WO2001046112A1 - Procede de prevention de la polymerisation d'un compose vinylique - Google Patents

Procede de prevention de la polymerisation d'un compose vinylique Download PDF

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Publication number
WO2001046112A1
WO2001046112A1 PCT/JP2000/008714 JP0008714W WO0146112A1 WO 2001046112 A1 WO2001046112 A1 WO 2001046112A1 JP 0008714 W JP0008714 W JP 0008714W WO 0146112 A1 WO0146112 A1 WO 0146112A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
vinyl compound
polymerization
preventing polymerization
phenothiazine
Prior art date
Application number
PCT/JP2000/008714
Other languages
English (en)
Japanese (ja)
Inventor
Kouji Tomita
Takashi Nakagawa
Original Assignee
Idemitsu Petrochemical Co., Ltd.
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 Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2001046112A1 publication Critical patent/WO2001046112A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives

Definitions

  • the present invention relates to a method for preventing polymerization of a vinyl compound, and more particularly, to a method for distilling a vinyl compound, particularly acrylic acid and / or methacrylic acid (both are collectively referred to as (meth) acrylic acid) and esters thereof.
  • the present invention relates to a method for effectively preventing polymerization in a production process.
  • (meth) acrylic acid and its esters are useful monomers as raw materials for various organic materials such as paints, adhesives, and water-absorbing resins, and are widely used.
  • products with higher purity have been required.
  • these monomers are extremely easily polymerized by heat, light, peroxides, etc., in the production process, troubles in the distillation system often occur due to the produced polymer. Specifically, it is known that the performance of the distillation column is reduced, the heat transfer performance of the distillation column reboiler is reduced, and furthermore, the distillation column is clogged, which is a great obstacle to the production process. Therefore, development of a method for preventing polymerization of these monomers is an important industrial issue.
  • Typical polymerization inhibitors include phenols such as hydroquinone and hydroquinone monomethyl ether; amines such as phenothiazine and diphenylamine; heavy metal salts such as copper dibutyldithiocarbamate and manganese acetate; nitroso compounds; Aminoxyls such as nitro compounds and tetramethylbiperidinoxyl (TEMPO) derivatives are known.
  • phenols such as hydroquinone and hydroquinone monomethyl ether
  • amines such as phenothiazine and diphenylamine
  • heavy metal salts such as copper dibutyldithiocarbamate and manganese acetate
  • nitroso compounds Aminoxyls such as nitro compounds and tetramethylbiperidinoxyl (TEMPO) derivatives are known.
  • TEMPO tetramethylbiperidinoxyl
  • phenols, phenothiazines essentially require oxygen to produce their effects, and are not sufficiently effective in a reduced pressure system.
  • copper dibutyldithiocarbamate works effectively even in the absence of oxygen, it hardly dissolves in water and is not suitable for preventing polymerization in the presence of water.
  • TEMPOs are water-soluble and effective, but expensive. Therefore, there is a demand for the development of a low-cost and effective polymerization inhibitor even in the absence of oxygen or in the presence of water. Disclosure of the invention
  • the present invention has been made in view of the above, and an object of the present invention is to provide a method for preventing polymerization of a vinyl compound using an inexpensive polymerization inhibitor effective in a small amount even in the absence of oxygen or in the presence of water. Things.
  • the present inventors have conducted intensive studies and have found that the above object of the present invention can be effectively achieved by using funothiazine and a strong acid as polymerization inhibitors, and have completed the present invention.
  • the present invention provides a method for preventing polymerization of a vinyl compound, which comprises using phenothiazine and a strong acid as polymerization inhibitors.
  • Examples of the vinyl compound to which the method of the present invention can be applied include (meth) acrylic acid, (meth) acrylic acid ester, styrene, acrylonitrile, and the like. Among them, (meth) acrylic acid is particularly preferable. is there.
  • phenothiazine is used as one component of the polymerization inhibitor for the bullet compound.
  • phenothiazine commercially available phenothiazine can be used, High purity is desirable from the viewpoint of the effect.
  • the amount of phenothiazine used is not particularly limited, but is usually 1 to 300 ppm by weight, preferably 10 to 500 ppm by weight, based on the butyl compound. If the amount is too small, the effect of preventing polymerization may not be sufficiently exhibited, and if the amount is too large, the effect may not be improved for the amount.
  • a strong acid is used as another component of the polymerization inhibitor of the present invention.
  • strong acids include mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and chloric acids, and organic acids such as p-toluenesulfonic acid and trifluoroacetic acid. Ensulphonic acid is preferred.
  • the amount of the strong acid is not particularly limited, but is usually 1 to 50 times, preferably 2 to 20 times the molar amount of phenothiazine. If the amount is too small, the effect of preventing polymerization may not be sufficiently exerted. If the amount is too large, the effect may not be improved for the amount thereof, and a problem of corrosion may occur.
  • the method of adding the polymerization inhibitor is not particularly limited, but may be added after previously mixing phenothiazine and a strong acid, or may be added separately.
  • oxygen concentration in the distillation column is not limited.
  • Example 1 the same procedure was performed except that the polymerization inhibitor was not added, and clouding was observed in 5 minutes.
  • Example 4 100 phosphoric acid 2,000 > 360 minutes
  • Example 2 was repeated except that PZT was replaced with hydroquinone (HQ). The results are shown in Table 4.
  • the combined use of funinothiazine and a strong acid as polymerization inhibitors effectively prevents polymerization in the vinyl compound production process even in the absence of oxygen and in the presence of water. It can be effectively applied to the vacuum distillation purification process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un procédé de prévention de la polymérisation d'un composé vinylique au moyen d'un inhibiteur de polymérisation peu coûteux. Cet inhibiteur reste efficace en l'absence d'oxygène ou en présence d'eau, même en petite quantité. Ce procédé consiste à utiliser comme inhibiteur de polymérisation une association de phénothiazine et d'un acide fort.
PCT/JP2000/008714 1999-12-21 2000-12-08 Procede de prevention de la polymerisation d'un compose vinylique WO2001046112A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/362125 1999-12-21
JP36212599A JP2001172224A (ja) 1999-12-21 1999-12-21 ビニル化合物の重合防止方法

Publications (1)

Publication Number Publication Date
WO2001046112A1 true WO2001046112A1 (fr) 2001-06-28

Family

ID=18475989

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/008714 WO2001046112A1 (fr) 1999-12-21 2000-12-08 Procede de prevention de la polymerisation d'un compose vinylique

Country Status (4)

Country Link
JP (1) JP2001172224A (fr)
CN (1) CN1249012C (fr)
TW (1) TWI275584B (fr)
WO (1) WO2001046112A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021200390A1 (fr) * 2020-03-30 2021-10-07 日東電工株式会社 Film polarisant, film polarisant stratifié, panneau d'affichage d'image et dispositif d'affichage d'image

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4834250B2 (ja) * 2001-07-31 2011-12-14 伯東株式会社 芳香族ビニル化合物の重合抑制方法
JP4548821B2 (ja) * 2004-03-25 2010-09-22 伯東株式会社 （メタ）アクリル酸および（メタ）アクリル酸エステルの重合抑制方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0302697A1 (fr) * 1987-08-07 1989-02-08 Rohm And Haas Company Inhibition de la polymérisation d'acides insaturés en phase vapeur
JPH0834748A (ja) * 1994-07-27 1996-02-06 Hakuto Co Ltd ビニル化合物を扱う工程でのファウリング防止方法
JPH0881397A (ja) * 1994-09-12 1996-03-26 Sumitomo Chem Co Ltd ビニル化合物の重合防止方法
JP2000234002A (ja) * 1999-02-16 2000-08-29 Chisso Corp ラジカル重合禁止剤

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53137909A (en) * 1977-05-06 1978-12-01 Nippon Oil & Fats Co Ltd Purification of fatty acid
EP0863131B1 (fr) * 1997-03-05 2000-05-17 Dainippon Ink And Chemicals, Inc. Monomères acryliques, polymères de ceux-ci, et composition réticulante

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0302697A1 (fr) * 1987-08-07 1989-02-08 Rohm And Haas Company Inhibition de la polymérisation d'acides insaturés en phase vapeur
JPH0834748A (ja) * 1994-07-27 1996-02-06 Hakuto Co Ltd ビニル化合物を扱う工程でのファウリング防止方法
JPH0881397A (ja) * 1994-09-12 1996-03-26 Sumitomo Chem Co Ltd ビニル化合物の重合防止方法
JP2000234002A (ja) * 1999-02-16 2000-08-29 Chisso Corp ラジカル重合禁止剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021200390A1 (fr) * 2020-03-30 2021-10-07 日東電工株式会社 Film polarisant, film polarisant stratifié, panneau d'affichage d'image et dispositif d'affichage d'image

Also Published As

Publication number Publication date
CN1362943A (zh) 2002-08-07
TWI275584B (en) 2007-03-11
JP2001172224A (ja) 2001-06-26
CN1249012C (zh) 2006-04-05

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