WO2005049542A1 - Tertiary carboxylic acid - Google Patents
Tertiary carboxylic acid Download PDFInfo
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- WO2005049542A1 WO2005049542A1 PCT/JP2004/017237 JP2004017237W WO2005049542A1 WO 2005049542 A1 WO2005049542 A1 WO 2005049542A1 JP 2004017237 W JP2004017237 W JP 2004017237W WO 2005049542 A1 WO2005049542 A1 WO 2005049542A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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- the present invention relates to a tertiary carboxylic acid having 14 or more carbon atoms obtained by reacting a bi-lidene type olefin having 13 or more carbon atoms with carbon monoxide and water, and more particularly to a paint.
- the present invention relates to tertiary carboxylic acids having 14 or more carbon atoms, which are expected to develop into technologies such as adhesives, pharmaceuticals, agricultural chemical intermediates, paint additives (heat resistance improvers), and resin additives (heat resistance improvers).
- Carboxylic acids react corresponding olefins with carbon monoxide and water to synthesize carboxylic acids having one more carbon atom than the olefins as raw materials, V, the so-called Koch reaction, etc.
- the carboxylic acid obtained by synthesis is generally obtained as a carboxylic acid mixture in which a cation obtained by adding a proton to the olefins used is isomerized and carbonylated.
- a cation obtained by adding a proton to the olefins used is isomerized and carbonylated.
- bi-lidene type olefin as a raw material satisfying the conditions, and there has been reported an example of synthesizing a carboxylic acid using a bi-lidene type olefin having 12 or less carbon atoms.
- a corresponding carboxylic acid having 14 or more carbon atoms was synthesized from a bi-lidene type olefin having 13 or more carbon atoms as a raw material.
- Patent Document 1 Japanese Patent Application Laid-Open No. 62-164645
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel tertiary carboxylic acid having 14 or more carbon atoms, which is useful for various uses.
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that It has been found that a tertiary carboxylic acid having 14 or more carbon atoms can be obtained by the reaction of the above bilidene type olefin, carbon monoxide and water.
- the present invention has been completed based on powerful knowledge.
- the present invention relates to a carboxylic acid obtained by reacting a bi-lidene type olefin having 13 or more carbon atoms, carbon monoxide and water, and represented by the following general formula (1)
- R 1 and R 2 represent a linear hydrocarbon group having a total carbon number of 11 or more.
- a tertiary carboxylic acid having 14 or more carbon atoms can be efficiently provided by a carboxylation reaction using a bilidene type olefin having 13 or more carbon atoms as a raw material.
- the tertiary carboxylic acid of the present invention has the following general formula (1)
- R 1 and R 2 each represent a linear hydrocarbon group having a total carbon number of 11 or more.
- the linear hydrocarbon group for R 1 and R 2 includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, and an n-ota group.
- Straight-chain alkyl groups such as a tyl group, an n-decyl group and an n-pentadecyl group;
- the R 1 and R 2 may be the same or different from each other, but have a total carbon number of 11 or more.
- tertiary carboxylic acid of the present invention examples include 2-xyl-2-enedecanic acid, 2-octyl-2-tridecanoic acid and the like.
- the tertiary carboxylic acid of the present invention is obtained by reacting a bi-lidene type olefin having 13 or more carbon atoms with carbon monoxide and water.
- a bi-lidene type olefin having 13 or more carbon atoms used as a raw material can be efficiently obtained by diluting an ⁇ -age olefin having 7 or more carbon atoms by a known method.
- Examples of hyolephine having 7 or more carbon atoms include 1 heptene, 1 otaten, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1 eicosene.
- Examples of the ⁇ -olefin dimer obtained by dimerizing an ⁇ -olefin having 7 or more carbon atoms include 2-hexyl-2-decene and 2-octyl-2-dodecene.
- the tertiary carboxylic acid of the present invention can be produced as follows. As a catalyst
- Sulfuric acid or a catalyst comprising sulfuric acid and phosphoric acid and metal or a metal compound.
- a catalyst selected from sulfuric acid, sulfuric acid and phosphoric acid, sulfuric acid and a metal compound, and sulfuric acid, phosphoric acid and a metal compound is used.
- the metal compound include metal oxides such as cuprous oxide, cupric oxide, silver oxide, and gold oxide, and mixtures of divalent copper compounds such as metallic copper and cupric oxide with metallic copper. .
- cuprous oxide, cupric oxide and silver oxide are preferred. These metal compounds may be used alone or in combination of two or more.
- the concentration of the aqueous sulfuric acid solution containing water used as a reaction raw material is usually about 40 to 98% by mass, preferably 60 to 95% by mass.
- the usage ratio of sulfuric acid and phosphoric acid is usually about 0.05 to 2.5 mol, preferably 0.2 to 1.5 mol, per mol of sulfuric acid.
- the ratio of the sulfuric acid to the metal compound is usually about 0.1 to 15 moles, preferably 0.2 to 5 moles per mole of sulfuric acid.
- the corresponding carboxylic acid is produced by a carbonyl reaction of the bi-lidene type olefin having 13 or more carbon atoms, carbon monoxide and water in the presence of the catalyst.
- the reaction conditions at this time are not particularly limited, but the reaction temperature is usually about 0 to 100 ° C, Preferably it is 0-40 ° C.
- the reaction pressure is usually about 0.1-lOMPa'G, preferably 14 MPa'G, and the partial pressure of carbon monoxide is usually 0.1 OlMPa or more.
- the reaction time is usually from 1 to 48 hours, preferably from 2 to 10 hours, after supplying the bi-lidene type olefin having 14 or more carbon atoms. In addition, this reaction can be basically performed without a solvent.
- the post-treatment of the carboxylation reaction product is not particularly limited, but the following method is preferred.
- the carbonylation reaction product obtained by the reaction of the above raw materials is subjected to extraction treatment with an organic solvent.
- the organic solvent it is preferable to use at least one hexane selected from n-hexane and cyclohexanecaprol.
- the amount of hexane used is usually about 100 to 500% by mass, and 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 as 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 added. It is preferable to separate the hexane phase containing carboxylic acid and the aqueous phase containing sulfuric acid (dilute sulfuric acid phase) by washing, 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.
- potassium hydroxide and the like having a concentration of about 0.1 mol Z liter can be used.
- To neutralize sulfate groups quantified It is preferable to use an aqueous solution containing three or less equivalents of an alkali of the amount of sulfate group. An aqueous solution containing one to three times equivalent of an 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 After neutralizing the sulfate groups with an aqueous alkali solution, the carboxylic acid is recovered from the hexane phase to obtain the desired carboxylic acid. 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 0.38 mmol of sulfate. Therefore, 0.1 mol / l of an aqueous solution of sodium hydroxide (1.1 mol / l) was added, stirred, and allowed to stand. After about 1 hour, the cyclohexane phase and aqueous phase And separated into. From the cyclohexane phase, a tertiary carboxylic acid having 17 carbon atoms was recovered by distillation. The yield was 73%. When the obtained tertiary carboxylic acid was analyzed, the following results were obtained. In the NMR measurement data, (1)-(17) indicate the position of the hydrocarbon group in the following chemical formula.
- the tertiary carboxylic acid of the present invention has been applied to paints, adhesives, pharmaceuticals, agricultural chemical intermediates, paint additives (heat resistance improvers), resin additives (heat resistance improvers), and the like. Be expected.
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Abstract
Description
明 細 書 Specification
第三級カルボン酸 Tertiary carboxylic acid
技術分野 Technical field
[0001] 本発明は、炭素数 13以上のビ -リデン型ォレフインと一酸ィ匕炭素と水との反応によ り得られる炭素数 14以上の第三級カルボン酸に関し、さらに詳しくは、塗料、接着剤 、医薬'農薬中間体、塗料添加剤 (耐熱性向上剤)、樹脂添加剤 (耐熱性向上剤)等 への技術展開が期待される炭素数 14以上の第三級カルボン酸に関する。 The present invention relates to a tertiary carboxylic acid having 14 or more carbon atoms obtained by reacting a bi-lidene type olefin having 13 or more carbon atoms with carbon monoxide and water, and more particularly to a paint. The present invention relates to tertiary carboxylic acids having 14 or more carbon atoms, which are expected to develop into technologies such as adhesives, pharmaceuticals, agricultural chemical intermediates, paint additives (heat resistance improvers), and resin additives (heat resistance improvers).
背景技術 Background art
[0002] カルボン酸は、これに対応するォレフイン類と一酸化炭素と水とを反応させ、原料の ォレフィン類よりも炭素数が一つ多 、カルボン酸を合成する、 V、わゆるコッホ反応等 により合成することができる。また、触媒成分として銅酸化物を加えることにより、低圧 でカルボン酸を合成する方法も開示されて 1ヽる（例えば、特許文献 1参照)。 [0002] Carboxylic acids react corresponding olefins with carbon monoxide and water to synthesize carboxylic acids having one more carbon atom than the olefins as raw materials, V, the so-called Koch reaction, etc. Can be synthesized by There is also disclosed a method of synthesizing a carboxylic acid at a low pressure by adding a copper oxide as a catalyst component (for example, see Patent Document 1).
一方、合成により得られるカルボン酸は、一般には、用いるォレフィン類にプロトン が付加したカチオンが異性ィ匕され、カルボニル化されたカルボン酸混合物として得ら れる。より選択的に目的とするカルボン酸を得るには、炭素骨格が破壊されることなく 安定なカルボカチオンが生成することが必要である。その条件を満たす原料として、 ビ-リデン型のォレフィンを用いることが考えられ、従来、炭素数 12以下のビ-リデン 型ォレフインを用いてカルボン酸を合成した例は報告されている。しかしながら、炭素 数 13以上のビ -リデン型ォレフインを原料として、これに対応する炭素数 14以上の カルボン酸を合成した例は報告されて 、な!/、。 On the other hand, the carboxylic acid obtained by synthesis is generally obtained as a carboxylic acid mixture in which a cation obtained by adding a proton to the olefins used is isomerized and carbonylated. To obtain the desired carboxylic acid more selectively, it is necessary to generate a stable carbocation without breaking the carbon skeleton. It is conceivable to use bi-lidene type olefin as a raw material satisfying the conditions, and there has been reported an example of synthesizing a carboxylic acid using a bi-lidene type olefin having 12 or less carbon atoms. However, there has been reported an example in which a corresponding carboxylic acid having 14 or more carbon atoms was synthesized from a bi-lidene type olefin having 13 or more carbon atoms as a raw material.
[0003] 特許文献 1：特開昭 62— 164645号公報 [0003] Patent Document 1: Japanese Patent Application Laid-Open No. 62-164645
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0004] 本発明は、上記事情に鑑みなされたもので、各種の用途に有用な新規な炭素数 1 4以上の第三級カルボン酸を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel tertiary carboxylic acid having 14 or more carbon atoms, which is useful for various uses.
課題を解決するための手段 Means for solving the problem
[0005] 本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、炭素数 13以 上のビ-リデン型ォレフインと一酸ィ匕炭素と水との反応により、炭素数 14以上の第三 級カルボン酸が得られることを見出した。本発明は力かる知見に基づいて完成したも のである。 [0005] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that It has been found that a tertiary carboxylic acid having 14 or more carbon atoms can be obtained by the reaction of the above bilidene type olefin, carbon monoxide and water. The present invention has been completed based on powerful knowledge.
すなわち、本発明は、炭素数 13以上のビ -リデン型ォレフインと一酸ィ匕炭素と水と の反応により得られるカルボン酸であって、下記一般式（1) That is, the present invention relates to a carboxylic acid obtained by reacting a bi-lidene type olefin having 13 or more carbon atoms, carbon monoxide and water, and represented by the following general formula (1)
[0006] [化 1] [0006] [Formula 1]
CH3 CH 3
R1 ― 广 R2 ( 1 ) R 1 ― Hiroshima R 2 (1)
COOH COOH
(式中、 R1及び R2は、その合計炭素数が 11以上の直鎖状炭化水素基を示す。 ) [0007] で表される第三級カルボン酸を提供するものである。 (Wherein, R 1 and R 2 represent a linear hydrocarbon group having a total carbon number of 11 or more.) [0007] The present invention provides a tertiary carboxylic acid represented by the following formula:
発明の効果 The invention's effect
[0008] 本発明によれば、炭素数 13以上のビ -リデン型ォレフインを原料とするカルボ-ル 化反応により、炭素数 14以上の第三級カルボン酸を効率よく提供することができる。 発明を実施するための最良の形態 [0008] According to the present invention, a tertiary carboxylic acid having 14 or more carbon atoms can be efficiently provided by a carboxylation reaction using a bilidene type olefin having 13 or more carbon atoms as a raw material. BEST MODE FOR CARRYING OUT THE INVENTION
[0009] 本発明の第三級カルボン酸は、下記一般式（1) The tertiary carboxylic acid of the present invention has the following general formula (1)
[0010] [化 2] [0010] [Formula 2]
CH3 CH 3
R1 — †一 R2 ( 1 ) R 1 — R 一 R 2 (1)
COOH COOH
(式中、 R1及び R2は、その合計炭素数が 11以上の直鎖状炭化水素基を示す。 ) [0011] で表されるものである。上記一般式（1)において、 R1及び R2の直鎖状炭化水素基と しては、メチル基、ェチル基、 n—プロピル基、 n—ブチル基、 n—へキシル基、 n—オタ チル基、 n—デシル基、 n—ゥンデシル基などの直鎖状アルキル基を挙げることができ る。 R1及び R2は、互いに同一でも異なっていてもよいが、それらの合計炭素数は 11 以上である。 (In the formula, R 1 and R 2 each represent a linear hydrocarbon group having a total carbon number of 11 or more.) [0011] In the general formula (1), the linear hydrocarbon group for R 1 and R 2 includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, and an n-ota group. Straight-chain alkyl groups such as a tyl group, an n-decyl group and an n-pentadecyl group; The R 1 and R 2 may be the same or different from each other, but have a total carbon number of 11 or more.
本発明の第三級カルボン酸として具体的には、 2 キシルー 2—ゥンデカン酸、 2— ォクチルー 2—トリデカン酸などが挙げられる。 Specific examples of the tertiary carboxylic acid of the present invention include 2-xyl-2-enedecanic acid, 2-octyl-2-tridecanoic acid and the like.
本発明の第三級カルボン酸は、炭素数 13以上のビ -リデン型ォレフインと一酸ィ匕 炭素と水との反応により得られる。原料として用いる炭素数 13以上のビ -リデン型ォ レフインは、炭素数 7以上の α—才レフインを公知の方法でニ量ィ匕することによって効 率よく得ることができる。炭素数 7以上のひーォレフィンとしては、 1 ヘプテン、 1 オタ テン、 1ーデセン、 1—ドデセン、 1ーテトラデセン、 1—へキサデセン、 1ーォクタデセン、 1 エイコセンなどが挙げられる。炭素数 7以上の α—ォレフィンのニ量ィ匕によって得 られる α—才レフイン二量体としては、 2—へキシルー 2—デセン、 2—才クチルー 2—ドデ センなどが挙げられる。 The tertiary carboxylic acid of the present invention is obtained by reacting a bi-lidene type olefin having 13 or more carbon atoms with carbon monoxide and water. A bi-lidene type olefin having 13 or more carbon atoms used as a raw material can be efficiently obtained by diluting an α-age olefin having 7 or more carbon atoms by a known method. Examples of hyolephine having 7 or more carbon atoms include 1 heptene, 1 otaten, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1 eicosene. Examples of the α-olefin dimer obtained by dimerizing an α-olefin having 7 or more carbon atoms include 2-hexyl-2-decene and 2-octyl-2-dodecene.
本発明の第三級カルボン酸は以下のようにして製造することができる。触媒としては The tertiary carboxylic acid of the present invention can be produced as follows. As a catalyst
、硫酸、又は硫酸とリン酸及び Ζ又は金属化合物からなる触媒を用いる。具体的に は、硫酸、硫酸及びリン酸、硫酸及び金属化合物、並びに硫酸、リン酸及び金属化 合物の中から選ばれる触媒を用いる。金属化合物としては、酸化第一銅、酸化第二 銅、酸化銀、酸化金などの金属酸化物、金属銅、酸化第二銅などの二価の銅化合 物と金属銅の混合物などが挙げられる。本発明においては、酸化第一銅、酸化第二 銅及び酸ィ匕銀が好ましい。これらの金属化合物は、一種を単独で用いてもよぐ二種 以上を組み合わせて用いてもょ 、。 , Sulfuric acid, or a catalyst comprising sulfuric acid and phosphoric acid and metal or a metal compound. Specifically, a catalyst selected from sulfuric acid, sulfuric acid and phosphoric acid, sulfuric acid and a metal compound, and sulfuric acid, phosphoric acid and a metal compound is used. Examples of the metal compound include metal oxides such as cuprous oxide, cupric oxide, silver oxide, and gold oxide, and mixtures of divalent copper compounds such as metallic copper and cupric oxide with metallic copper. . In the present invention, cuprous oxide, cupric oxide and silver oxide are preferred. These metal compounds may be used alone or in combination of two or more.
反応原料として用いられる水を含む硫酸水溶液の濃度は、通常 40— 98質量％程 度、好ましくは 60— 95質量％である。硫酸とリン酸の使用割合は、硫酸 1モルに対し て、通常、リン酸 0. 05-2. 5モル程度、好ましくは 0. 2-1. 5モルである。硫酸と金 属化合物の使用割合は、硫酸 1モルに対して、通常、金属化合物 0. 1— 15モル程 度、好ましくは 0. 2— 5モノレである。 The concentration of the aqueous sulfuric acid solution containing water used as a reaction raw material is usually about 40 to 98% by mass, preferably 60 to 95% by mass. The usage ratio of sulfuric acid and phosphoric acid is usually about 0.05 to 2.5 mol, preferably 0.2 to 1.5 mol, per mol of sulfuric acid. The ratio of the sulfuric acid to the metal compound is usually about 0.1 to 15 moles, preferably 0.2 to 5 moles per mole of sulfuric acid.
本発明においては、上記炭素数 13以上のビ -リデン型ォレフインと一酸ィ匕炭素と 水とを、上記触媒の存在下にカルボニル反応させて、対応するカルボン酸を製造す る。その際の反応条件には特に制限はないが、反応温度は、通常 0— 100°C程度、 好ましくは 0— 40°Cである。反応圧力は、通常 0. 1— lOMPa'G程度、好ましくは 1 一 4MPa'Gであり、一酸化炭素分圧は、通常 0. OlMPa以上である。反応時間は、 炭素数 14以上のビ -リデン型ォレフインを供給した後、通常 1一 48時間、好ましくは 2— 10時間である。なお、この反応は基本的に無溶媒で行うことができる。 In the present invention, the corresponding carboxylic acid is produced by a carbonyl reaction of the bi-lidene type olefin having 13 or more carbon atoms, carbon monoxide and water in the presence of the catalyst. The reaction conditions at this time are not particularly limited, but the reaction temperature is usually about 0 to 100 ° C, Preferably it is 0-40 ° C. The reaction pressure is usually about 0.1-lOMPa'G, preferably 14 MPa'G, and the partial pressure of carbon monoxide is usually 0.1 OlMPa or more. The reaction time is usually from 1 to 48 hours, preferably from 2 to 10 hours, after supplying the bi-lidene type olefin having 14 or more carbon atoms. In addition, this reaction can be basically performed without a solvent.
[0013] 本発明に係る第三級カルボン酸の製造方法にお!、ては、カルボ-ル化反応生成 物の後処理については特に制限はないが、以下に示す方法が好適である。まず、上 記原料の反応により得られたカルボニル化反応生成物を有機溶剤により抽出処理す る。この有機溶剤としては、 n—へキサン及びシクロへキサンカゝら選ばれる少なくとも一 種のへキサンを用いることが好ましい。へキサンの使用量は、反応生成物に対して、 通常 100— 500質量％程度であり、好ましくは 150— 300質量％である。この場合、 へキサンに対して 5— 20質量％程度の水を併用してもよい。へキサンによる抽出は、 攪拌し、静置すること〖こより行うことができる。 [0013] In the method for producing a tertiary carboxylic acid according to the present invention, the post-treatment of the carboxylation reaction product is not particularly limited, but the following method is preferred. First, the carbonylation reaction product obtained by the reaction of the above raw materials is subjected to extraction treatment with an organic solvent. As the organic solvent, it is preferable to use at least one hexane selected from n-hexane and cyclohexanecaprol. The amount of hexane used is usually about 100 to 500% by mass, and 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.
へキサンで抽出することにより、カルボ-ルイ匕反応生成物は、カルボン酸を含むへ キサン相（油相）と硫酸を含む水相とに分離する。このへキサン相には、抽出された力 ルボン酸のモル数に比例した量の硫酸力 錯体硫酸として混入しているため、このへ キサン相に水を添加し、攪拌 (水洗処理)し、静置することにより、カルボン酸を含む へキサン相と硫酸を含む水相（希硫酸相）に分離させて、へキサン相中の硫酸を洗 い出すことが好ましい。添加する水の量は、カルボ-ル化反応に消費された水量 (理 論水量)の 0. 3— 3倍程度であれば、ほぼ完全に上記へキサン相中の錯体硫酸を回 収することができる。 By extracting with hexane, 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 as 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 added. It is preferable to separate the hexane phase containing carboxylic acid and the aqueous phase containing sulfuric acid (dilute sulfuric acid phase) by washing, 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.
[0014] このようにして得られたカルボン酸を含むへキサン相中には、依然として微量の硫 酸根が含まれる。そこで、この硫酸根を中和するために、アルカリ水溶液を添加する ことが好ましい。用いるアルカリの種類は特に限定されるものではないが、通常、水酸 化ナトリウム及び水酸ィ匕カリウムなどが用いられる。アルカリ水溶液の濃度は、通常 0 [0014] 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
. 01— 10モル Zリットル程度、好ましくは 0. 1— 1モル Zリットルである。 .01—about 10 mol Z liter, preferably 0.1—1 mol Z liter.
へキサン相に添加するアルカリの量を決定するために、硫酸を洗い出した後のへキ サン相を滴定することにより、硫酸根の量を定量する。滴定には、濃度 0. 1モル Zリ ットル程度の水酸ィ匕カリウムなどを用いることができる。硫酸根を中和には、定量した 硫酸根の量の 3倍当量以下のアルカリを含む水溶液を用いることが好ましぐ 1一 3倍 当量のアルカリを含む水溶液がより好ましい。定量した硫酸根の量の 3倍当量以下の アルカリを含む水溶液を用いることにより、ェマルジヨンの形成が抑制されて、へキサ ン相と水相とを 6時間以下で分離させることができる。 In order to determine the amount of alkali added to the hexane phase, the amount of sulfate 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. To neutralize sulfate groups, quantified It is preferable to use an aqueous solution containing three or less equivalents of an alkali of the amount of sulfate group. An aqueous solution containing one to three times equivalent of an alkali is more preferable. By using an aqueous solution containing an alkali not more than 3 equivalents of the determined amount of sulfate, the formation of emulsion can be suppressed, and the hexane phase and the aqueous phase can be separated in 6 hours or less.
アルカリ水溶液で硫酸根を中和した後、へキサン相カゝらカルボン酸を回収すること により、 目的とするカルボン酸を得ることができる。得られたカルボン酸を精製するに は、蒸留等の公知の処理を行えばよい。 After neutralizing the sulfate groups with an aqueous alkali solution, the carboxylic acid is recovered from the hexane phase to obtain the desired carboxylic acid. In order to purify the obtained carboxylic acid, a known treatment such as distillation may be performed.
実施例 Example
次に、本発明を実施例によりさらに詳細に説明する力 本発明はこれらの例によつ てなんら限定されるものではな 、。 Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.
濃度 98質量％の硫酸 48g、水 1. 5g及び酸化第一銅 (Cu O) 1. 4gを反応器に仕 48 g of 98% by mass sulfuric acid, 1.5 g of water and 1.4 g of cuprous oxide (CuO) were charged to the reactor.
2 2
込み、この反応器内を十分に一酸ィ匕炭素で置換した後、攪拌しながら、一酸化炭素 圧を 1. 5MPa'Gに維持しつつ飽和になるまで一酸ィ匕炭素を供給し、反応器内に、 1 オタテンの二量化により得られた 2—へキシルー 2—デセン 7. 7g (0. 035モル）を添 カロした。添加後、温度 15°C、圧力 1. 5MPa'Gで約 2時間反応を継続した。反応中 に消費されて減少した分の一酸ィ匕炭素は、新たに補給した。 After sufficiently replacing the inside of the reactor with carbon monoxide, while stirring, supplying carbon monoxide until saturation while maintaining the carbon monoxide pressure at 1.5 MPa'G, The reactor was charged with 7.7 g (0.035 mol) of 2-hexyl-2-decene obtained by dimerization of 1 otaten. After the addition, the reaction was continued at a temperature of 15 ° C and a pressure of 1.5 MPa'G for about 2 hours. The reduced amount consumed by the reaction during the reaction was replenished.
このようにして得られた反応混合物に、シクロへキサン 30ミリリットルと水 2. 8gを添 加し、攪拌し、約 30分間静置し、シクロへキサン相と水相 (触媒相）とに分離させた。 その後、水相を除去した。 To the reaction mixture thus obtained, 30 ml of cyclohexane and 2.8 g of water were added, and the mixture was stirred, allowed to stand for about 30 minutes, and separated into a cyclohexane phase and an aqueous phase (catalyst phase). I let it. Thereafter, the aqueous phase was removed.
このシクロへキサン相に水 1. 5gを添加し、攪拌して洗浄した後、約 1時間静置して シクロへキサン相と希硫酸相とに分離させることにより、シクロへキサン相 28. 24gを 回収した。 1.5 g of water was added to the cyclohexane phase, and the mixture was stirred and washed, and allowed to stand for about 1 hour to separate into a cyclohexane phase and a dilute sulfuric acid phase, thereby obtaining 28.24 g of a cyclohexane phase. Was recovered.
回収したシクロへキサン相を 0. 1モル Zリットルの水酸ィ匕カリウム水溶液で滴定し、 硫酸根の量を定量した。その結果、回収したシクロへキサン相には 0. 38ミリモルの 硫酸根が含まれることがわ力つた。そこで、この硫酸根の 1. 1倍当量の、 0. 1モル/ リットルの水酸ィ匕ナトリウム水溶液を添加し、攪拌した後、静置したところ、約 1時間で シクロへキサン相と水相とに分離した。このシクロへキサン相から、蒸留により炭素数 17の第三級カルボン酸を回収した。収率は 73%であった。 [0016] 得られた第三級カルボン酸について分析したところ、下記の結果が得られた。なお 、 NMR測定のデータにおいて、（1)一 (17)は下記化学式における炭化水素基の位 置を示す。 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 0.38 mmol of sulfate. Therefore, 0.1 mol / l of an aqueous solution of sodium hydroxide (1.1 mol / l) was added, stirred, and allowed to stand. After about 1 hour, the cyclohexane phase and aqueous phase And separated into. From the cyclohexane phase, a tertiary carboxylic acid having 17 carbon atoms was recovered by distillation. The yield was 73%. When the obtained tertiary carboxylic acid was analyzed, the following results were obtained. In the NMR measurement data, (1)-(17) indicate the position of the hydrocarbon group in the following chemical formula.
分子量 M+ = 270 Molecular weight M + = 270
NMR (d— DMSO 2. 50ppm基準） NMR (d—DMSO 2.50ppm standard)
0. 86ppm (CH , t, 6Η, (1) , (16))、 1. OOppm(CH , s, 3Η, (8) )、 1. 24ppm ( 0.86 ppm (CH, t, 6Η, (1), (16)), 1.OOppm (CH, s, 3Η, (8)), 1.24 ppm (
3 3 3 3
CH , m, 20H, (2) , (3) , (4) , (5) , (10), (11), (12), (13), (14), (15))、 1. 33ppm ( CH, m, 20H, (2), (3), (4), (5), (10), (11), (12), (13), (14), (15)), 1.33 ppm (
2 2
CH , dt, 2H, (6) , (9) )、 1. 51ppm (CH , dt, 2H, (6) , (9) )、 11. 89ppm (OH, CH, dt, 2H, (6), (9)), 1.51 ppm (CH, dt, 2H, (6), (9)), 11.89 ppm (OH,
2 2 twenty two
s, 1H, (17)) s, 1H, (17))
13C— NMR(d— DMSO 39. 5ppm基準） 13 C—NMR (d—DMSO 39.5 ppm standard)
14. 38, 14. 36ppm (CH , (1) , (16))、 21. 65ppm (CH , (8) )、 22. 60, 22. 64 14.38, 14.36ppm (CH, (1), (16)), 21.65ppm (CH, (8)), 22.60, 22.64
3 3 3 3
ppm (CH , (2) , (15))、 24. 57ppm (CH , (5) , (10))、 29. 23ppm (CH , (13))、 2 ppm (CH, (2), (15)), 24.57 ppm (CH, (5), (10)), 29.23 ppm (CH, (13)), 2
2 2 2 2 2 2
9. 47ppm (CH , (12))、 29. 87ppm (CH , (4) )、 30. 27ppm (CH , (11))、 31. 7 9.47 ppm (CH, (12)), 29.87 ppm (CH, (4)), 30.27 ppm (CH, (11)), 31.7
2 2 2 2 2 2
4ppm (CH , (14))、 31. 86ppm (CH , (2) )、 39. 34ppm (CH , (6) , (9) )、 45. 3 4ppm (CH, (14)), 31.86ppm (CH, (2)), 39.34ppm (CH, (6), (9)), 45.3
2 2 2 2 2 2
Oppm (C, (7) )、 178. 71ppm(C = 0, (17) ) Oppm (C, (7)), 178.71 ppm (C = 0, (17))
IRスペクトル（サンドイッチ法） IR spectrum (sandwich method)
3400— 3000cm"1 (C = OOH) , 1699cm"1 (C = 0) , 2956, 2857cm"1 (CH , CH 3400—3000cm " 1 (C = OOH), 1699cm" 1 (C = 0), 2956, 2857cm " 1 (CH, CH
3 Three
)、 1467, 1380cm"1 (CH , CH ) ), 1467, 1380cm " 1 (CH, CH)
2 3 2 2 3 2
[0017] [化 3] [0017] [Formula 3]
(17) COOH 産業上の利用可能性 (17) COOH industrial applicability
[0018] 本発明の第三級カルボン酸は、塗料、接着剤、医薬'農薬中間体、塗料添加剤 (耐 熱性向上剤)、榭脂添加剤 (耐熱性向上剤)等への技術展開が期待される。 [0018] The tertiary carboxylic acid of the present invention has been applied to paints, adhesives, pharmaceuticals, agricultural chemical intermediates, paint additives (heat resistance improvers), resin additives (heat resistance improvers), and the like. Be expected.
Claims
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10584083B2 (en) | 2017-09-29 | 2020-03-10 | Exxonmobile Chemical Patents Inc. | Neo-alcohol compounds, processes for making same and use thereof |
| US10597347B2 (en) | 2017-09-29 | 2020-03-24 | Exxonmobil Chemical Patents Inc. | Neo-acids and process for making the same |
| US10683464B2 (en) | 2017-09-29 | 2020-06-16 | Exxonmobil Chemical Patents Inc. | Ester compounds, lubricating oil compositions containing same and processes for making same |
| CN111328326A (en) * | 2017-09-29 | 2020-06-23 | 埃克森美孚化学专利公司 | New acid and preparation method thereof |
| US10711216B2 (en) | 2017-09-29 | 2020-07-14 | Exxonmobil Chemical Patents Inc. | Ester compounds, lubricating oil compositions containing same and processes for making same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011151123A1 (en) * | 2010-06-04 | 2011-12-08 | Exxonmobil Chemical Patents Inc. | Extraction towers and processes for using the same |
| CN102718646B (en) * | 2011-11-23 | 2014-06-25 | 西南化工研究设计院有限公司 | Method for producing tertiary carboxylic acid |
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