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WO1996039376A1 - Procede de synthese de cyanoacrylate - Google Patents

Procede de synthese de 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
Authority
WO
WIPO (PCT)
Prior art keywords
formate
reaction
cyanoacrylate
phase transfer
acrylonitrile
Prior art date
Application number
PCT/CN1995/000066
Other languages
English (en)
Chinese (zh)
Inventor
Sing Shiang
Original Assignee
Sing Shiang
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sing Shiang filed Critical Sing Shiang
Priority to AU32514/95A priority Critical patent/AU3251495A/en
Publication of WO1996039376A1 publication Critical patent/WO1996039376A1/fr

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Classifications

    • 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.

Landscapes

  • 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

L'invention concerne un procédé de synthèse de cyanoacrylate au moyen d'acrylonitrile comme matériau de départ principal, ledit procédé consistant en trois étapes, à savoir: addition d'acide hypochlorique, condensation de transfert de phase et déshydratation intramoléculaire. Un tel procédé évite d'avoir à utiliser, directement ou indirectement, de l'acide hydrocyanique, ou un sel de celui-ci, qui est extrêmement toxique.
PCT/CN1995/000066 1995-06-06 1995-08-18 Procede de synthese de cyanoacrylate WO1996039376A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32514/95A AU3251495A (en) 1995-06-06 1995-08-18 A synthetic method for cyanoacrylate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN95106908.X 1995-06-06
CN 95106908 CN1138573A (zh) 1995-06-06 1995-06-06 一种合成氰丙烯酸酯的方法

Publications (1)

Publication Number Publication Date
WO1996039376A1 true WO1996039376A1 (fr) 1996-12-12

Family

ID=5076111

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN1995/000066 WO1996039376A1 (fr) 1995-06-06 1995-08-18 Procede de synthese de cyanoacrylate

Country Status (3)

Country Link
CN (1) CN1138573A (fr)
AU (1) AU3251495A (fr)
WO (1) WO1996039376A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013079849A1 (fr) 2011-12-01 2013-06-06 Arkema France Procede de coupure de chaines grasses insaturees

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 (de) * 1983-04-07 1984-10-11 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von 2-cyanacrylaten
CN1070636A (zh) * 1991-09-19 1993-04-07 西南师范大学 制备α-氰基丙烯酸酯的工艺

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 (de) * 1983-04-07 1984-10-11 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von 2-cyanacrylaten
CN1070636A (zh) * 1991-09-19 1993-04-07 西南师范大学 制备α-氰基丙烯酸酯的工艺

Cited By (2)

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

Also Published As

Publication number Publication date
AU3251495A (en) 1996-12-24
CN1138573A (zh) 1996-12-25

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