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WO2005040086A1 - Composition d'acides carboxyliques tertiaires - Google Patents

Composition d'acides carboxyliques tertiaires Download PDF

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Publication number
WO2005040086A1
WO2005040086A1 PCT/JP2004/015693 JP2004015693W WO2005040086A1 WO 2005040086 A1 WO2005040086 A1 WO 2005040086A1 JP 2004015693 W JP2004015693 W JP 2004015693W WO 2005040086 A1 WO2005040086 A1 WO 2005040086A1
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WO
WIPO (PCT)
Prior art keywords
carboxylic acid
tertiary carboxylic
tertiary
carbon atoms
mass
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.)
Ceased
Application number
PCT/JP2004/015693
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English (en)
Japanese (ja)
Inventor
Tetsuya Saruwatari
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan 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 Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of WO2005040086A1 publication Critical patent/WO2005040086A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids

Definitions

  • the present invention relates to a tertiary carboxylic acid composition having high biodegradability.
  • This tertiary carboxylic acid composition has high biodegradability and is suitable as a raw material for a tertiary carboxylic acid ester or a metal salt thereof.
  • Tertiary carboxylic acid esters or metal salts thereof are widely used as compounding agents for paints, solvents for paints, and the like.
  • a biodegradable compound is used as a compounding agent of a paint used for painting a structure used in water such as the bottom of a ship (see, for example).
  • Patent Document 1 When the tertiary carboxylic acid ester or its metal salt is used as a compounding agent for a paint used for painting a structure used in water, it is desirable to impart biodegradability.
  • the carboxylic acid composition containing a tertiary carboxylic acid as a main component used for the production of the tertiary carboxylic acid ester or its metal salt used for the above-mentioned applications, etc. includes hydrochloric acid, sulfuric acid, phosphoric acid and trifluoride.
  • the olefins are reacted with carbon monoxide and water in the presence of an acid catalyst containing boron or the like to synthesize a carboxylic acid having one more carbon atom than the olefins as a raw material, that is, a so-called Koch reaction. (For example, see Patent Document 2).
  • a carboxylic acid composition produced by such a known Koch reaction generally contains a plurality of types of tertiary carboxylic acids due to the kind of olefins used as a raw material. Therefore, depending on the type of tertiary carboxylic acid contained in the carboxylic acid composition, the degree of biodegradability of the tertiary carboxylic acid ester or a metal salt thereof synthesized using this carboxylic acid composition is high. Will change. Tertiary carboxylic acid esters or metal salts thereof synthesized using conventional carboxylic acid compositions have been difficult to say, but have sufficient biodegradability.
  • Patent Document 1 JP-A-7-109339
  • Patent Document 2 Japanese Patent Publication No. 30-3362 Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and provides a novel tertiary carboxylic acid composition having high biodegradability and suitable as a raw material for a tertiary carboxylic acid ester or a metal salt thereof. It is intended to do so.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, a tertiary carboxylic acid composition containing a tertiary carboxylic acid having 7 to 17 carbon atoms as a main component, It has been found that the above object is achieved by a tertiary carboxylic acid composition containing a specific amount of a tertiary carboxylic acid having a specific structure.
  • the present invention has been completed based on powerful knowledge. That is, the present invention relates to a tertiary carboxylic acid composition containing a tertiary carboxylic acid having 7 to 17 carbon atoms as a main component, wherein a carbon atom bonded to four carbon atoms is included in the molecular structure.
  • the tertiary carboxylic acid composition of the present invention contains a tertiary carboxylic acid having 7 to 17 carbon atoms as a main component, and has one carbon atom in the molecular structure bonded to four carbon atoms. It has a tertiary carboxylic acid content of 90% by mass or more, preferably 95% by mass or more, which does not contain a carbon atom bonded to three or more carbon atoms in the molecular structure.
  • a tertiary carboxylic acid composition having one carbon atom bonded to four carbon atoms in the molecular structure and not including a carbon atom bonded to three or more carbon atoms in the molecular structure.
  • the tertiary carboxylic acid having 7 to 17 carbon atoms used in the present invention is obtained by reacting a olefin having 6 to 16 carbon atoms with carbon monoxide and water.
  • the C6-16 olefin used as a raw material is not particularly limited as long as it is a C6-16 monoolefin, but in the case of industrial production, it can be obtained at relatively low cost. Is preferred.
  • Examples of the ⁇ -olefin include 1-hexene, 1-otaten, 1-decene, 1-dodecene, 1-tetradecene, and 11-hexadecene.
  • Examples of the catalyst used in the above reaction include sulfuric acid, sulfuric acid and phosphoric acid and sulfur or boron trifluoride, a catalyst comprising boron trifluoride or boron trifluoride and phosphoric acid, 60 to 98% by mass, preferably 80 to 95% by mass.
  • a metal compound a metal compound.
  • metal compound examples include metal oxides such as cuprous oxide, cupric oxide, silver oxide, and gold oxide; mixtures of divalent copper compounds such as silver sulfate, metallic copper, and cupric oxide; and metallic copper. Is mentioned.
  • metal oxides such as cuprous oxide, cupric oxide, silver oxide, silver sulfate and gold oxide
  • these metal compounds may be used alone or in a combination of two or more.
  • the concentration of the aqueous sulfuric acid solution containing water used as a reaction raw material is generally about 60 to 98% by mass, preferably 80 to 95% by mass.
  • the concentration of the aqueous solution of boron trifluoride containing water used as a reaction raw material is usually about 60 to 98% by mass, preferably 80 to 95% by mass.
  • the usage ratio of sulfuric acid and phosphoric acid is usually about 0.1-0.6 mol, preferably 0.2-0.5 mol, of phosphoric acid per mol of sulfuric acid.
  • the usage ratio of sulfuric acid and boron trifluoride is usually about 0.1 to 3 mol, preferably 112 mol, per mol of sulfuric acid.
  • the usage ratio of boron trifluoride and phosphoric acid is usually about 0.1 to 12 mol, preferably 0.5 to 1.5 mol, per mol of phosphoric acid.
  • the ratio of sulfuric acid to the metal compound is usually about 0.001 to 0.1 mol, preferably 0.005 to 0.05 mol, per mol of sulfuric acid.
  • the amount of these catalysts to be used is generally 0.3 mol or more, preferably 5 to 20 mol, per 1 mol of the starting olefins.
  • a carboxylic acid is produced by subjecting the above olefins, carbon monoxide and water to a carbonyl reaction in the presence of the above catalyst.
  • the reaction system may be any of a batch system, a semi-batch system and a continuous system.
  • the reaction conditions at this time are not particularly limited, but the reaction temperature is usually about ⁇ 10 to 80 ° C., preferably 0 to 30 ° C.
  • the reaction pressure is generally about 0-lOMPa'G, preferably 0.2-5 MPa'G. By setting the reaction pressure within the above range, it is possible to suppress the isomerization of the carbon skeleton and control the generation of a carboxylic acid which is difficult to esterify.
  • the carbon monoxide partial pressure is usually at least 0.1 OlMPa.
  • the reaction time is usually 10 to 180 minutes, preferably 60 to 120 minutes after feeding the olefins.
  • a carbonyl distillate reaction product obtained by the reaction of the above-mentioned raw materials is subjected to extraction treatment with an organic solvent.
  • the organic solvent it is preferable to use at least one kind of hexane selected from n-hexane and cyclohexanecapane.
  • the amount of hexane used is usually about 100 to 500% by mass, preferably 150 to 300% by mass, based on the reaction product. In this case, about 5 to 20% by mass of water may be used in combination with hexane. Extraction with hexane can be carried out by stirring and standing.
  • the carbo-ludani reaction product is separated into a hexane phase (oil phase) containing carboxylic acid and an aqueous phase containing sulfuric acid. Since this hexane phase is mixed with a sulfuric acid complex sulfuric acid in an amount proportional to the number of moles of the extracted carboxylic acid, water is added to the hexane phase, and the mixture is stirred (washed with water) and statically mixed. Containing carboxylic acid It is preferable to separate the hexane phase and the aqueous phase containing sulfuric acid (dilute sulfuric acid phase) and wash out the sulfuric acid in the hexane phase. If the amount of water to be added is about 0.3 to 3 times the amount of water consumed in the carboxylation reaction (theoretical water amount), the complex sulfuric acid in the hexane phase should be almost completely recovered. Can be.
  • the hexane phase containing the carboxylic acid thus obtained still contains a trace amount of sulfate groups. Therefore, it is preferable to add an aqueous alkali solution to neutralize the sulfate groups.
  • the kind of the alkali used is not particularly limited, but usually, sodium hydroxide, potassium hydroxide and the like are used.
  • the concentration of the aqueous alkali solution is usually 0
  • the amount of alkali added to the hexane phase is determined by titrating the hexane phase after washing out the sulfuric acid. For titration, potassium hydroxide and the like having a concentration of about 0.1 mol Z liter can be used. In order to neutralize the sulfate, it is preferable to use an aqueous solution containing an alkali not more than three times the amount of the sulfate determined, and an aqueous solution containing one to three times equivalent of the alkali is more preferable.
  • the formation of emulsion can be suppressed, and the hexane phase and the aqueous phase can be separated in 6 hours or less.
  • the carboxylic acid of interest can be obtained by collecting the carboxylic acid from the hexane phase after neutralizing the sulfate with an aqueous alkali solution. In order to purify the obtained carboxylic acid, a known treatment such as distillation may be performed.
  • the recovered cyclohexane phase was titrated with a 0.1 mol Z liter aqueous potassium hydroxide solution to quantify the amount of sulfate groups.
  • the results showed that the recovered cyclohexane phase contained 0.29 mmol of sulfate. Therefore, 0.1 mol / l of an aqueous solution of sodium hydroxide, which is 1.1 equivalents of the sulfate, was added, and the mixture was stirred and allowed to stand. And separated into. From the cyclohexane phase, the following structure (in order of force, 13% by mass, 22% by mass, 21% by mass, 25% by mass, 11% by mass, and the other 8% by mass) is distilled. 4.5 g of a carboxylic acid having 13 carbon atoms was recovered.
  • a biochemical oxygen demand (BOD) test was performed on the obtained carboxylic acid. As a result, the biodegradation rate in 28 days was 58%.
  • the biochemical oxygen demand (BOD) refers to the amount of dissolved acid consumed when stirring at 25 ° C for 28 days in accordance with JIS K0102-1989.
  • the biodegradation rate was calculated according to the following equation.
  • Biodegradation rate (%) (BOD / TOD) x 100
  • a tertiary carboxylic acid composition containing 50% by mass or more of a tertiary carboxylic acid having a) has a BOD test performed in the same manner as described above. there were.

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

Abstract

L'invention se rapporte à une nouvelle composition d'acides carboxyliques tertiaires qui peut être utilisée en tant que matière première pour la production d'esters d'acides carboxyliques tertiaires ou de sels métalliques associés qui sont hautement biodégradables. Cette composition comporte des acides carboxyliques tertiaires C1-17 en tant qu'ingrédients principaux, et la proportion d'acides carboxyliques tertiaires ayant, dans la molécule, un atome de carbone lié à quatre atomes de carbone et ne contenant, dans la molécule, aucun atome de carbone lié à au moins trois atomes de carbone est supérieure ou égale à 90 % en poids.
PCT/JP2004/015693 2003-10-27 2004-10-22 Composition d'acides carboxyliques tertiaires Ceased WO2005040086A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003366109A JP2005126392A (ja) 2003-10-27 2003-10-27 第三級カルボン酸組成物
JP2003-366109 2003-10-27

Publications (1)

Publication Number Publication Date
WO2005040086A1 true WO2005040086A1 (fr) 2005-05-06

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PCT/JP2004/015693 Ceased WO2005040086A1 (fr) 2003-10-27 2004-10-22 Composition d'acides carboxyliques tertiaires

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WO (1) WO2005040086A1 (fr)

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US9583411B2 (en) 2014-01-17 2017-02-28 Invensas Corporation Fine pitch BVA using reconstituted wafer with area array accessible for testing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6176434A (ja) * 1984-09-21 1986-04-18 Idemitsu Petrochem Co Ltd 第３級カルボン酸の製造方法
JP2000327620A (ja) * 1999-05-24 2000-11-28 Agency Of Ind Science & Technol 強酸性固体酸触媒を用いた第三級カルボン酸の製造法
JP2001039918A (ja) * 1999-08-02 2001-02-13 Agency Of Ind Science & Technol 金属イオン交換ゼオライトを用いた第三級カルボン酸及びそのエステルの製造方法
JP2002069028A (ja) * 2000-08-31 2002-03-08 National Institute Of Advanced Industrial & Technology 金属カルボニル触媒による第三級カルボン酸および第三級カルボン酸エステルの合成方法並びに合成用触媒

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6176434A (ja) * 1984-09-21 1986-04-18 Idemitsu Petrochem Co Ltd 第３級カルボン酸の製造方法
JP2000327620A (ja) * 1999-05-24 2000-11-28 Agency Of Ind Science & Technol 強酸性固体酸触媒を用いた第三級カルボン酸の製造法
JP2001039918A (ja) * 1999-08-02 2001-02-13 Agency Of Ind Science & Technol 金属イオン交換ゼオライトを用いた第三級カルボン酸及びそのエステルの製造方法
JP2002069028A (ja) * 2000-08-31 2002-03-08 National Institute Of Advanced Industrial & Technology 金属カルボニル触媒による第三級カルボン酸および第三級カルボン酸エステルの合成方法並びに合成用触媒

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