WO1996039376A1 - A synthetic method for cyanoacrylate - Google Patents

A synthetic method for cyanoacrylate Download PDF

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Publication number
WO1996039376A1
WO1996039376A1 PCT/CN1995/000066 CN9500066W WO9639376A1 WO 1996039376 A1 WO1996039376 A1 WO 1996039376A1 CN 9500066 W CN9500066 W CN 9500066W WO 9639376 A1 WO9639376 A1 WO 9639376A1
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Prior art keywords
formate
reaction
cyanoacrylate
phase transfer
acrylonitrile
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PCT/CN1995/000066
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French (fr)
Chinese (zh)
Inventor
Sing Shiang
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Sing Shiang
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Priority to AU32514/95A priority Critical patent/AU3251495A/en
Publication of WO1996039376A1 publication Critical patent/WO1996039376A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the invention relates to the field of organic synthesis. Specifically, it relates to a method for synthesizing cyanoacrylate (three-step method). Background technique
  • Cyanoacrylate is the monomer of the adhesive, and ethyl cyanoacrylate is one of the more common monomers of this type of adhesive.
  • cyanoacrylates There are many methods for synthesizing cyanoacrylates. They may require highly toxic raw materials, or the process steps are complicated, and the process conditions are harsh. As a result, the cost of cyanoacrylates and their series of esters is higher, which affects further development and application.
  • the inventor invented a process route for synthesizing cyanoacrylates using acrylonitrile as a starting material, including a three-step process, namely: hypochlorous acid addition, phase transfer catalysis Condensation and intramolecular dehydration.
  • the purpose of the present invention is to provide a method for synthesizing cyanoacrylates using acrylonitrile as a starting material through a three-step common process, wherein the synthetic process includes a hypochlorous acid addition reaction, a phase transfer catalytic condensation reaction, and an intramolecular method. Dehydration reaction.
  • the bond in the acrylonitrile molecule can be subjected to an addition reaction with hypochlorous acid under certain conditions to form a hydroxychloride.
  • the present invention is prepared according to this principle. Chlorine ⁇ -hydroxypropionitrile.
  • hypochlorous acid is carried out by passing chlorine through an aqueous solution of acrylonitrile of pH 4-7 at a temperature lower than 15 ° F to allow the addition reaction to proceed.
  • the end point of the addition depends on the detection of double bonds. After the double bonds have basically disappeared, slowly pass the chlorine for 15-20 minutes. After the addition is completed, the pressure is slightly reduced to remove unreacted chlorine, and the oil layer is left to separate and the crude ⁇ -chloro- ⁇ -hydroxypropionitrile is separated, which can be directly sent to the process without purification.
  • Phase transfer catalysis is an organic synthesis method developed in the 1970s.
  • the present invention uses this synthetic reaction to take the synthesis of ethyl cyanoacrylate as an example. Chloro ⁇ -hydroxypropionitrile and ethyl formate were subjected to a dehydrochlorination condensation reaction to obtain ⁇ -cyano ⁇ -hydroxypropionate.
  • methyl cyanoacrylate referred to as methyl ester, the following
  • use methyl formate for the production of propyl ester, use methyl formate
  • a liquid-liquid two-phase or a solid-liquid two-phase can be used.
  • a solid-liquid two-phase reaction is used.
  • An organic solvent is used as a phase (such as benzene).
  • C chloride ⁇ hydroxypropionitrile is added.
  • a phase transfer catalyst is added.
  • Solid sodium hydroxide is added to control the reaction temperature.
  • Ethyl formate (to make other cyanoacrylates, add other corresponding formate).
  • the condensation reaction started, and the stirring was continued. After the dropwise addition was completed, the reaction was kept under stirring for 0.5 hours. After the reaction was completed, the inorganic matter was filtered off, and the solvent was recovered as benzene. The residue was crude ⁇ -cyano ⁇ -hydroxypropionate.
  • the catalyst for the phase transfer reaction may be a chromium salt, a macrocyclic polyether, an acyclic polyether, or a phase transfer catalytic resin.
  • the amount of catalyst, the temperature of the phase transfer reaction, the phase transfer reaction time, and the organic solvent used are all carried out according to the conventional phase transfer catalysis reaction.
  • the intramolecular dehydration process may be a chemical dehydration method, which uses phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, chlorosulfonic acid, potassium hydrogen sulfate, thiosulfonium, or phosphorous phosphonium as the dehydrating agent.
  • This can be catalytic thermal dehydration, i.e. heating in the presence of alumina or iodine to remove intramolecular water.
  • Intramolecular dehydration can also occur under simple heating conditions.
  • sulfuric acid is used as a dehydrating agent as an example, and a concentration of 95-100% sulfuric acid is used to dehydrate conventionally at 70-160'C to form cyanoacrylate, which is the target product.
  • sulfur dioxide was used as a protective atmosphere, and the distillation was appropriately performed under reduced pressure to evaporate ethyl cyanoacrylate in time.
  • the above solution was slightly decompressed to remove unreacted chlorine, and then a phase transfer catalysis reaction was performed. If a liquid-liquid two-phase reaction is used, the above reaction liquid can be directly put into a phase transfer reaction. If With a solid-liquid two-phase reaction, the above reaction solution is left to stand and the aqueous layer is separated, and the remaining organic layer is depressurized to remove water, and then a solid-liquid two-phase phase transfer catalytic reaction is performed. Add an organic solvent (such as benzene) with a volume of about 1 / 3-1 of the total volume of acrylonitrile, and then add sodium hydroxide particles and a phase transfer catalyst (phosphonium salt, polyether, or phase transfer resin).
  • a phase transfer catalyst phosphonium salt, polyether, or phase transfer resin
  • Ethyl formate was added dropwise with stirring and temperature control. After the dropwise addition is completed, the mixture is kept warm and stirred for 15-30 minutes. Then, it is filtered to remove inorganic substances (assuming that a phase transfer resin is used as a catalyst, the catalyst is recovered in this step). Then, the organic solvent is recovered by distillation, and the remaining is crude alpha cyano beta hydroxypropionate and a part of the catalyst (if a chromium salt or a polyether is used as a catalyst). The temperature was controlled at 70-95'C, and under the protection of a sulfur dioxide atmosphere, 1.5 equivalents of concentrated sulfuric acid was added dropwise to the above materials, and after about 0.5 hours, the temperature was raised to 150'C.
  • the above device was changed to a vacuum distillation device, and the temperature was gradually raised to 60-70'C, and the unreacted chlorine was distilled off. Then, the water was distilled off, and after the water was removed, the atmospheric pressure was restored.
  • methyl formate In the production of methyl cyanoacrylate, methyl formate is used.
  • propyl cyanoacrylate propyl formate is used.
  • Butyl formate is used when producing butyl cyanopropene butyl cyanoacrylate.
  • octyl cyanoacrylate methyloctyl octyl is used.
  • benzyl cyanoacrylate benzyl formate is used.
  • phenol cyanoacrylate phenol formate is used. That is, when producing various cyanoacrylates, the corresponding formazan esters are used, and the corresponding reaction temperature and vacuum distillation temperature are used to adapt to the boiling points of the relevant reactants.
  • the condensation step uses a liquid-liquid two-phase phase transfer to catalyze the condensation reaction.
  • the other processes are basically the same as in Example 1.
  • the solvent benzene was recovered in the oil layer first, and the remaining materials were mainly crude c cyano beta hydroxypropionate, which was directly subjected to the next intramolecular dehydration reaction, which was the same as in Example 1.
  • the invention initiates a new method for synthesizing cyanoacrylate products, which has many advantages compared with the old process route based on highly toxic hydrocyanic acid salts, which not only reduces costs, but also reduces environmental protection costs, and also makes labor safety more Guaranteed.
  • the application of cyanoacrylate adhesives has a better prospect.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

This invention relates to a synthetic method for cyanoacrylate (three steps), it utilizes acrylonitrile as major starting material, and comprises hypochloric acid addition, phase transfer condensation and intramolecular dehydration. It avoids to use directly or indirectly hydrocyanic acid or salt thereof, which is highly toxic.

Description

一种合成氰丙烯酸酯的方法 技术领域  Method for synthesizing cyanoacrylate
本发明涉及有机合成领域。 具体地说涉及氰丙烯酸酯的合成方法 (三步法）。 背景技术  The invention relates to the field of organic synthesis. Specifically, it relates to a method for synthesizing cyanoacrylate (three-step method). Background technique
氰丙烯酸酯是胶粘剂的单体，氰丙烯酸乙酯为此类胶粘剂较常见 的一种单体。 氰丙烯酸酯的合成方法有多种，它们或需剧毒的原料，或 工艺步骤较繁琐，并且工艺条件都较苛刻，以致氰丙烯酸酯和其系列酯 的成本较高，影响进一步开拓应用。  Cyanoacrylate is the monomer of the adhesive, and ethyl cyanoacrylate is one of the more common monomers of this type of adhesive. There are many methods for synthesizing cyanoacrylates. They may require highly toxic raw materials, or the process steps are complicated, and the process conditions are harsh. As a result, the cost of cyanoacrylates and their series of esters is higher, which affects further development and application.
为了简化工艺，不用剧毒原料，降低成本，本发明人发明了一条以 丙烯腈为起始原料合成氰丙烯酸酯的工艺路线，包含三步工艺过程， 即：次氯酸加成，相转移催化缩合及分子内脱水。 发明内容  In order to simplify the process without using highly toxic raw materials and reduce costs, the inventor invented a process route for synthesizing cyanoacrylates using acrylonitrile as a starting material, including a three-step process, namely: hypochlorous acid addition, phase transfer catalysis Condensation and intramolecular dehydration. Summary of the Invention
本发明的目的是提供一种通过三步普通的工艺过程，以丙烯腈为 起始原料合成氰丙烯酸酯的方法，其中合成工艺过程包含次氯酸加成 反应、相转移催化缩合反应以及分子内脱水反应。  The purpose of the present invention is to provide a method for synthesizing cyanoacrylates using acrylonitrile as a starting material through a three-step common process, wherein the synthetic process includes a hypochlorous acid addition reaction, a phase transfer catalytic condensation reaction, and an intramolecular method. Dehydration reaction.
丙烯腈分子中的 鍵，在一定条件下能和次氯酸进行加成反应而 生成羟基氯化物，本发明就是依此原理制得。氯 β羟基丙腈的。  The bond in the acrylonitrile molecule can be subjected to an addition reaction with hypochlorous acid under certain conditions to form a hydroxychloride. The present invention is prepared according to this principle. Chlorine β-hydroxypropionitrile.
次氯酸的加成，是在低于 15 Ό的温度下，在 ρΗ4—7的丙烯腈水溶 液中通氯以使加成反应进行。加成的终点以检测双鍵而定，双鍵基本消 失后，再慢通氯 15— 20分钟。加成完毕，稍减压以除去未反应氯，静置， 分取油层，为粗 α氯 β羟基丙腈，可不经精制直接送下工序。  The addition of hypochlorous acid is carried out by passing chlorine through an aqueous solution of acrylonitrile of pH 4-7 at a temperature lower than 15 ° F to allow the addition reaction to proceed. The end point of the addition depends on the detection of double bonds. After the double bonds have basically disappeared, slowly pass the chlorine for 15-20 minutes. After the addition is completed, the pressure is slightly reduced to remove unreacted chlorine, and the oil layer is left to separate and the crude α-chloro-β-hydroxypropionitrile is separated, which can be directly sent to the process without purification.
相转移催化反应，是七十年代开始发展起来的有机合成方法。本发 明采用该合成反应，以合成氰丙烯酸乙酯为例，使。氯 β羟基丙腈和甲 酸乙酯进行脱氯化氢的缩合反应以制得 α氰基 β羟基丙酸乙酯。 生产 氰丙烯酸甲酯时（简称甲酯，以下类此），用甲酸甲酯；生产丙酯时，用甲  Phase transfer catalysis is an organic synthesis method developed in the 1970s. The present invention uses this synthetic reaction to take the synthesis of ethyl cyanoacrylate as an example. Chloroβ-hydroxypropionitrile and ethyl formate were subjected to a dehydrochlorination condensation reaction to obtain α-cyano β-hydroxypropionate. For the production of methyl cyanoacrylate (referred to as methyl ester, the following), use methyl formate; for the production of propyl ester, use methyl formate
认太 酸丙酯；生产丁酯时，用甲酸丁酯；生产辛酯时，用甲酸辛酯；生产苄酯 时，用甲酸苄酯；生产苯酚酯时，用甲酸苯酚酯等等。也就是生产各种氰 丙烯酸酯时，用相对应的甲酸酯为辅原料。 Recognition Propyl ester; butyl formate, butyl formate; octyl ester, octyl formate; benzyl ester, benzyl formate; phenol ester, phenol formate, etc. That is, when producing various cyanoacrylates, the corresponding formate is used as an auxiliary raw material.
在相转移催化缩合反应中，可采用液-液二相，也可采用固 -液二 相。 例如要用固-液二相反应，以有机溶剂为一相（如：苯），加入 C 氯 β 羟基丙腈，加入相转移催化剂，加入固体氢氧化钠，控制好反应温度，搅 拌下滴加甲酸乙酯，（制别的氰丙烯酸酯，加入别的相对应的甲酸酯）。 缩合反应便开始，不停搅拌，滴加毕，再保温搅拌反应 0. 5小时，反应 毕，滤去无机物，滤液回收溶剂苯，残余物即为粗 α氰基 β羟基丙酸乙 酯。  In the phase transfer catalytic condensation reaction, a liquid-liquid two-phase or a solid-liquid two-phase can be used. For example, a solid-liquid two-phase reaction is used. An organic solvent is used as a phase (such as benzene). C chloride β hydroxypropionitrile is added. A phase transfer catalyst is added. Solid sodium hydroxide is added to control the reaction temperature. Ethyl formate, (to make other cyanoacrylates, add other corresponding formate). The condensation reaction started, and the stirring was continued. After the dropwise addition was completed, the reaction was kept under stirring for 0.5 hours. After the reaction was completed, the inorganic matter was filtered off, and the solvent was recovered as benzene. The residue was crude α-cyano β-hydroxypropionate.
相转移反应的催化剂，可以是铬盐，可以是大环多醚，可以是非环 多醚，也可以是相转移催化树脂。  The catalyst for the phase transfer reaction may be a chromium salt, a macrocyclic polyether, an acyclic polyether, or a phase transfer catalytic resin.
催化剂的用量，相转移反应的温度，相转移反应时间及所用有机溶 剂，都依相转移催化反应的常规进行。  The amount of catalyst, the temperature of the phase transfer reaction, the phase transfer reaction time, and the organic solvent used are all carried out according to the conventional phase transfer catalysis reaction.
α氰基 β羟基丙鲮乙酯在一定工艺条件下，发生分子内脱水反应 而生成氰丙烯酸乙酯，即本发明的一种目标产物。 该分子内脱水的工 艺，可以是化学脱水法，即用五氧化二磷、三氯氧磷、五氯化磷、氯磺酸、 硫酸氢钾、硫鲮或亚磷鲛作为脱水剂。 可以是催化热脱水，即在氧化铝 或碘存在时加热以脱分子内水。 也可以在单纯的加热条件下产生分子 内脱水。  α-cyano-β-hydroxypropylammonium ethyl ester undergoes an intramolecular dehydration reaction under certain process conditions to produce ethyl cyanoacrylate, which is a target product of the present invention. The intramolecular dehydration process may be a chemical dehydration method, which uses phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, chlorosulfonic acid, potassium hydrogen sulfate, thiosulfonium, or phosphorous phosphonium as the dehydrating agent. This can be catalytic thermal dehydration, i.e. heating in the presence of alumina or iodine to remove intramolecular water. Intramolecular dehydration can also occur under simple heating conditions.
在分子内脱水反应中，以硫酸为脱水剂为例，用浓度 95— 100 %硫 酸，按常规于 70— 160'C脱水而生成氰丙烯酸酯，即目标产品。 同时也 按常规在进行脱水反应中，以二氧化硫为保护气氛，并适当减压精馏以 及时蒸出氰丙烯酸乙酯。  In the intramolecular dehydration reaction, sulfuric acid is used as a dehydrating agent as an example, and a concentration of 95-100% sulfuric acid is used to dehydrate conventionally at 70-160'C to form cyanoacrylate, which is the target product. At the same time, in the conventional dehydration reaction, sulfur dioxide was used as a protective atmosphere, and the distillation was appropriately performed under reduced pressure to evaporate ethyl cyanoacrylate in time.
在反应器中，加入丙烯腈（总重量的 1/10)及占总丙烯腈体积 3—5 倍的水，加入碳酸钠等碳酸盐作为酸碱调节剂，降温至 0— 5 °C，慢通氯 并快搅拌，整个通氯过程控制 pH在 5— 6，控温下滴加余下的丙烯腈。 当取样检测至双鍵基本消失，再继续控温搅拌通氯 10— 20分钟。  In the reactor, add acrylonitrile (1/10 of the total weight) and water 3-5 times the total acrylonitrile volume, add carbonates such as sodium carbonate as acid-base regulators, and lower the temperature to 0-5 ° C. Chlorine is passed slowly and stirred quickly. The pH of the entire process is controlled to 5-6, and the remaining acrylonitrile is added dropwise under temperature control. When the sampling detects that the double bond has basically disappeared, continue to control the temperature and stir for 10-20 minutes.
将上述溶液稍减压以除去未反应氯，随后进行相转移催化反应。假 使采用液-液二相反应，则上述反应液即可直接投入相转移反应。 假使 采用固-液二相反应，则上述反应液要进行静置并分去水层，余下有机 层再减压去水，然后进行固-液二相的相转移催化反应。 加入有机溶剂 (如：苯）的体积约为丙烯腈总体积 1/3— 1，再加入氢氧化钠碎粒及相 转移催化剂（镄盐、多醚或相转移树脂）。 在搅拌和控温下滴加甲酸乙 酯。滴加完毕，再保温搅拌使反应 15— 30分钟。然后，过滤以除去无机 物（假使以相转移树脂为催化剂，则这一工序即回收催化剂）。接着蒸馏 回收有机溶剂，余下为粗 α氰基 β羟基丙酸乙酯及部分催化剂（假使是 以铬盐或多醚为催化剂）。 控温 70— 95'C，在二氧化硫气氛保护下，向 上述物料搅拌滴加浓硫酸 1. 5 当量，经约 0. 5小时，升温至 150'C，经 15— 20分钟，反应毕，速冷至室温。 在二氧化硫气氛保护下，减压精馏 氰丙烯酸乙酯至装有五氧化二磷和对苯二酚的容器中，隔绝空气。收集 48— 49 - /3· 3 X 102— 3. 6 X 102Pa或 80— 9CTC /1. 3 X 103— 2. 7 X 103Pa 馏份。 The above solution was slightly decompressed to remove unreacted chlorine, and then a phase transfer catalysis reaction was performed. If a liquid-liquid two-phase reaction is used, the above reaction liquid can be directly put into a phase transfer reaction. If With a solid-liquid two-phase reaction, the above reaction solution is left to stand and the aqueous layer is separated, and the remaining organic layer is depressurized to remove water, and then a solid-liquid two-phase phase transfer catalytic reaction is performed. Add an organic solvent (such as benzene) with a volume of about 1 / 3-1 of the total volume of acrylonitrile, and then add sodium hydroxide particles and a phase transfer catalyst (phosphonium salt, polyether, or phase transfer resin). Ethyl formate was added dropwise with stirring and temperature control. After the dropwise addition is completed, the mixture is kept warm and stirred for 15-30 minutes. Then, it is filtered to remove inorganic substances (assuming that a phase transfer resin is used as a catalyst, the catalyst is recovered in this step). Then, the organic solvent is recovered by distillation, and the remaining is crude alpha cyano beta hydroxypropionate and a part of the catalyst (if a chromium salt or a polyether is used as a catalyst). The temperature was controlled at 70-95'C, and under the protection of a sulfur dioxide atmosphere, 1.5 equivalents of concentrated sulfuric acid was added dropwise to the above materials, and after about 0.5 hours, the temperature was raised to 150'C. After 15-20 minutes, the reaction was completed. Cool to room temperature. Under the protection of a sulfur dioxide atmosphere, ethyl cyanoacrylate was distilled under reduced pressure into a container containing phosphorus pentoxide and hydroquinone to isolate the air. Collect fractions of 48—49-/ 3 · 3 X 10 2 — 3. 6 X 10 2 Pa or 80 — 9CTC / 1. 3 X 10 3 — 2. 7 X 10 3 Pa.
实施例 1 Example 1
在一个四口烧瓶上装：电动搅拌器、温度计、滴液漏斗、气体导入 管，加入 53克（1摩尔）丙烯腈及 200克水，外冷却降至 5 °C，快搅拌，缓 慢通入氯气，用 10%碳酸钠溶液调 pH，使 pH值控制在 5—6左右，同 时控温 0—] (TC，不超过 15'C，滴加余下的丙烯腈 477克（9摩尔），滴 加毕，不时检测双键，至双鍵基本消失，再继续控温控 pH搅拌通氯气 10—20分钟。  Put a four-necked flask: electric stirrer, thermometer, dropping funnel, gas introduction tube, add 53 grams (1 mole) of acrylonitrile and 200 grams of water, cool to 5 ° C outside, stir quickly, and slowly pass in chlorine gas Use 10% sodium carbonate solution to adjust the pH so that the pH is controlled at 5-6 and the temperature is controlled at 0-] (TC, not more than 15'C. Add 477 grams (9 moles) of the remaining acrylonitrile dropwise. At the end, double bonds are detected from time to time until the double bonds have basically disappeared, and then continue to control the temperature and pH and stir the chlorine gas for 10-20 minutes.
将上述装置改成减压精馏装置，逐步升温至 60—70'C，蒸去未反 应的氯，接着蒸去水，去水毕，恢复常压。 加入溶剂苯 350克，相转移催 化剂 TBA (四丁基季胺盐） 12克，干燥氢氧化钠 400克，控温 30—5(TC 并快速搅拌，滴加甲酸乙酯 740克（10摩尔），滴加毕，继续剧烈搅拌并 保温反应 1一 0. 5小时，总缩合反应时间为 5— 8小时。 缩合反应毕，过 滤物料以除去无机物。 滤液以半倍体积 3 %硫酸洗涤，静置，分去水层。  The above device was changed to a vacuum distillation device, and the temperature was gradually raised to 60-70'C, and the unreacted chlorine was distilled off. Then, the water was distilled off, and after the water was removed, the atmospheric pressure was restored. Add 350 grams of benzene as solvent, 12 grams of phase transfer catalyst TBA (tetrabutyl quaternary amine salt), 400 grams of dry sodium hydroxide, control temperature 30-5 (TC and quickly stir, and add 740 grams of ethyl formate (10 moles) dropwise. After the dropwise addition, continue to stir vigorously and keep the reaction for 1.0 to 5 hours, and the total condensation reaction time is 5-8 hours. After the condensation reaction is completed, the material is filtered to remove inorganic matter. The filtrate is washed with half the volume of 3% sulfuric acid, Place and separate the water layer.
对油层，先减压回收水、溶剂苯，余下主要为 α氰基 β羟基丙酸乙 酯，通保护气体二氧化硫，在强搅拌下滴加浓度 100%的硫酸 1470克 ( 15摩尔），滴加毕，继续强搅拌，升温至 80— 95 °C，经半小时，再升至 150°C ,经 15— 20分钟，脱水反应毕，在有保护气体下，减压精馏出氰丙 烯酸乙酯，流入装有五氧化二磷和对苯二酚的溶器内，收集 80— 90'C / 1. 3 X 103— 2. 7 X 10 Pa馏份。 For the oil layer, first recover water and solvent benzene under reduced pressure. The remainder is mainly alpha cyano beta hydroxypropionate. Pass the protective gas sulfur dioxide. Add 1470 g (15 mol) of 100% sulfuric acid dropwise under strong stirring. After completion, continue to stir vigorously, raise the temperature to 80-95 ° C, and then rise to 150 ° C after half an hour. After 15-20 minutes, the dehydration reaction is completed. Under a protective gas, cyanopropane is distilled off under reduced pressure Acid ethyl ester, phosphorus pentoxide, and flows into the inside with dissolved hydroquinone, a collection 80- 90'C / 1. 3 X 10 3 - 2. 7 X 10 Pa fraction.
在生产氰丙烯酸甲酯时，用到甲酸甲酯。 生产氰丙烯酸丙酯时，用 到甲酸丙酯。生产氰丙烯鲛丁酯时，用到甲酸丁酯。生产氰丙烯酸辛酯 时，用到甲鲛辛酯。 生产氰丙烯酸苄酯时，用到甲酸苄酯。 生产氰丙烯 酸苯酚酯时，用到甲酸苯酚酯。 也即是生产各种氰丙烯酸酯时，用到相 对应的甲鲛酯，同时采用相应的反应温度和减压精馏温度，以适应有关 反应物的沸点。  In the production of methyl cyanoacrylate, methyl formate is used. For the production of propyl cyanoacrylate, propyl formate is used. Butyl formate is used when producing butyl cyanopropene butyl cyanoacrylate. For the production of octyl cyanoacrylate, methyloctyl octyl is used. When producing benzyl cyanoacrylate, benzyl formate is used. When producing phenol cyanoacrylate, phenol formate is used. That is, when producing various cyanoacrylates, the corresponding formazan esters are used, and the corresponding reaction temperature and vacuum distillation temperature are used to adapt to the boiling points of the relevant reactants.
实施例 2 Example 2
本实施例为在合成工艺过程中，缩合步骤采用液-液二相的相转移 催化缩合反应，其它工艺，基本上与实施例 1相同。  In this embodiment, during the synthesis process, the condensation step uses a liquid-liquid two-phase phase transfer to catalyze the condensation reaction. The other processes are basically the same as in Example 1.
在第一步工艺过程"次氯酸加成"完毕后，稍减压除去未反应的氯， 加入溶剂苯 350克，相转移催化剂新洁尔灭（慈溪药厂生产） 12克，甲 鲛乙酯 740克（10摩尔），控温 30— 50'C，强搅拌，滴加氢氧化钠水溶液 (氢氧化钠 400克，水 1000克），整个滴加过程，溶液 pH应控制在 8以 下，最好 7左右。 滴加完毕，继续保温反应 0. 5—1小时，然后静置，分 层，分取油层。  After the completion of the "hypochlorous acid addition" in the first step, remove the unreacted chlorine under reduced pressure, add 350 grams of benzene as a solvent, 12 grams of phase transfer catalyst Xinjieer (Cixi Pharmaceutical Factory), and 740 grams of methyl ethyl ester. (10 moles), temperature control 30-50'C, strong stirring, dropwise add sodium hydroxide aqueous solution (400 grams of sodium hydroxide, 1000 grams of water), the pH of the solution should be controlled below 8, preferably 7 about. After the dropwise addition, continue to incubate for 0.5 to 1 hour, then stand still, separate the layers and separate the oil layer.
油层先回收溶剂苯，余下物料主要为粗 c 氰基 β羟基丙酸乙酯，直 接进行下一步分子内脱水反应，和实施例 1 的相同。  The solvent benzene was recovered in the oil layer first, and the remaining materials were mainly crude c cyano beta hydroxypropionate, which was directly subjected to the next intramolecular dehydration reaction, which was the same as in Example 1.
本发明开创了氰丙烯酸酯类产品合成的新方法，与以剧毒氢氰酸 类盐为基础的老工艺路线相比具有很多优点，既降低成本，也降低环保 费用，同时也使劳动安全更有保障。 并且，也使氰丙烯酸酯类胶粘剂的 应用有一个更好的前景。  The invention initiates a new method for synthesizing cyanoacrylate products, which has many advantages compared with the old process route based on highly toxic hydrocyanic acid salts, which not only reduces costs, but also reduces environmental protection costs, and also makes labor safety more Guaranteed. In addition, the application of cyanoacrylate adhesives has a better prospect.

Claims

1. 一种通过三步工艺过程合成氰丙烯酸酯的方法，其特征在于起始 原料为丙烯腈，所述合成工艺过程包含次氯酸加成反应，相转移催化缩 合反应及分子内脱水反应。 1. A method for synthesizing cyanoacrylate through a three-step process, characterized in that the starting material is acrylonitrile, and the synthesis process includes a hypochlorous acid addition reaction, a phase transfer catalyzed condensation reaction, and an intramolecular dehydration reaction.
才  Only
2. 如权利要求 1所述的方法，其特征在于加成反应产物 α氯 β羟基 丙腈与一种甲鲛酯进行相转移催化缩合反应，所述的甲酸酯选自甲酸 甲酯、甲鲛乙酯、甲酸丙酯、甲酸丁酯、甲酸辛酯、甲酸苄酯或甲酸苯酚 酯。 2. The method according to claim 1, characterized in that the addition reaction product α chloride β hydroxypropionitrile is subjected to a phase transfer catalyzed condensation reaction with a formazan ester, the formate is selected from methyl formate, forma Ethyl acetate, propyl formate, butyl formate, octyl formate, benzyl formate or phenol formate.
书  Book
PCT/CN1995/000066 1995-06-06 1995-08-18 A synthetic method for cyanoacrylate WO1996039376A1 (en)

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CN 95106908 CN1138573A (en) 1995-06-06 1995-06-06 Method for synthetizing cyano-propenoic acid ester
CN95106908.X 1995-06-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013079849A1 (en) 2011-12-01 2013-06-06 Arkema France Method for cleaving unsaturated fatty chains

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5562057A (en) * 1978-11-01 1980-05-10 Matsumoto Seiyaku Kogyo Kk Synthesis of alpha-cyanoacrylate
DE3312426A1 (en) * 1983-04-07 1984-10-11 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING 2-CYANACRYLATE
CN1070636A (en) * 1991-09-19 1993-04-07 西南师范大学 The technology of preparation α-Qing Jibingxisuanzhi

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5562057A (en) * 1978-11-01 1980-05-10 Matsumoto Seiyaku Kogyo Kk Synthesis of alpha-cyanoacrylate
DE3312426A1 (en) * 1983-04-07 1984-10-11 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING 2-CYANACRYLATE
CN1070636A (en) * 1991-09-19 1993-04-07 西南师范大学 The technology of preparation α-Qing Jibingxisuanzhi

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013079849A1 (en) 2011-12-01 2013-06-06 Arkema France Method for cleaving unsaturated fatty chains
US9035079B2 (en) 2011-12-01 2015-05-19 Arkema France Method for cleaving unsaturated fatty chains

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