JP4363952B2 - Solid acid catalyst for producing carboxylic anhydride and method for producing carboxylic anhydride using the same - Google Patents
Solid acid catalyst for producing carboxylic anhydride and method for producing carboxylic anhydride using the same Download PDFInfo
- Publication number
- JP4363952B2 JP4363952B2 JP2003360885A JP2003360885A JP4363952B2 JP 4363952 B2 JP4363952 B2 JP 4363952B2 JP 2003360885 A JP2003360885 A JP 2003360885A JP 2003360885 A JP2003360885 A JP 2003360885A JP 4363952 B2 JP4363952 B2 JP 4363952B2
- Authority
- JP
- Japan
- Prior art keywords
- anhydride
- carboxylic acid
- producing
- acid
- catalyst
- 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.)
- Expired - Fee Related
Links
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title claims description 37
- 239000003054 catalyst Substances 0.000 title claims description 33
- 239000011973 solid acid Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 25
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 20
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000012043 crude product Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 4
- -1 (meth) acrylic acid Chemical class 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002862 amidating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、カルボン酸無水物を製造する際に使用される固体酸触媒、及びそれを用いてカルボン酸からその酸無水物を製造する方法に関するものである。 The present invention relates to a solid acid catalyst used in producing a carboxylic acid anhydride, and a method for producing the acid anhydride from the carboxylic acid using the solid acid catalyst.
カルボン酸無水物は、エステル化したりアミド化したりする際に、汎用されるアシル化剤である。中でも、(メタ)アクリル酸無水物は、種々の重合性化合物の原料等として有用である。 Carboxylic anhydride is a widely used acylating agent when esterifying or amidating. Among these, (meth) acrylic anhydride is useful as a raw material for various polymerizable compounds.
(メタ)アクリル酸のようなカルボン酸の無水物の製造方法については、例えば、非特許文献1に(メタ)アクリル酸と(メタ)アクリル酸クロライドとを反応させる方法、非特許文献2に(メタ)アクリル酸の金属塩と(メタ)アクリル酸クロライドとを反応させる方法、非特許文献3に塩化チオニルとアクリル酸とを4−ビニルピリジン存在下で反応させる方法、特許文献1に、メタクリル酸、無水酢酸、リン酸、及び4−ヒドロキシ−2,2,6,6−テトラメチル−ピペリジン−N−オキシルを反応させる方法、特許文献2に、(メタ)アクリル酸とカルボジイミド誘導体とを反応させる方法、特許文献3に、カルボン酸とスルホニルハライド化合物とを、3級アミン及び無機塩基の共存下で反応させる方法、特許文献4に、触媒であるカルボン酸金属塩存在下でメタクリル酸と無水酢酸とを反応させる方法が記載されている。 About the manufacturing method of the anhydride of carboxylic acid like (meth) acrylic acid, for example, the method of making (meth) acrylic acid and (meth) acrylic acid chloride react with nonpatent literature 1, A method of reacting a metal salt of (meth) acrylic acid with (meth) acrylic acid chloride, a method of reacting thionyl chloride and acrylic acid in the presence of 4-vinylpyridine in Non-Patent Document 3, and a method of reacting methacrylic acid in Patent Document 1 , Acetic anhydride, phosphoric acid, and a method of reacting 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, Patent Document 2 reacts (meth) acrylic acid with a carbodiimide derivative Method, Patent Document 3, a method of reacting a carboxylic acid and a sulfonyl halide compound in the presence of a tertiary amine and an inorganic base, Patent Document 4, a catalyst The method of reacting a methacrylic acid and acetic anhydride in the presence of a carboxylic acid metal salt is described that.
しかしこれら従来のカルボン酸無水物の製造方法は、塩化物やアミン類、及び溶媒等を除去する水洗等の精製操作が必要であって、煩雑である。また使用した触媒は、再使用することができず、経済的でないうえ、環境に悪影響を及ぼすという問題があった。 However, these conventional methods for producing carboxylic acid anhydrides are complicated because they require purification operations such as washing with water to remove chlorides, amines, solvents and the like. Further, the used catalyst cannot be reused, is not economical, and has an adverse effect on the environment.
本発明は前記の課題を解決するためになされたもので、高純度のカルボン酸無水物を、高収率で簡便かつ経済的に製造するための固体酸触媒、及びそれを使用し、触媒の除去が簡易で再使用でき、経済的にも環境的にも優れているカルボン酸無水物製造方法を提供することを目的とする。 The present invention has been made to solve the above-described problems. A solid acid catalyst for easily and economically producing a high-purity carboxylic acid anhydride in a high yield, and using the solid acid catalyst, An object of the present invention is to provide a method for producing a carboxylic acid anhydride which is easy to remove and can be reused, and which is economically and environmentally superior.
前記の目的を達成するためになされた本発明のカルボン酸無水物製造用固体酸触媒は、層構造を有しているモンモリロナイトの層間に存する金属カチオンが、Ti4+に交換したものである。 The solid acid catalyst for producing a carboxylic acid anhydride according to the present invention, which has been made to achieve the above object, is obtained by exchanging a metal cation existing between layers of montmorillonite having a layer structure with Ti 4+ .
本発明のカルボン酸無水物製造方法は、前記のカルボン酸無水物製造用固体酸触媒の存在下、高沸点のカルボン酸と、それよりも低沸点のカルボン酸が縮合した無水物とを、混合し、該高沸点のカルボン酸が縮合した無水物を得るというものである。 The method for producing a carboxylic acid anhydride of the present invention comprises mixing a carboxylic acid having a high boiling point and an anhydride condensed with a carboxylic acid having a lower boiling point in the presence of the solid acid catalyst for producing the carboxylic acid anhydride. Thus, an anhydride obtained by condensing the high-boiling point carboxylic acid is obtained.
この方法によれば、カルボン酸の無水物を、高純度かつ高収率で簡易に製造することができる。 According to this method, an anhydride of carboxylic acid can be easily produced with high purity and high yield.
このカルボン酸無水物を得た後、該固体酸触媒は濾別により簡単に除去することができる。 After obtaining the carboxylic acid anhydride, the solid acid catalyst can be easily removed by filtration.
カルボン酸無水物製造用固体酸触媒の量は、特段限定されないが、高沸点カルボン酸に対し0.1〜5重量%であることが好ましい。 The amount of the solid acid catalyst for producing carboxylic acid anhydride is not particularly limited, but is preferably 0.1 to 5% by weight based on the high-boiling point carboxylic acid.
カルボン酸無水物製造方法は、高沸点のカルボン酸が縮合した無水物を得た後、該固体酸触媒を濾別し、濾別したその固体酸触媒を用いて、繰り返してこの無水物を得るものであってもよい。 Carboxylic acid anhydride manufacturing method, after the carboxylic acid of high boiling point to obtain a anhydrides condensed and then filtered to remove the solid acid catalyst, using the solid acid catalyst was filtered off to give the anhydride repeating It may be a thing.
この触媒は、固体状であるので、反応終結後、濾過するだけで簡便に反応混合物から分離回収できるうえ、繰り返して触媒として使用することができ、原子効率が極めて高いものである。回収した触媒でカルボン酸無水物を製造しても、この無水物の反応収率や純度は低下しない。 Since this catalyst is in a solid state, it can be separated and recovered from the reaction mixture simply by filtering after the reaction is completed, and can be repeatedly used as a catalyst, so that the atomic efficiency is extremely high. Even if a carboxylic acid anhydride is produced with the recovered catalyst, the reaction yield and purity of this anhydride are not lowered.
低沸点カルボン酸の無水物は、高沸点カルボン酸1モルに対し0.2〜2.0モルであることが好ましく、0.4〜0.6モルであるとなお一層好ましい。 The low-boiling point carboxylic acid anhydride is preferably 0.2 to 2.0 moles, more preferably 0.4 to 0.6 moles per mole of the high-boiling point carboxylic acid.
この製造方法によるカルボン酸無水物製造の途中で、生じた低沸点カルボン酸を、加熱又は減圧を併用して留去すると、高沸点カルボン酸の無水物の生成量が向上するため、好ましい。 It is preferable to distill off the generated low-boiling carboxylic acid during the production of the carboxylic acid anhydride by this production method in combination with heating or decompression, since the amount of high-boiling carboxylic acid anhydride produced is improved.
低沸点のカルボン酸が縮合した無水物は、安価で入手が容易な無水酢酸であることが好ましい。 The anhydride condensed with a low-boiling carboxylic acid is preferably acetic anhydride which is inexpensive and easily available.
高沸点のカルボン酸は、飽和、及び不飽和のいずれのカルボン酸であってもよい。重合し易いアクリル酸やメタクリル酸であってもよい。 The high-boiling carboxylic acid may be either a saturated or unsaturated carboxylic acid. It may be acrylic acid or methacrylic acid that is easily polymerized.
高沸点のカルボン酸が、(メタ)アクリル酸のような不飽和カルボン酸であるとき、重合禁止剤を共存させることが好ましい。重合禁止剤は、特段限定されないが、例えばパラベンゾキノン、ハイドロキノン、2,6−ジターシャリーブチルパラクレゾール、フェノチアジン、パラメトキシフェノール、酸素等が、1種又は2種以上を併用して用いられる。 When the high-boiling carboxylic acid is an unsaturated carboxylic acid such as (meth) acrylic acid, it is preferable to allow a polymerization inhibitor to coexist. Although the polymerization inhibitor is not particularly limited, for example, parabenzoquinone, hydroquinone, 2,6-ditertiary butylparacresol, phenothiazine, paramethoxyphenol, oxygen, and the like are used alone or in combination of two or more.
以上、詳細に説明したように、本発明のカルボン酸無水物製造用固体酸触媒を用いたカルボン酸無水物の製造方法によれば、高沸点のカルボン酸から、高純度かつ高収率で、それの酸無水物を簡便かつ経済的に製造することができる。特に、重合し易い不安定な(メタ)アクリル酸からその無水物を製造するのに好適である。 As described above in detail, according to the method for producing a carboxylic acid anhydride using the solid acid catalyst for producing a carboxylic acid anhydride of the present invention, from a carboxylic acid having a high boiling point, with a high purity and a high yield, The acid anhydride can be easily and economically produced. In particular, it is suitable for producing the anhydride from unstable (meth) acrylic acid which is easily polymerized.
触媒は濾別により回収して繰り返し使用することができ、経済的である。 The catalyst can be recovered by filtration and used repeatedly, which is economical.
この製造方法によれば、産業廃棄物を殆ど発生させず、環境汚染を惹き起さない。 According to this manufacturing method, industrial waste is hardly generated and environmental pollution is not caused.
以下、本発明のカルボン酸無水物製造用固体酸触媒と、それを用いた不均一系のカルボン酸無水物製造方法の実施例を詳細に説明する。 Examples of the solid acid catalyst for producing a carboxylic acid anhydride and a method for producing a heterogeneous carboxylic acid anhydride using the same will be described in detail below.
この触媒は、次のようにして調製される。
(カルボン酸無水物製造用固体酸触媒の調製例)
Na0.66(OH)4Si8(Al3.34Mg0.66Fe0.19)O20で示され層間の鎖状水酸化金属種がNa+である原材モンモリロナイト(Na+−mont)としてKunipia F(クニミネ工業社製の商品名)を用いた。その3.0gを、1.8MのTiCl4水溶液100mL中で50℃、24時間撹拌した。得られたスラリーを濾過し、1000mLの蒸留水で洗浄して塩化物を完全に除去した。次いで110℃で乾燥すると、灰白色粉末のカルボン酸無水物製造用固体酸触媒2.5gが得られた。
このカルボン酸無水物製造用固体酸触媒は、元素分析値が、Na,0.06;Al,11.2;Ti,3.25;Fe,1.34%であり、X線光分光分析(XPS)が、Ti 2p2/3 = 458.7eV;Al 2p=74.1eV;Ti:Al=0.21であった。この酸触媒は、原材モンモリロナイトのNa+に対するTi4+への交換率が97.7%である。X線回折パターンによって確認したこの酸触媒の層間距離は、2.7Åと推定され、原材モンモリロナイトの層間距離2.9Åより僅かに小さかった。
This catalyst is prepared as follows.
(Preparation example of solid acid catalyst for carboxylic anhydride production)
Raw material montmorillonite (Na + -mont) represented by Na 0.66 (OH) 4 Si 8 (Al 3.34 Mg 0.66 Fe 0.19 ) O 20 and having an inter-chain metal hydroxide species of Na + ) Kunipia F (trade name of Kunimine Kogyo Co., Ltd.) was used. 3.0 g of the mixture was stirred in 100 mL of 1.8 M TiCl 4 aqueous solution at 50 ° C. for 24 hours. The resulting slurry was filtered and washed with 1000 mL distilled water to completely remove chloride. Next, drying at 110 ° C. yielded 2.5 g of a solid acid catalyst for the production of carboxylic acid anhydride as an off-white powder.
This solid acid catalyst for producing carboxylic acid anhydride has elemental analysis values of Na, 0.06; Al, 11.2; Ti, 3.25; Fe, 1.34%, and X-ray spectroscopic analysis ( XPS) was Ti2p2 / 3 = 458.7 eV; Al2p = 74.1 eV; Ti: Al = 0.21. This acid catalyst has a 97.7% conversion rate of the raw material montmorillonite to Ti 4+ for Na + . The interlayer distance of this acid catalyst confirmed by the X-ray diffraction pattern was estimated to be 2.7 mm, which was slightly smaller than the interlayer distance of 2.9 mm of the raw material montmorillonite.
得られたカルボン酸無水物製造用固体酸触媒を用いて、本発明を適用するカルボン酸無水物製造方法を実施した例を、実施例1〜3に示す。 Examples of carrying out the carboxylic acid anhydride production method to which the present invention is applied using the obtained solid acid catalyst for carboxylic acid anhydride production are shown in Examples 1 to 3.
(実施例1)
メタクリル酸204g、無水酢酸121g、重合禁止剤0.6g、及び前記調製例で得たカルボン酸無水物製造用固体酸触媒2.0gを反応容器に入れて加熱撹拌し、80℃、常圧で1時間反応させた後、生成する酢酸を150〜15mmHgの減圧にすることにより取り出しながら6時間反応を行った。反応終了後、酸触媒を濾別し、粗生成物を得た。この粗生成物について、ガスクロマトグラフィーにより分析したところ、メタクリル酸無水物であることが確認された。粗生成物は、収率85%で、純度96.6%であった。
Example 1
204 g of methacrylic acid, 121 g of acetic anhydride, 0.6 g of polymerization inhibitor, and 2.0 g of the solid acid catalyst for producing carboxylic acid anhydride obtained in the above preparation example were placed in a reaction vessel, and heated and stirred. After making it react for 1 hour, it reacted for 6 hours, taking out the produced | generated acetic acid by making it the reduced pressure of 150-15 mmHg. After completion of the reaction, the acid catalyst was filtered off to obtain a crude product. When this crude product was analyzed by gas chromatography, it was confirmed to be methacrylic anhydride. The crude product had a yield of 85% and a purity of 96.6%.
(実施例2)
触媒として、実施例1で濾別して回収した酸触媒を再使用した以外は、実施例1と同様にして粗生成物を得た。この粗生成物について、ガスクロマトグラフィーにより分析したところ、メタクリル酸無水物であることが確認された。粗生成物は、収率83%で、純度96.4%であった。
(Example 2)
A crude product was obtained in the same manner as in Example 1 except that the acid catalyst recovered by filtration in Example 1 was reused as the catalyst. When this crude product was analyzed by gas chromatography, it was confirmed to be methacrylic anhydride. The crude product had a yield of 83% and a purity of 96.4%.
(実施例3)
アクリル酸288g、無水酢酸204g、重合禁止剤0.9g及び調製例で得たカルボン酸無水物製造用固体酸触媒2.0gを反応容器に入れて加熱撹拌し、80℃、常圧で1時間反応させた後、生成する酢酸を150〜15mmHgの減圧にすることにより取り出しながら6時間反応を行った。反応終了後、酸触媒を濾別し、粗生成物を得た。この粗生成物について、ガスクロマトグラフィーにより分析したところ、アクリル酸無水物であることが確認された。粗生成物は、収率80%で、純度94.3%であった。
(Example 3)
288 g of acrylic acid, 204 g of acetic anhydride, 0.9 g of polymerization inhibitor, and 2.0 g of the solid acid catalyst for production of carboxylic acid anhydride obtained in the preparation example were placed in a reaction vessel and heated and stirred, and then at 80 ° C. and normal pressure for 1 hour. After the reaction, the reaction was performed for 6 hours while taking out the produced acetic acid by reducing the pressure to 150 to 15 mmHg. After completion of the reaction, the acid catalyst was filtered off to obtain a crude product. When this crude product was analyzed by gas chromatography, it was confirmed to be acrylic anhydride. The crude product had a yield of 80% and a purity of 94.3%.
(比較例1)
メタクリル酸204g、無水酢酸121g、重合禁止剤0.6gを反応容器に入れて加熱撹拌し、80℃、常圧で1時間反応させた後、生成する酢酸を150〜15mmHgの減圧にすることにより取り出しながら6時間反応を行い、粗生成物を得た。この粗生成物について、ガスクロマトグラフィーにより分析したところ、メタクリル酸無水物であることが確認された。粗生成物は、収率65%で、純度90.3%であった。
(Comparative Example 1)
By adding 204 g of methacrylic acid, 121 g of acetic anhydride, and 0.6 g of a polymerization inhibitor into a reaction vessel, heating and stirring, reacting at 80 ° C. and normal pressure for 1 hour, and then reducing the generated acetic acid to a reduced pressure of 150 to 15 mmHg. While taking out, the reaction was carried out for 6 hours to obtain a crude product. When this crude product was analyzed by gas chromatography, it was confirmed to be methacrylic anhydride. The crude product had a yield of 65% and a purity of 90.3%.
(比較例2)
アクリル酸288g、無水酢酸204g、重合禁止剤0.9gを反応容器に入れて加熱撹拌し、80℃、常圧で1時間反応させた後、生成する酢酸を150〜15mmHgの減圧にすることにより取り出しながら6時間反応を行い、粗生成物を得た。この粗生成物について、ガスクロマトグラフィーにより分析したところ、アクリル酸無水物であることが確認された。粗生成物は、収率44%で、純度83.2%であった。
(Comparative Example 2)
By placing 288 g of acrylic acid, 204 g of acetic anhydride, and 0.9 g of polymerization inhibitor in a reaction vessel, heating and stirring, reacting at 80 ° C. and normal pressure for 1 hour, and then reducing the generated acetic acid to a reduced pressure of 150 to 15 mmHg. While taking out, the reaction was carried out for 6 hours to obtain a crude product. When this crude product was analyzed by gas chromatography, it was confirmed to be acrylic anhydride. The crude product had a yield of 44% and a purity of 83.2%.
このように、実施例ではカルボン酸無水物が高収率かつ高純度で得られた。それに対し、比較例ではカルボン酸無水物が低収率で低純度しか得られなかった。 Thus, in the Examples, carboxylic acid anhydrides were obtained with high yield and high purity. On the other hand, in the comparative example, only low purity and low purity of the carboxylic acid anhydride was obtained.
本発明の固体酸触媒を用いたカルボン酸無水物の製造方法より得た酸無水物は、広範なスケールで種々のアルコール類をエステル化したり、アミン類をアミド化したりするためのアシル化剤として使用される。特に(メタ)アクリル酸無水物は、コーティング剤、接着剤、塗料添加剤、建材、光学部材、フォトレジストをはじめとする種々の樹脂を形成するためのモノマーの原料として、有用である。 The acid anhydride obtained from the method for producing a carboxylic acid anhydride using the solid acid catalyst of the present invention is an acylating agent for esterifying various alcohols and amidating amines on a wide scale. used. In particular, (meth) acrylic anhydride is useful as a raw material for monomers for forming various resins including coating agents, adhesives, paint additives, building materials, optical members, and photoresists.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003360885A JP4363952B2 (en) | 2003-10-21 | 2003-10-21 | Solid acid catalyst for producing carboxylic anhydride and method for producing carboxylic anhydride using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003360885A JP4363952B2 (en) | 2003-10-21 | 2003-10-21 | Solid acid catalyst for producing carboxylic anhydride and method for producing carboxylic anhydride using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005125154A JP2005125154A (en) | 2005-05-19 |
JP4363952B2 true JP4363952B2 (en) | 2009-11-11 |
Family
ID=34641064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003360885A Expired - Fee Related JP4363952B2 (en) | 2003-10-21 | 2003-10-21 | Solid acid catalyst for producing carboxylic anhydride and method for producing carboxylic anhydride using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4363952B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006029318B3 (en) * | 2006-06-23 | 2007-10-11 | Röhm Gmbh | Continuous preparation of unsaturated carboxylic acid anhydride comprises reacting a ketene with an unsaturated carboxylic acid in apparatus comprising reaction mediums, and collecting the anhydride from rectification column |
DE102006029320B3 (en) * | 2006-06-23 | 2007-10-11 | Röhm Gmbh | Continuous preparation of unsaturated carboxylic acid anhydride comprises anhydrating aliphatic carboxylic acid anhydride with carboxylic acid in rectification column, recycling the non-reacted educt in reaction medium and collecting |
DE102006060162A1 (en) * | 2006-12-18 | 2008-06-19 | Evonik Röhm Gmbh | Improved process for the preparation of unsaturated carboxylic acid hybrids |
JP5886113B2 (en) * | 2012-04-16 | 2016-03-16 | 花王株式会社 | Method for producing monocarboxylic anhydride |
-
2003
- 2003-10-21 JP JP2003360885A patent/JP4363952B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2005125154A (en) | 2005-05-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4342940B2 (en) | Process for producing 5-methyl-1-phenyl-2 (1H) pyridinone | |
JP4363952B2 (en) | Solid acid catalyst for producing carboxylic anhydride and method for producing carboxylic anhydride using the same | |
WO2022127410A1 (en) | Catalyst, preparation method therefor, and use thereof in preparation of 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy | |
JP5309318B2 (en) | Process for producing esters, carboxylic acids and amides | |
JPH0967306A (en) | Production of isobornyl (meth)acrylate | |
JP6086163B2 (en) | Method for producing 2'-trifluoromethyl group-substituted aromatic ketone | |
JP4065689B2 (en) | 2-Adamantanone production method | |
JP5018067B2 (en) | Method for producing fluorine-containing alkane esters | |
JP4169370B2 (en) | Process for producing acetophenones having a fluoroalkyl-substituted aromatic nucleus | |
JP2005132790A (en) | Method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate | |
EP1463706B1 (en) | Process for production of 3,3-dimethyl-2-formylcyclopropanecarboxylic acid derivatives | |
JPH09249657A (en) | Purification of glycidyl (meth)acrilate | |
JP4066544B2 (en) | Method for producing cyclopentenone | |
JP2003267915A (en) | Method for producing 3,3-dimethyl-2- formylcyclopropanecarboxylic acid derivative | |
JP2007230873A (en) | Method for producing hydroxy group-containing vinyl compound | |
JP2002105022A (en) | Method for producing 2-alkyl-2-adamantyl ester | |
Ghonchepour et al. | One-pot Efficient Oximation-Beckmann Rearrangement of Ketones Catalyzed by Fe3O4 Under Solvent-free Conditions | |
JP6024410B2 (en) | Method for producing hydroxyadamantane polycarboxylic acid compound | |
JP2008247746A (en) | Method for producing haloiodoaniline compounds | |
JPH10218832A (en) | Purification of acrylic acid | |
JPS6210095A (en) | Method of recovering tert-butyldimethylchloro silane | |
JP5175460B2 (en) | Process for producing (meth) acrylic acid oxoadamantyl esters | |
JP4153075B2 (en) | Method for producing chloro-benzoyl chlorides | |
CN116813508A (en) | Method for synthesizing 5-halogeno-2-methylbenzoic acid with high selectivity | |
JP4143295B2 (en) | Method for producing 9,9-disubstituted-2,3,6,7-xanthenetetracarboxylic dianhydride |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061013 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090518 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090602 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090714 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090804 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090818 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120828 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4363952 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130828 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |