JPH11152249A - Method for producing unsaturated carboxylic acid ester - Google Patents
Method for producing unsaturated carboxylic acid esterInfo
- Publication number
- JPH11152249A JPH11152249A JP9321020A JP32102097A JPH11152249A JP H11152249 A JPH11152249 A JP H11152249A JP 9321020 A JP9321020 A JP 9321020A JP 32102097 A JP32102097 A JP 32102097A JP H11152249 A JPH11152249 A JP H11152249A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated carboxylic
- carboxylic acid
- acid
- reaction
- alcohol
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 title 1
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 239000003930 superacid Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003456 ion exchange resin Substances 0.000 abstract description 7
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 6
- 239000003377 acid catalyst Substances 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- -1 alkyl titanate Chemical compound 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-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
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- GKDATSDYQKXWPA-UHFFFAOYSA-L oxygen(2-);zirconium(4+);dichloride;octahydrate Chemical compound O.O.O.O.O.O.O.O.[O-2].[Cl-].[Cl-].[Zr+4] GKDATSDYQKXWPA-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は不飽和カルボン酸エ
ステルの製造方法に関するものであり、詳しくはアルコ
ールと不飽和カルボン酸との接触エステル化反応により
対応する不飽和カルボン酸エステルを高収率に製造する
ための触媒に関するものである。本発明によって製造さ
れる不飽和カルボン酸エステルは各種樹脂製造用のモノ
マー、コモノマーとして有用かつ重要な化合物である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an unsaturated carboxylic acid ester, and more particularly to a method for producing a corresponding unsaturated carboxylic acid ester by a catalytic esterification reaction between an alcohol and an unsaturated carboxylic acid in a high yield. It relates to a catalyst for production. The unsaturated carboxylic acid ester produced by the present invention is a useful and important compound as a monomer or comonomer for producing various resins.
【０００２】[0002]
【従来の技術】不飽和カルボン酸エステルの代表的な製
造方法としては、不飽和カルボン酸とアルコールとを酸
性触媒の存在下で反応させて、対応する不飽和カルボン
酸エステルを得る方法が知られている（特開昭６１−２
７１２４７号公報）。ここで触媒として用いられる酸と
しては、硫酸、ｐ−トルエンスルホン酸、ベンゼンスル
ホン酸、及びアルキルチタン酸エステル等のようなブレ
ンステッド酸またはルイス酸型の酸触媒が一般的であ
る。2. Description of the Related Art As a typical method for producing an unsaturated carboxylic acid ester, a method is known in which an unsaturated carboxylic acid and an alcohol are reacted in the presence of an acidic catalyst to obtain a corresponding unsaturated carboxylic acid ester. (Japanese Patent Laid-Open No. 61-2)
No. 71247). As the acid used as a catalyst here, a Bronsted acid or Lewis acid type acid catalyst such as sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, and alkyl titanate is generally used.
【０００３】強酸を触媒として用いた場合は、エステル
化反応終了後、反応生成液からこれを除去する必要があ
る。このような強酸を除去するための後処理方法として
は反応生成液をアルカリ水溶液で洗浄する方法が多く用
いられ、これに関する改良も種々試みられている（特開
昭６１−２４３０４６号公報、特開平３−３４９６５
号、特開平４−２３０２４０号公報等）。しかしなが
ら、エステル化反応液を、そのままアルカリ水溶液で中
和処理すると、エステル化触媒である強酸も未反応で残
留している不飽和カルボン酸も、アルカリ水溶液中に溶
解してしまい、高濃度の有機酸塩を含んだ廃水が多量に
発生するという欠点を有している。このアルカリ水溶液
から触媒や不飽和カルボン酸などを分離回収することは
極めて困難であるので廃棄する以外になく、歩留まりが
低下し、廃水処理が必要となる他に、上記中和処理のた
めのアルカリも必要であるという問題がある。When a strong acid is used as a catalyst, it must be removed from the reaction product after the esterification reaction is completed. As a post-treatment method for removing such a strong acid, a method of washing a reaction product solution with an aqueous alkali solution is often used, and various improvements have been attempted (JP-A-61-243046, JP-A-61-243046). 3-34965
No. JP-A-4-230240). However, if the esterification reaction solution is neutralized with an aqueous alkali solution as it is, both the strong acid as the esterification catalyst and the unsaturated carboxylic acid remaining unreacted will be dissolved in the aqueous alkali solution, resulting in a high concentration of organic acid. It has the disadvantage that a large amount of wastewater containing acid salts is generated. It is extremely difficult to separate and recover the catalyst and the unsaturated carboxylic acid from the aqueous alkali solution.Therefore, there is no choice but to dispose of the catalyst, the yield is reduced, and wastewater treatment is required. Is also necessary.
【０００４】更に、強酸を触媒としたエステル化反応
は、反応の選択性が低い、即ち仕込まれた不飽和カルボ
ン酸が、エステル化されることなく分解したり重合した
りして消費されてしまう、といった欠点がある。そこで
上記のような強酸触媒以外の触媒として、強酸性イオン
交換樹脂、ヘテロポリ酸（特公平０７−０１２４３５号
公報）などが提案されている。Further, the esterification reaction using a strong acid as a catalyst has low selectivity for the reaction, that is, the charged unsaturated carboxylic acid is consumed without being esterified by decomposition or polymerization. There is a disadvantage, such as. Accordingly, as a catalyst other than the above strong acid catalyst, a strongly acidic ion exchange resin, a heteropoly acid (Japanese Patent Publication No. 07-012435) and the like have been proposed.
【０００５】イオン交換樹脂は濾別により触媒が反応液
から容易に分離可能であり、またその再生時以外は廃水
の問題もないが反応速度が遅く、またヘテロポリ酸は装
置の腐食がほとんどなく、触媒の選択性も優れている
が、廃水処理の問題は解決されていない。以上のよう
に、不飽和カルボン酸とアルコールとの接触エステル化
反応による不飽和カルボン酸エステルの製造に用いる触
媒の選択には、経済性や廃水処理において多くの課題が
残されている。[0005] In the case of the ion exchange resin, the catalyst can be easily separated from the reaction solution by filtration, and there is no problem of wastewater except during regeneration, but the reaction speed is slow. Although the selectivity of the catalyst is excellent, the problem of wastewater treatment has not been solved. As described above, the selection of a catalyst used for the production of an unsaturated carboxylic acid ester by the catalytic esterification reaction between an unsaturated carboxylic acid and an alcohol has many problems in economics and wastewater treatment.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、不飽
和カルボン酸とアルコールとからエステル化反応により
不飽和カルボン酸エステルを製造する際に発生する、前
記のような廃水処理や反応速度等の問題点を解決し、高
い選択性で不飽和カルボン酸エステルを製造する方法を
提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an unsaturated carboxylic acid ester produced by an esterification reaction from an unsaturated carboxylic acid and an alcohol. And a method for producing an unsaturated carboxylic acid ester with high selectivity.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の従
来技術の現状に鑑み、エステル化触媒に関して鋭意研究
を重ねた結果、不飽和カルボン酸とアルコールとの接触
エステル化反応において、触媒としてジルコニウムを含
有する固体超強酸を用いることにより、これらの問題が
解決できることを見出し、本発明を完成した。Means for Solving the Problems In view of the above-mentioned state of the art, the present inventors have conducted intensive studies on esterification catalysts. As a result, in the catalytic esterification reaction between an unsaturated carboxylic acid and an alcohol, the catalyst was used. It has been found that these problems can be solved by using a solid superacid containing zirconium as the above, and the present invention has been completed.
【０００８】即ち、本発明の要旨は、以下の諸点に存し
ている。 （１） アルコールと不飽和カルボン酸とを反応させて
不飽和カルボン酸エステルを製造するに際して、触媒と
してジルコニウムを含有する固体超強酸を用いる不飽和
カルボン酸エステルの製造方法。 （２） アルコールとして炭素原子数が１〜８の脂肪族
一価アルコールを用いる上記第（１）項に記載の不飽和
カルボン酸エステルの製造方法。 （３） 不飽和カルボン酸としてアクリル酸又はメタク
リル酸を用いる上記（１）又は（２）項に記載の製造方
法。 （４） ジルコニウムを含有する固体超強酸として水酸
化ジルコニウムと硫酸との反応生成物を用いる上記
（１）〜（３）項のいずれか１項に記載の製造方法。 （５） 反応に供するアルコールと不飽和カルボン酸と
のモル比が１／１０〜１０／１（アルコール／不飽和カ
ルボン酸）の範囲にある上記（１）〜（４）項のいずれ
か１項に記載の製造方法。 （６） 反応温度が３０〜１５０℃、反応時間が０．１
〜１０時間の範囲にある反応条件でエステル化反応を行
う上記（１）〜（５）項のいずれか１項に記載の製造方
法。That is, the gist of the present invention resides in the following points. (1) A method for producing an unsaturated carboxylic acid ester using a solid superacid containing zirconium as a catalyst when producing an unsaturated carboxylic acid ester by reacting an alcohol with an unsaturated carboxylic acid. (2) The method for producing an unsaturated carboxylic acid ester according to the above (1), wherein an aliphatic monohydric alcohol having 1 to 8 carbon atoms is used as the alcohol. (3) The production method according to the above (1) or (2), wherein acrylic acid or methacrylic acid is used as the unsaturated carboxylic acid. (4) The method according to any one of the above (1) to (3), wherein a reaction product of zirconium hydroxide and sulfuric acid is used as the zirconium-containing solid superacid. (5) Any one of the above items (1) to (4), wherein the molar ratio of the alcohol and the unsaturated carboxylic acid to be subjected to the reaction is in the range of 1/10 to 10/1 (alcohol / unsaturated carboxylic acid). The production method described in 1. (6) The reaction temperature is 30 to 150 ° C and the reaction time is 0.1
The method according to any one of the above (1) to (5), wherein the esterification reaction is carried out under a reaction condition in a range of from 10 hours to 10 hours.
【０００９】[0009]
【発明の実施の形態】以下本発明を詳細に説明する。本
発明でエステル化触媒として使用するジルコニウムを含
有する固体超強酸は、ハメットの酸度関数Ｈ0で表した
時に、Ｈ0として１００％硫酸のＨ0＝−１１．９３より
も小さな値を有する、ジルコニウムを含有する固体酸で
あり、例えば水酸化ジルコニウムと硫酸との反応生成物
や水酸化ジルコニウムと硫酸アンモニウムとの反応生成
物が例示できる。中でも水酸化ジルコニウムと硫酸との
反応生成物がエステル化の選択性が高く、好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The solid superacid containing zirconium used as the esterification catalyst in the present invention has a value smaller than H 0 of 100% sulfuric acid as H 0 = -11.93 when expressed by Hammett's acidity function H 0 , It is a solid acid containing zirconium, for example, a reaction product of zirconium hydroxide and sulfuric acid or a reaction product of zirconium hydroxide and ammonium sulfate. Among them, a reaction product of zirconium hydroxide and sulfuric acid is preferable because of high selectivity for esterification.
【００１０】本発明に使用するジルコニウムを含有する
固体超強酸を調製するためには、上記のように水酸化ジ
ルコニウムを原料とする他、酸化ジルコニウムを用いる
こともできる。この場合、結晶化した酸化物を用いるよ
りも、Ｘ線回折で無定形のものが好ましい。また、上述
のようにジルコニウムの水酸化物や酸化物と硫酸等とを
反応させてジルコニウムを含有する固体超強酸を調製す
る際に、固体触媒を取得するために反応生成物を焼成す
るのが好適である。この時の焼成温度としては、５５０
〜７００℃、好ましくは５７５〜６７５℃とするのがよ
い。In order to prepare the solid superacid containing zirconium used in the present invention, zirconium oxide can be used in addition to zirconium hydroxide as described above. In this case, an amorphous thing is preferable by X-ray diffraction rather than using a crystallized oxide. In addition, when preparing a solid superacid containing zirconium by reacting a hydroxide or oxide of zirconium with sulfuric acid or the like as described above, it is necessary to calcine the reaction product to obtain a solid catalyst. It is suitable. The firing temperature at this time is 550
It is good to be -700 degreeC, Preferably it is 575-675 degreeC.
【００１１】焼成温度が５５０℃未満では、ジルコニウ
ム成分と硫酸成分との結合が不十分となりやすく、エス
テル化反応中に硫酸成分が溶出して活性が急激に低下す
ることがあるので好ましくない。一方、７００℃を超え
る高温で焼成を行うと、焼成中に硫酸成分が分解し、選
択性は高くなるものの触媒活性が低下するので、やはり
好ましくない。If the calcination temperature is lower than 550 ° C., the bonding between the zirconium component and the sulfuric acid component tends to be insufficient, and the sulfuric acid component is eluted during the esterification reaction, which is not preferable because the activity may be rapidly lowered. On the other hand, when calcination is performed at a high temperature exceeding 700 ° C., the sulfuric acid component is decomposed during the calcination, and although the selectivity is increased, the catalytic activity is reduced, which is not preferable.
【００１２】反応原料の不飽和カルボン酸としてはアク
リル酸、メタクリル酸等の脂肪族一価カルボン酸、マレ
イン酸等の脂肪族二価カルボン酸、更にケイ皮酸などの
芳香族不飽和カルボン酸が例示されるが、中でもアクリ
ル酸、メタクリル酸が好ましい。エステル化反応に使用
されるアルコールとしては、特に限定されないが、メタ
ノール、エタノール、プロパノール、ｎ−ブタノール、
ｉ−ブタノール、ｔ−ブタノール、ｎ−ペンタノール、
ｉ−ヘプタノール、ｎ−オクタノール、及び２−エチル
ヘキサノールのような炭素原子数が１〜８の脂肪族一価
アルコールが好ましい。Examples of the unsaturated carboxylic acid used as the reaction raw material include aliphatic monocarboxylic acids such as acrylic acid and methacrylic acid, aliphatic dicarboxylic acids such as maleic acid, and aromatic unsaturated carboxylic acids such as cinnamic acid. Among them, acrylic acid and methacrylic acid are preferable. The alcohol used in the esterification reaction is not particularly limited, but may be methanol, ethanol, propanol, n-butanol,
i-butanol, t-butanol, n-pentanol,
Aliphatic monohydric alcohols having 1 to 8 carbon atoms such as i-heptanol, n-octanol and 2-ethylhexanol are preferred.
【００１３】本発明におけるアルコールと不飽和カルボ
ン酸との使用割合については、そののモル比が１／１０
〜１０／１（アルコール／不飽和カルボン酸）の範囲に
あるのが好ましく、特に好ましいのは１／２〜５／１で
ある。なお、過剰に用いたアルコールや不飽和カルボン
酸は反応後に生成エステル等と分離した後、循環再使用
することができる。In the present invention, the molar ratio of the alcohol to the unsaturated carboxylic acid is 1/10.
It is preferably in the range of from 10/1 to 10/1 (alcohol / unsaturated carboxylic acid), and particularly preferably from 1/2 to 5/1. In addition, the alcohol and unsaturated carboxylic acid used in excess can be recycled and reused after separation from the formed ester and the like after the reaction.
【００１４】エステル化反応条件は目的とする製品エス
テルの種類等によって異なるが、温度としては３０〜１
５０℃、反応時間は０．１〜１０時間の範囲とするのが
好適である。またエステル化反応は気相又は液相のいず
れでも行うことができ、その反応型式としては流動床、
固定床どちらでもよい。エステル化反応を液相で行う場
合は、本発明の目的、効果を損なわない範囲で、重合禁
止剤を併用することができる。使用できる重合禁止剤と
しては例えばハイドロキノン、メトキシハイドロキノ
ン、ヒドロキシルアミン、フェニレンジアミンなどが挙
げられる。The esterification reaction conditions vary depending on the kind of the desired product ester and the like.
It is preferable that the reaction time is 50 ° C. and the reaction time is in the range of 0.1 to 10 hours. The esterification reaction can be performed in either the gas phase or the liquid phase, and the reaction type is a fluidized bed,
Either fixed floor may be used. When the esterification reaction is performed in a liquid phase, a polymerization inhibitor can be used in combination as long as the object and effects of the present invention are not impaired. Examples of the polymerization inhibitor that can be used include hydroquinone, methoxyhydroquinone, hydroxylamine, phenylenediamine and the like.
【００１５】[0015]
【実施例】以下、実施例を用いて、本発明を更に具体的
に説明するが、本発明はこれらの実施例によって限定さ
れるものではない。なお、実施例及び比較例はガスクロ
マトグラフの分析結果に基づく生成物の組成及び仕込量
から、下記の式により計算された「転化率（％）」及び
「エステル選択率（％）」によって評価した。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The examples and comparative examples were evaluated by the “conversion (%)” and the “ester selectivity (%)” calculated from the following formulas based on the product composition and the charged amount based on the analysis results of the gas chromatograph. .
【００１６】[0016]
【数１】転化率（モル％）＝（生成したエステルのモル
数／供給した不飽和カルボン酸のモル数）Ｘ１００Conversion ratio (mol%) = (mol number of ester formed / mol number of unsaturated carboxylic acid supplied) × 100
【００１７】[0017]
【数２】エステル選択率（モル％）＝（生成したエステ
ルのモル数／消費された不飽和カルボン酸のモル数）Ｘ
１００## EQU2 ## Ester selectivity (mol%) = (mol number of ester formed / mol number of unsaturated carboxylic acid consumed) X
100
【００１８】＜実施例＞ジルコニウムをベースとした固体超強酸の調製 撹拌機と温度計とを備えた１００ｍｌのガラス製反応器
中で８．８ｇの酸化二塩化ジルコニウム八水和物（Ｚｒ
ＯＣｌ2・８Ｈ2０）を室温で８０ｍｌの水に溶解した。
室温のまま撹拌しながら、２８％水酸化アンモニウム
（ＮＨ4ＯＨ）を徐々に添加し、反応混合物を塩基性
（ｐＨ＝約８〜９）に調節した。生成した白色沈殿物
（Ｚｒ(ＯＨ)4）を蒸留水で洗浄して塩素イオンを除去
し、減圧下１００℃のオーブン中で一昼夜乾燥して、約
４ｇの乾燥した水酸化ジルコニウムを得た。EXAMPLES Preparation of Zirconium-Based Solid Superacids 8.8 g of zirconium oxide dichloride octahydrate (Zr) in a 100 ml glass reactor equipped with stirrer and thermometer.
The OCl 2 · 8H 2 0) was dissolved in water 80ml at room temperature.
While stirring at room temperature, 28% ammonium hydroxide (NH 4 OH) was gradually added to adjust the reaction mixture to basic (pH = about 8 to 9). The resulting white precipitate (Zr (OH) 4 ) was washed with distilled water to remove chloride ions, and dried in an oven at 100 ° C. under reduced pressure overnight to obtain about 4 g of dried zirconium hydroxide.
【００１９】この水酸化ジルコニウムに硫酸（Ｈ2Ｓ
Ｏ4）を徐々に添加して、十分混合し、生成した固体を
乾燥空気中で６００℃で焼成し、ジルコニウムを含有す
る固体超強酸（以下、これを「ＳＯ4 2-／ＺｒＯ2」と記
す）を得た。（焼成は「荒田一志他、”表面”、２８
巻、第４８１頁（１９９０年発行）」に記載の方法に従
って実施した。）The zirconium hydroxide is added to sulfuric acid (H 2 S
O 4 ) was gradually added thereto, mixed well, and the resulting solid was fired at 600 ° C. in dry air to obtain a solid superacid containing zirconium (hereinafter referred to as “SO 4 2− / ZrO 2 ”). Described below). (Firing is "Kazushi Arata et al.," Surface ", 28
Volume, page 481 (issued in 1990) ". )
【００２０】エステル化反応 温度計と水冷冷却器とを備えた１００ｍｌの３つ口ガラ
ス製フラスコに、４３．７ｍｍｏｌ（４ｍｌ）のブタノ
ールと、４３．７ｍｍｏｌ（３ｍｌ）のアクリル酸、及
び溶媒として５ｍｌのトルエンを仕込み、触媒として上
記のように調製したＳＯ4 2-／ＺｒＯ2を１．０ｇ添加し
た。反応器を閉じ、反応温度を８０℃に維持して、激し
く撹拌しながら反応を行った。反応開始から１時間、２
時間、及び４時間経過した時に、反応混合物をそれぞれ
少量ずつ採取し、ガスクロマトグラフにより分析した。
分析結果に基づいて、転化率及びエステル選択率を計算
した。結果を表に示す。In a 100 ml three-necked glass flask equipped with an esterification thermometer and a water-cooled condenser, 43.7 mmol (4 ml) of butanol, 43.7 mmol (3 ml) of acrylic acid, and 5 ml of a solvent were used. Was charged, and 1.0 g of SO 4 2− / ZrO 2 prepared as described above was added as a catalyst. The reactor was closed, the reaction temperature was maintained at 80 ° C., and the reaction was carried out with vigorous stirring. 1 hour from the start of the reaction, 2
After a lapse of 4 hours, the reaction mixture was sampled in small portions, and analyzed by gas chromatography.
Based on the analysis results, the conversion and ester selectivity were calculated. The results are shown in the table.
【００２１】＜比較例１〜４＞触媒をＳＯ4 2-／ＺｒＯ2
から市販の硫酸（関東化学（株）製）、パラトルエンス
ルホン酸（和光純薬工業（株）製）、リンタングステン
酸（（Ｈ3ＰＷ12Ｏ40）日本無機化学工業（株）製）、
及び市販のスルホン基を有する酸性イオン交換樹脂アン
バーリスト１５（オルガノ（株）製）に、それぞれ代え
たこと以外は実施例と同様にエステル化反応を行った。
触媒の使用量及び反応結果を表に併せて示す。なお、表
中「Ｈ＋」で示された数値は、これらの触媒の水素イオ
ン含有量である。<Comparative Examples 1 to 4> The catalyst was SO 4 2− / ZrO 2
Commercially available sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), paratoluenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.), phosphotungstic acid ((H 3 PW 12 O 40 ) manufactured by Nippon Inorganic Chemical Industry Co., Ltd.),
An esterification reaction was carried out in the same manner as in the Example, except that each was replaced with a commercially available acidic ion exchange resin Amberlyst 15 having a sulfone group (manufactured by Organo Corporation).
The amount of the catalyst used and the reaction results are shown in the table. In addition, the numerical value shown by "H +" in a table | surface is a hydrogen ion content of these catalysts.
【００２２】＜結果の評価＞上記の実施例及び比較例よ
り以下の諸点が判明する。 （１）本発明のジルコニウムを含有する固体超強酸を触
媒として用いるエステル化反応においては、選択率が９
９％以上と極めて良好である。また反応速度も、通常の
強酸触媒ほどではないが、廃水処理の問題のない濾別可
能なイオン交換樹脂触媒に比べ速い。 （２）強酸触媒（比較例１、２）では、選択率が９５％
未満である。 （３）本発明の範囲外の改良触媒（ヘテロポリ酸：比較
例３、イオン交換樹脂：比較例４）では、選択率の向上
は見られるが、本発明には及ばない。またイオン交換樹
脂では反応速度が遅い。<Evaluation of Results> The following points are evident from the above Examples and Comparative Examples. (1) In the esterification reaction using the zirconium-containing solid superacid of the present invention as a catalyst, the selectivity is 9
It is as good as 9% or more. The reaction rate is not as high as that of a normal strong acid catalyst, but is higher than that of a filterable ion exchange resin catalyst which does not have a problem of wastewater treatment. (2) With the strong acid catalyst (Comparative Examples 1 and 2), the selectivity was 95%.
Is less than. (3) With an improved catalyst (heteropolyacid: Comparative Example 3, ion-exchange resin: Comparative Example 4) outside the range of the present invention, the selectivity is improved, but does not fall within the present invention. The reaction rate of an ion exchange resin is low.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明のジルコニウムを含有する固体超
強酸を触媒としてエステル化反応を行う方法によって、 （１）不飽和カルボン酸エステルの選択率が高く、従っ
て生産性及び歩留まりが向上して、工業的に有利であ
る。 （２）固体触媒であるため触媒と目的物との分離が容易
であり、アルカリ水溶液による洗浄が不要となり、廃水
を処理する必要がない。 等の効果が得られる。According to the method of the present invention for carrying out an esterification reaction using a zirconium-containing solid superacid as a catalyst, (1) the selectivity of the unsaturated carboxylic acid ester is high, and thus the productivity and the yield are improved. It is industrially advantageous. (2) Since it is a solid catalyst, it is easy to separate the catalyst and the target substance, washing with an alkaline aqueous solution becomes unnecessary, and there is no need to treat wastewater. And the like.
Claims (6)
させて不飽和カルボン酸エステルを製造するに際して、
触媒としてジルコニウムを含有する固体超強酸を用いる
不飽和カルボン酸エステルの製造方法。1. When producing an unsaturated carboxylic acid ester by reacting an alcohol with an unsaturated carboxylic acid,
A method for producing an unsaturated carboxylic acid ester using a solid superacid containing zirconium as a catalyst.
脂肪族一価アルコールを用いる請求項１に記載の不飽和
カルボン酸エステルの製造方法。2. The method for producing an unsaturated carboxylic acid ester according to claim 1, wherein an aliphatic monohydric alcohol having 1 to 8 carbon atoms is used as the alcohol.
メタクリル酸を用いる請求項１又は２記載の製造方法。3. The production method according to claim 1, wherein acrylic acid or methacrylic acid is used as the unsaturated carboxylic acid.
て水酸化ジルコニウムと硫酸との反応生成物を用いる請
求項１〜３のいずれか１項に記載の製造方法。4. The method according to claim 1, wherein a reaction product of zirconium hydroxide and sulfuric acid is used as the zirconium-containing solid superacid.
ン酸とのモル比が１／１０〜１０／１（アルコール／不
飽和カルボン酸）の範囲にある請求項１〜４のいずれか
１項に記載の製造方法。5. The method according to claim 1, wherein the molar ratio between the alcohol and the unsaturated carboxylic acid used in the reaction is in the range of 1/10 to 10/1 (alcohol / unsaturated carboxylic acid). Manufacturing method.
０．１〜１０時間の範囲にある反応条件でエステル化反
応を行う請求項１〜５のいずれか１項に記載の製造方
法。6. The method according to claim 1, wherein the esterification reaction is carried out under a reaction temperature of 30 to 150 ° C. and a reaction time of 0.1 to 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9321020A JPH11152249A (en) | 1997-11-21 | 1997-11-21 | Method for producing unsaturated carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9321020A JPH11152249A (en) | 1997-11-21 | 1997-11-21 | Method for producing unsaturated carboxylic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11152249A true JPH11152249A (en) | 1999-06-08 |
Family
ID=18127907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9321020A Pending JPH11152249A (en) | 1997-11-21 | 1997-11-21 | Method for producing unsaturated carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11152249A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006083068A (en) * | 2004-09-14 | 2006-03-30 | Toagosei Co Ltd | Method for producing aromatic ester compound |
| JP2006256998A (en) * | 2005-03-16 | 2006-09-28 | Tosoh F-Tech Inc | METHOD FOR PRODUCING alpha-PERFLUOROALKYLACRYLIC ACID |
| CN1301155C (en) * | 2004-09-20 | 2007-02-21 | 南京工业大学 | Preparation and application of solid acid catalyst for synthesizing tetraisooctyl pyromellitate |
| JP2008050302A (en) * | 2006-08-24 | 2008-03-06 | Idemitsu Kosan Co Ltd | Process for producing (meth) acrylic acid oxoadamantyl esters |
| JP2011507695A (en) * | 2007-12-27 | 2011-03-10 | エルジー・ケム・リミテッド | Esterification catalyst composition containing zirconium compound and method for producing ester compound using the same |
| CN102250158A (en) * | 2011-05-23 | 2011-11-23 | 中国科学技术大学 | Method for preparing levoglucosenone |
| CN102380402A (en) * | 2011-08-25 | 2012-03-21 | 华北电力大学 | Titanium-based magnetic solid super-acid catalyst and preparation thereof and method for preparing laevoglucose ketone by means of catalytic pyrolysis of cellulose or biomass |
| CN104496804A (en) * | 2014-12-31 | 2015-04-08 | 浙江嘉澳环保科技股份有限公司 | Synthetic method of dichloropropanol aliphatic ester |
-
1997
- 1997-11-21 JP JP9321020A patent/JPH11152249A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006083068A (en) * | 2004-09-14 | 2006-03-30 | Toagosei Co Ltd | Method for producing aromatic ester compound |
| CN1301155C (en) * | 2004-09-20 | 2007-02-21 | 南京工业大学 | Preparation and application of solid acid catalyst for synthesizing tetraisooctyl pyromellitate |
| JP2006256998A (en) * | 2005-03-16 | 2006-09-28 | Tosoh F-Tech Inc | METHOD FOR PRODUCING alpha-PERFLUOROALKYLACRYLIC ACID |
| JP2008050302A (en) * | 2006-08-24 | 2008-03-06 | Idemitsu Kosan Co Ltd | Process for producing (meth) acrylic acid oxoadamantyl esters |
| JP2011507695A (en) * | 2007-12-27 | 2011-03-10 | エルジー・ケム・リミテッド | Esterification catalyst composition containing zirconium compound and method for producing ester compound using the same |
| CN102250158A (en) * | 2011-05-23 | 2011-11-23 | 中国科学技术大学 | Method for preparing levoglucosenone |
| CN102380402A (en) * | 2011-08-25 | 2012-03-21 | 华北电力大学 | Titanium-based magnetic solid super-acid catalyst and preparation thereof and method for preparing laevoglucose ketone by means of catalytic pyrolysis of cellulose or biomass |
| CN104496804A (en) * | 2014-12-31 | 2015-04-08 | 浙江嘉澳环保科技股份有限公司 | Synthetic method of dichloropropanol aliphatic ester |
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