JP2005125154A - Solid acid catalyst for manufacturing carboxylic acid anhydrate and carboxylic acid anhydrate manufacturing method using it - Google Patents
Solid acid catalyst for manufacturing carboxylic acid anhydrate and carboxylic acid anhydrate manufacturing method using it Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000011973 solid acid Substances 0.000 title claims abstract description 26
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 41
- 238000009835 boiling Methods 0.000 claims abstract description 24
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 16
- 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 abstract description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 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
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims 1
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 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
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- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
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 and (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 of the present invention, which has been made to achieve the above object, is obtained by exchanging metal cations 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、濾別した該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。 The carboxylic acid anhydride production method may be such that after obtaining an anhydride condensed with a carboxylic acid having a high boiling point, the anhydride is repeatedly obtained using the solid acid catalyst separated by filtration.
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 completion of the reaction, 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, manufactured by 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, when dried at 110 ° C., 2.5 g of a solid acid catalyst for producing a carboxylic acid anhydride as an off-white powder was obtained.
This solid acid catalyst for producing carboxylic acid anhydride has an elemental analysis value 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 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. The reaction was carried out for 6 hours while taking out 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.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009541407A (en) * | 2006-06-23 | 2009-11-26 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Continuous production method of unsaturated carboxylic acid anhydride |
| JP2009541408A (en) * | 2006-06-23 | 2009-11-26 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Continuous production method of unsaturated carboxylic acid anhydride |
| JP2010513365A (en) * | 2006-12-18 | 2010-04-30 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Improved process for the production of unsaturated carboxylic acid anhydrides |
| JP2013221006A (en) * | 2012-04-16 | 2013-10-28 | Kao Corp | Method of manufacturing monocarboxylic acid anhydride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009541407A (en) * | 2006-06-23 | 2009-11-26 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Continuous production method of unsaturated carboxylic acid anhydride |
| JP2009541408A (en) * | 2006-06-23 | 2009-11-26 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Continuous production method of unsaturated carboxylic acid anhydride |
| JP2010513365A (en) * | 2006-12-18 | 2010-04-30 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Improved process for the production of unsaturated carboxylic acid anhydrides |
| KR101387180B1 (en) * | 2006-12-18 | 2014-05-19 | 에보니크 룀 게엠베하 | Improved Method for the Production of Unsaturated Carboxylic Acid Anhydrides |
| JP2013221006A (en) * | 2012-04-16 | 2013-10-28 | Kao Corp | Method of manufacturing monocarboxylic acid anhydride |
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