトム液を遠心分離２Ｋ
にかけ、含水した塩化ナトリウム２７６ｇと廃水２７２
．５ｇ（ロス８．０ｇ）に分離した。この廃水を全量１
■循環液として使用して、比較例１と同じ操作を行なっ
た。Example 3 The aqueous layer containing sodium chloride that remained in Comparative Example 1 was removed under reduced pressure! i'i distillation was carried out, and 350 g of water (including loss) was distilled out. Centrifuge the bottom liquid after the second distillation at 2K
276g of hydrated sodium chloride and 272g of waste water
．． It was separated into 5g (loss 8.0g). The total amount of this wastewater is 1
(2) The same operation as in Comparative Example 1 was carried out using it as a circulating fluid.
それにより、得られたアリルジメチルアミン層４０２
ｇを分析した結果、アリルジメチルアミンの収量は、新
たに仕込んだ塩化アリルの量を基準にして８９．１％で
あった。Thereby, the obtained allyldimethylamine layer 402
The yield of allyldimethylamine was 89.1% based on the amount of newly charged allyl chloride.
実施例４
実施例２で遠心分離を行なった後の廃水７０６ｇに水酸
化ナトリウム１０５．９ｇを添加し、室温にて３０分撹
拌した後、静置分離を行ない、ジアリルジメチルアンモ
ニウムクロライドを含む上層と、水酸化ナトリウム及び
塩化ナトリウムを含む下層のそれぞれの水溶液の層に分
離した。この上層の全量８９ｇを再循環液として使用し
、比較例１と同じ操作を行なった。Example 4 105.9 g of sodium hydroxide was added to 706 g of waste water after centrifugation in Example 2, and after stirring at room temperature for 30 minutes, static separation was performed to separate the upper layer containing diallyldimethylammonium chloride. , the lower layers containing sodium hydroxide and sodium chloride were separated into respective aqueous layers. A total of 89 g of this upper layer was used as a recirculating liquid, and the same operation as in Comparative Example 1 was performed.
それにより得られたアリルジメチルアミン層４１０ｇを
分析した結果、アリルジメチルアミンの収用は、新たに
仕込んだ塩化アリルの計を基準にして９０．５％であっ
た。As a result of analysis of 410 g of the allyldimethylamine layer thus obtained, the expropriation of allyldimethylamine was 90.5% based on the total amount of newly charged allyl chloride.
実施例５
実施例３で用いた再循環液に、更に水酸化ナトｊウム４
１ｇを添加し、室ζ品にて３０分撹拌した後、静置分離
を行なってジアリルジメチルアンモニウムクロライドを
含も上層と、水酸化ナトリウム及び塩化ナトリウムを含
む下層のそれぞれの層に分離した。この上層の全量３１
ｇを再循環液として使用した以外は、比較例１と同じ
操作を行なった。Example 5 In addition to the recirculating liquid used in Example 3, sodium hydroxide 4
After stirring in a room for 30 minutes, the mixture was separated by standing to separate into an upper layer containing diallyldimethylammonium chloride and a lower layer containing sodium hydroxide and sodium chloride. The total amount of this upper layer is 31
The same operation as in Comparative Example 1 was performed except that g was used as the recirculating liquid.
それにより得られたアリルジメチルアミン層４０ｇを分
析した結果、アリルジメチルアミンの収（１は、新たに
仕込んだ塩化アリルの量を基準にして９１４％であった
。As a result of analysis of 40 g of the allyldimethylamine layer thus obtained, the yield of allyldimethylamine (1) was 914% based on the amount of allyl chloride newly charged.
１発明の効果］
本発明の方法は、無磯アルカリの存在下に本市媒中で第
二級アミンとハロゲン化アリルとを反応させるアリルジ
アルキルアミンの製造方法において、反応液から分離さ
れた廃水を反応系にμ■循環せしめることによって、従
来技術に見られるような多量の有機溶媒を用いる煩雑な
Ｔ程及び生産性の悪さ等の問題を解決すると共に、高収
量でアリルジアルキルアミンが得られ、さらに、廃水遣
を大幅に減少せしめることによって、従来、考虜が払わ
れなかった廃水処理問題を軽減し、廃水処理コストを低
減せしめ、従来技ＩＩｉにおける２つの大きな問題を同
時に解決したものでル〕す、工業的に非常に有利な方法
である。1. Effects of the invention] The method of the present invention is a method for producing allyl dialkylamine in which a secondary amine and an allyl halide are reacted in the present medium in the presence of an alkali-free alkali. By circulating μ into the reaction system, problems such as complicated T process using a large amount of organic solvent and poor productivity, which are seen in conventional techniques, can be solved, and allyl dialkylamine can be obtained in high yield. Furthermore, by significantly reducing wastewater consumption, it alleviates wastewater treatment problems that have not been considered in the past, reduces wastewater treatment costs, and solves two major problems in conventional technology IIi at the same time. This is a very industrially advantageous method.
Claims (3)
とハロゲン化アリルとを反応させるアリルジアルキルア
ミンの製造方法において、反応液から分離された廃水を
反応系に再循環せしめることを特徴とするアリルジアル
キルアミンの製造方法。(1) A method for producing allyl dialkylamine in which a secondary amine and an allyl halide are reacted in an aqueous solvent in the presence of an inorganic alkali, characterized in that waste water separated from the reaction solution is recycled to the reaction system. A method for producing allyl dialkylamine.
ロゲン化アルカリを分離除去した後、反応系に再循環せ
しめることを特徴とする請求項１に記載の方法。(2) The method according to claim 1, characterized in that the waste water separated from the reaction solution is concentrated, the precipitated alkali halide is separated and removed, and then recycled to the reaction system.
ン化アルカリを除去した後、無機アルカリを溶解させ、
ジアリルジアルキルアンモニウムハライドを含む上層液
を反応系に再循環せしめることを特徴とする、請求項１
又は２に記載の方法。(3) After removing the precipitated alkali halide from the waste water separated from the reaction solution, dissolving the inorganic alkali,
Claim 1, characterized in that the upper layer liquid containing diallyldialkylammonium halide is recycled to the reaction system.
Or the method described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63239958A JPH0288544A (en) | 1988-09-26 | 1988-09-26 | Production of allyldialkylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63239958A JPH0288544A (en) | 1988-09-26 | 1988-09-26 | Production of allyldialkylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0288544A true JPH0288544A (en) | 1990-03-28 |
Family
ID=17052362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63239958A Pending JPH0288544A (en) | 1988-09-26 | 1988-09-26 | Production of allyldialkylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0288544A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060468C (en) * | 1998-06-01 | 2001-01-10 | 贵州群星科学技术经济合作公司 | Refining method of dimethyl allylamine and its salt |
-
1988
- 1988-09-26 JP JP63239958A patent/JPH0288544A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060468C (en) * | 1998-06-01 | 2001-01-10 | 贵州群星科学技术经济合作公司 | Refining method of dimethyl allylamine and its salt |
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