JPS649975B2 - - Google Patents
Info
- Publication number
- JPS649975B2 JPS649975B2 JP56189495A JP18949581A JPS649975B2 JP S649975 B2 JPS649975 B2 JP S649975B2 JP 56189495 A JP56189495 A JP 56189495A JP 18949581 A JP18949581 A JP 18949581A JP S649975 B2 JPS649975 B2 JP S649975B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- carboxylic acid
- alcohol
- water
- aluminum
- 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
Links
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 150000002148 esters Chemical class 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- -1 aluminum ions Chemical class 0.000 claims description 25
- 208000012839 conversion disease Diseases 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 150000001339 alkali metal compounds Chemical class 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DEVXQDKRGJCZMV-UHFFFAOYSA-K Aluminum acetoacetate Chemical compound [Al+3].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O DEVXQDKRGJCZMV-UHFFFAOYSA-K 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はカルボン酸エステルの製造方法に関
し、更に詳しくは、アルミニウム化合物及びアル
カリ金属化合物を触媒として用いる製造品質が優
れかつ反応時間の短いカルボン酸エステルの製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carboxylic esters, and more particularly, to a method for producing carboxylic esters with excellent production quality and short reaction time using aluminum compounds and alkali metal compounds as catalysts. be.
カルボン酸とアルコールの反応によりエステル
を製造する場合、工業的には硫酸等の酸触媒が常
用されている。 When producing esters by reacting carboxylic acids and alcohols, acid catalysts such as sulfuric acid are commonly used industrially.
しかしながら酸触媒を用いるとエステル化の過
程において副反応が生じ易いので、合成されたエ
ステル製品は熱安定性が劣り体積固有抵抗値が小
さく、可塑剤として用いる場合には品質的に劣つ
たものとなる欠点があつた。 However, when acid catalysts are used, side reactions tend to occur during the esterification process, so the synthesized ester products have poor thermal stability and low volume resistivity, and are of inferior quality when used as plasticizers. There was a drawback.
かかる欠点を除くため、金属化合物等の酸以外
の触媒が種々提案され、なかでも、比較的安価な
アルミナ系触媒が注目されているが、通常、エス
テル化に長時間を要するためアルミナ系化合物を
触媒とするエステルの製法は工業的実施が困難な
ものであつた。 In order to eliminate this drawback, various catalysts other than acids such as metal compounds have been proposed, and among them, relatively inexpensive alumina-based catalysts are attracting attention. The method for producing esters used as catalysts has been difficult to implement industrially.
本発明は上記従来の方法に鑑みて、短時間の反
応で充分な到達反応転化率に達しかつ品質のすぐ
れた製品が得られるカルボン酸エステルの製造方
法を提供することを目的とするもので、アルミニ
ウム化合物を触媒としてエステル化反応を行う場
合、反応後半において反応速度が著しく減少する
が反応転化率が70重量％以上に到達しのちに反応
系に水を加えると上記反応速度の著しい減少が軽
減されるという知見を得て完成されたものであ
る。しかして本発明の要旨は、カルボン酸又はカ
ルボン酸無水物とアルコールからエステルを製造
するに際して、アルミニウムイオン及びアルカリ
金属イオンの存在下でカルボン酸又はカルボン酸
無水物とアルコールを反応させ、カルボン酸又は
カルボン酸無水物の反応転化率が約70重量％以上
に到達したのちに反応系に水を加えることを特徴
とするカルボン酸エステルの製造方法に存する。 In view of the above-mentioned conventional methods, it is an object of the present invention to provide a method for producing carboxylic acid esters that can reach a sufficient reaction conversion rate in a short reaction time and produce products of excellent quality. When performing an esterification reaction using an aluminum compound as a catalyst, the reaction rate decreases significantly in the latter half of the reaction, but if water is added to the reaction system after the reaction conversion reaches 70% by weight or more, the significant decrease in reaction rate can be alleviated. It was completed with the knowledge that it would be possible. Therefore, the gist of the present invention is that when producing an ester from a carboxylic acid or carboxylic acid anhydride and an alcohol, the carboxylic acid or carboxylic acid anhydride is reacted with the alcohol in the presence of aluminum ions and alkali metal ions, and the carboxylic acid or carboxylic acid anhydride is reacted with the alcohol. The present invention resides in a method for producing a carboxylic acid ester, characterized in that water is added to the reaction system after the reaction conversion rate of the carboxylic acid anhydride reaches about 70% by weight or more.
本発明におけるカルボン酸としては、フタル
酸、イソフタル酸、テレフタル酸、トリメツト酸
などの芳香族多価カルボン酸、安息香酸などの芳
香族モノカルボン酸、アジビン酸、セバシン酸な
どの脂肪族飽和多価カルボン酸、マレイン酸、フ
マル酸などの脂肪族不飽和多価カルボン酸、及び
オレイン酸、ステアリン酸などの脂肪族モノカル
ボン酸などが用いられる。そしてこれ等の有機酸
若しくはその無水物のうち、芳香族多価カルボン
酸およびこの酸無水物が好適に用いられ、フタル
酸及びフタル酸無水物は特に好適に用いられる。 The carboxylic acids in the present invention include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and trimethic acid, aromatic monocarboxylic acids such as benzoic acid, and aliphatic saturated polycarboxylic acids such as adivic acid and sebacic acid. Carboxylic acids, aliphatic unsaturated polycarboxylic acids such as maleic acid and fumaric acid, and aliphatic monocarboxylic acids such as oleic acid and stearic acid are used. Among these organic acids and their anhydrides, aromatic polyhydric carboxylic acids and their acid anhydrides are preferably used, and phthalic acid and phthalic anhydride are particularly preferably used.
又、アルコールとしてはたとえばｎ−ブチルア
ルコール、イソ−ブチルアルコール、第二級ブチ
ルアルコール、イソ−ヘプチルアルコール、ネオ
ペンチルアルコール、ｎ−オクチルアルコール、
２−エチルヘキシルアルコール、イソオクチルア
ルコール、ノニルアルコール、デシルアルコール
等の脂肪族飽和−価アルコールやたとえばエチレ
ングリコール、ジエチレングリコール、プロピレ
ングリコール、ブタンジオール、ペンタエリスリ
トールなどの脂肪族多価アルコールが用いられ、
これ等のアルコールの混合物が用いられてもよ
い。そしてこれ等のアルコールのうち特に炭素原
子数４〜10の脂肪族飽和−価アルコールが好適に
用いられる。 Examples of the alcohol include n-butyl alcohol, iso-butyl alcohol, secondary butyl alcohol, iso-heptyl alcohol, neopentyl alcohol, n-octyl alcohol,
Aliphatic saturated-hydric alcohols such as 2-ethylhexyl alcohol, isooctyl alcohol, nonyl alcohol, and decyl alcohol, and aliphatic polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, and pentaerythritol are used,
Mixtures of these alcohols may also be used. Among these alcohols, aliphatic saturated alcohols having 4 to 10 carbon atoms are particularly preferably used.
本発明において触媒として用いるアルミニウム
イオン及びアルカリ金属イオンは、例えば、カル
ボン酸又はカルボン酸無水物とアルコールよりな
るエステル原料中に後述するアルミニウム化合物
及びアルカリ金属化合物を加えてエステル化反応
温度とほぼ同じ温度にて加熱することにより容易
に得られる。未溶解アルミニウム化合物は必要に
応じて過、遠心分離、沈降分離等の適宜の操作
により分離除去される。アルカリ金属化合物は通
常水溶液として用いられ、アルミニウム化合物と
共に水の沸点より高い温度で調整される間に触媒
中の水分は適宜蒸発される。上記アルミニウム化
合物の具体例としては、水酸化アアルミニウム、
アルミナ水和物、活性アルミナ、アルミナゲル、
アルミン酸ソーダ等の酸化アルミニウム化合物、
硫酸アルミニウム、硝酸アルミニウム、塩化アル
ミニウム等の強酸のアルミニウム塩、トリ−エト
キシ−アルミネート、トリ−イソプロポキシーア
ルミネート等のアルコキシアルミネート、酢酸ア
ルミニウム、炭酸アルミニウム等の弱酸の塩、ア
ルミニウム−アセチルアセトネート等のキレート
型アルミニウム化合物が挙げられ、活性アルミナ
やトリエトキシアルミネート等が特に好適に用い
られる。 The aluminum ions and alkali metal ions used as catalysts in the present invention can be prepared, for example, by adding the aluminum compounds and alkali metal compounds described below to an ester raw material consisting of a carboxylic acid or carboxylic acid anhydride and alcohol at a temperature approximately the same as the esterification reaction temperature. It can be easily obtained by heating at . Undissolved aluminum compounds are separated and removed by appropriate operations such as filtration, centrifugation, and sedimentation, if necessary. The alkali metal compound is usually used as an aqueous solution, and the water in the catalyst is appropriately evaporated while the alkali metal compound is adjusted together with the aluminum compound at a temperature higher than the boiling point of water. Specific examples of the above aluminum compounds include aluminum hydroxide,
Alumina hydrate, activated alumina, alumina gel,
Aluminum oxide compounds such as sodium aluminate,
Aluminum salts of strong acids such as aluminum sulfate, aluminum nitrate, and aluminum chloride; alkoxyaluminates such as tri-ethoxy-aluminate and tri-isopropoxy aluminate; salts of weak acids such as aluminum acetate and aluminum carbonate; aluminum acetylacetate; Examples include chelate type aluminum compounds such as aluminate, and activated alumina, triethoxyaluminate, etc. are particularly preferably used.
又、上記アルカリ金属化合物の具体例として
は、水酸化ナトリウム、炭酸ナトリウム、炭酸ナ
トリウム、炭酸水素ナトリウム、水酸化カリウ
ム、炭酸カリウム、炭酸水素カリウム、水酸化リ
チウム、炭酸リチウム等が挙げられ特に水酸化ナ
トリウムが多用されれる。 Specific examples of the alkali metal compounds include sodium hydroxide, sodium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, lithium hydroxide, and lithium carbonate. Sodium is often used.
反応速度を高めるためには、エステル原料中に
溶解せしめたアルミニウムの初期濃度が高い方が
好ましいが高過ぎると触媒除去操作が煩雑になる
ので、該イオン濃度は通常20〜10000ppmの範囲
とされ、好ましくは50〜5000ppmの範囲で用いら
れる。又、通常の反応温度で比較的短時間に充分
高い到達転化率を得るためには反応終了時のアル
ミニウムイオン濃度を200ppm以下とするのが好
ましい。又上記アルカリ金属化合物の使用量は溶
存アルカリ金属イオンが溶存アルミニウムイオン
１当量に対し0.1〜２当量の範囲になる量とされ
る。 In order to increase the reaction rate, it is preferable that the initial concentration of aluminum dissolved in the ester raw material is high, but if it is too high, the catalyst removal operation becomes complicated, so the ion concentration is usually in the range of 20 to 10,000 ppm, It is preferably used in a range of 50 to 5000 ppm. Further, in order to obtain a sufficiently high conversion rate in a relatively short time at a normal reaction temperature, it is preferable that the aluminum ion concentration at the end of the reaction is 200 ppm or less. The amount of the alkali metal compound used is such that the amount of dissolved alkali metal ions is in the range of 0.1 to 2 equivalents per equivalent of dissolved aluminum ions.
本発明においては上記少くとも二種のイオンの
存在下でカルボン酸又はカルボン酸無水物とアル
コールとを反応させ、カルボン酸又はカルボン酸
無水物の反応転化率が70重量％以上、好ましくは
80重量％以上、更に好ましくは90重量％以上に到
達したのちに反応系に水を加えるのである。かく
することにより、反応後半においても反応速度が
著しく低下することがなく短時間に充分な反応転
化率に到達させることができる。反応転化率が70
％未満の状態で水を加えてもその後の反応速度の
著しい低下を充分に防止することはできない。加
える水の量はカルボン酸又はカルボン酸無水物の
仕込量100重量部に対して0.01〜20重量部、好ま
しくは0.1〜10重量部とされる。この量が少な過
ぎると反応後半における反応速度の低下を防止す
ることが難しく、多過ぎると水を蒸発させるため
に要する潜熱として消費されるエネルギーが大と
なる。反応系に水を加える際は全量を一度に加え
てもよく、或いは適宜分割したり連続しても加え
てもよい。添加温度は特に限定されないが通常は
80℃以上とされる。 In the present invention, a carboxylic acid or carboxylic acid anhydride is reacted with an alcohol in the presence of at least two types of ions, and the reaction conversion rate of the carboxylic acid or carboxylic acid anhydride is preferably 70% by weight or more, preferably
Water is added to the reaction system after reaching 80% by weight or more, more preferably 90% by weight or more. By doing so, the reaction rate does not drop significantly even in the latter half of the reaction, and a sufficient reaction conversion rate can be reached in a short time. Reaction conversion rate is 70
Even if water is added in an amount less than %, it is not possible to sufficiently prevent a significant decrease in the subsequent reaction rate. The amount of water added is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the carboxylic acid or carboxylic acid anhydride. If this amount is too small, it will be difficult to prevent the reaction rate from decreasing in the latter half of the reaction, and if it is too large, the energy consumed as latent heat required to evaporate water will increase. When adding water to the reaction system, the entire amount may be added at once, or may be added in appropriate portions or continuously. The addition temperature is not particularly limited, but usually
It is considered to be over 80℃.
尚、本発明において後半の反応速度の著しい低
下を防止し得る理由は明確ではない、反応後半で
水を加えることにより反応に強く関与する系にお
いて過剰となつていたアルミニウムイオンを何ら
かの理由でその系外に移行せしめ、従つて反応系
が初期の程度の活性を取り戻すものと推定され
る。 It should be noted that in the present invention, it is not clear why the remarkable decrease in the reaction rate in the second half of the reaction can be prevented. It is assumed that the reaction system regains its initial level of activity.
本発明方法によりカルボン酸エステルを得るに
は、上記カルボン酸又はカルボン酸無水物にこれ
らと反応するアルコール量よりやや過剰のアルコ
ールを添加し、通常はその後、例えば上記の方法
で調整した触媒又は触媒を含む粗エステル溶液等
を添加し、アルコールの還流下で減圧下に通常
150〜200℃の温度、場合によつては200℃〜250℃
の如き高温域で反応を行なわしめる。反応系の酸
価が0.1以下になれば反応を終了するが、反応時
間は１時間〜２時間、通常は長くても４時間で済
む。その後、未反応のカルボン酸を取り除く為に
反応系を50〜100℃に冷却し粗エステルに対して
0.003〜３重量％の水酸化ナトリウム水溶液又は
炭酸ナトリウム水溶液等のアルカリを加え、更に
水を投入して撹拌し、未反応カルボン酸を水中に
抽出する。その後過剰のアルコールを蒸溜により
除き、活性炭もしくは活性白土等で処理して反応
系中に残存する触媒に吸着除去することによつて
製品とする。 In order to obtain a carboxylic acid ester by the method of the present invention, an alcohol slightly in excess of the amount of alcohol to be reacted with the carboxylic acid or carboxylic acid anhydride is added to the carboxylic acid or carboxylic acid anhydride, and then, for example, a catalyst prepared by the above method or a catalyst is added. Add the crude ester solution etc. containing the alcohol, usually under reduced pressure under reflux of alcohol.
Temperatures of 150-200℃, sometimes 200℃-250℃
The reaction is carried out in a high temperature range such as The reaction is terminated when the acid value of the reaction system becomes 0.1 or less, and the reaction time is 1 to 2 hours, usually 4 hours at most. After that, in order to remove unreacted carboxylic acid, the reaction system was cooled to 50-100℃, and the crude ester was
An alkali such as a 0.003 to 3% by weight aqueous sodium hydroxide solution or an aqueous sodium carbonate solution is added, and water is further added and stirred to extract unreacted carboxylic acid into the water. Thereafter, excess alcohol is removed by distillation, treated with activated carbon or activated clay, etc., and removed by adsorption onto the catalyst remaining in the reaction system to produce a product.
本発明カルボン酸エステルの製造方法は上述の
通りの構成になされており、アルミニウムイオン
及びアルカリ金属イオンの存在下でエステル化反
応を行ないカルボン酸又はその無水物の反応転化
率が70重量％以上に到達したのちに反応系に水を
加えるので、副反応を殆んど生じることなく反応
を完結せしめ得るという従来のアルミニウム化合
物を触媒とするエステル化法の長所を維持し且つ
反応速度を高めることができる。即ち本発明製造
方法は副反応より生じる種々の物質を生成エステ
ル中より除去する為の水洗又は全蒸溜等の工程を
必要とせず、且つ反応後半において反応速度が著
しく低下することがなく、アルミニウム化合物を
触媒とする従来の製造法に比して反応時間が短く
て済むのである。本発明によれば、着色が殆んど
なく体積固有抵抗が充分大きい、例えば可塑剤と
して用いて品質の極めて良好なエステルが得られ
るのである。以下本発明方法の実施例について説
明する。 The method for producing a carboxylic acid ester of the present invention is configured as described above, in which the esterification reaction is carried out in the presence of aluminum ions and alkali metal ions, and the reaction conversion rate of carboxylic acid or its anhydride is 70% by weight or more. Since water is added to the reaction system after reaching this point, it is possible to maintain the advantage of the conventional esterification method using an aluminum compound as a catalyst, which allows the reaction to be completed with almost no side reactions, and to increase the reaction rate. can. In other words, the production method of the present invention does not require steps such as washing with water or total distillation to remove various substances resulting from side reactions from the produced ester, and does not significantly reduce the reaction rate in the latter half of the reaction. The reaction time is shorter than that of the conventional production method using a catalyst. According to the present invention, it is possible to obtain an ester with very good quality, which has almost no coloring and has a sufficiently high volume resistivity, for example, when used as a plasticizer. Examples of the method of the present invention will be described below.
なお以下において示される体積固有抵抗値、酸
価及び色相ハーゼン値はJIS−Ｋ−6751（フタル酸
エステル試験法）に準拠して測定した。又、溶存
アルミニウムイオン濃度は試料中のアルミニウム
イオンのオキシン錯塩の390mμの吸光度より求
め、反応転化率は酸価より求めた。単に部とある
のは重量部、％とあるのは重量％を表わす。 Note that the volume resistivity, acid value, and hue Hazen value shown below were measured in accordance with JIS-K-6751 (phthalate ester test method). Further, the dissolved aluminum ion concentration was determined from the absorbance at 390 mμ of the oxine complex salt of aluminum ions in the sample, and the reaction conversion rate was determined from the acid value. Simply "part" means part by weight, and "%" means percent by weight.
実施例 １
還流コンデンサー、分水器を備えた撹拌式反応
器に無水フタル酸148.1部、２−エチルヘキシル
アルコール143.3部、活性アルミナ（組成Al2O3、
含有料54％）8.5部、20％水酸ナトリウム水溶液
2.7部を加えて160℃で１時間、２−エチルヘキシ
ルアルコール還流下で反応させ、ついで未溶解活
性アルミナを別し溶存アルミニウムイオン
380ppmを含有する粗エステル溶液Ａを調整した。
このときの無水フタル酸の反応転化率は24.3％で
あつた。Example 1 148.1 parts of phthalic anhydride, 143.3 parts of 2-ethylhexyl alcohol, and activated alumina (composition Al 2 O 3 ,
Contains 54%) 8.5 parts, 20% sodium hydroxide aqueous solution
2.7 parts was added and reacted at 160°C for 1 hour under refluxing 2-ethylhexyl alcohol, then undissolved activated alumina was separated and dissolved aluminum ions were removed.
A crude ester solution A containing 380 ppm was prepared.
The reaction conversion rate of phthalic anhydride at this time was 24.3%.
還流コンデンサー、分水器を備えた撹拌式反応
器に上記粗エステル溶液A291部及び２−エチル
ヘキシルアルコール156.2部を加えて190℃に昇温
し、２−エチルヘキシルアルコール還流下で反応
水を除去しながら反応させた。反応開始１時間後
に水５部を加え（このときの無水フタル酸の反応
転化率は96.2％であつた。）反応開始後190℃に保
つて２時間（水を加えてから１時間）反応させ
た。得られた粗エステルはフイルターで過して
析出した不溶の触媒を除去した。このものの反応
転化率は99.8％でアルミニウムイオン濃度は、
60ppmであつた。ついで中和、水洗し、水、アル
コール、触媒を除去して得られたエステルの酸価
は0.007、色相ハーゼン値は10、体積固有抵抗値
は２×1012Ωcmであつた。 291 parts of the above crude ester solution A and 156.2 parts of 2-ethylhexyl alcohol were added to a stirred reactor equipped with a reflux condenser and a water separator, the temperature was raised to 190°C, and the reaction water was removed while refluxing the 2-ethylhexyl alcohol. Made it react. One hour after the start of the reaction, 5 parts of water was added (the reaction conversion rate of phthalic anhydride at this time was 96.2%). After the start of the reaction, the temperature was maintained at 190°C and the reaction was allowed to proceed for 2 hours (1 hour after adding water). Ta. The obtained crude ester was passed through a filter to remove the precipitated insoluble catalyst. The reaction conversion rate of this product is 99.8%, and the aluminum ion concentration is
It was 60ppm. The ester obtained by neutralization and washing with water to remove water, alcohol, and catalyst had an acid value of 0.007, a hue Hazen value of 10, and a volume resistivity value of 2×10 12 Ωcm.
比較例 １
エステル化反応の途中で水を添加しない以外は
実施例１と全く同様に２時間反応させてエステル
を製造した。得られた粗エステルの反応転化率は
98.3％でアルミニウムイオン濃度は330ppmであ
つた。さらに反応を２時間継続して行つた場合の
粗エステルの反応転化率は99.0％で、アルミニウ
ムイオン濃度は320ppmであつた。Comparative Example 1 An ester was produced by reacting for 2 hours in the same manner as in Example 1 except that water was not added during the esterification reaction. The reaction conversion rate of the obtained crude ester is
The aluminum ion concentration was 330 ppm at 98.3%. When the reaction was continued for 2 hours, the reaction conversion rate of the crude ester was 99.0%, and the aluminum ion concentration was 320 ppm.
反応時間と反応転化率の関係を第１図に示す。 The relationship between reaction time and reaction conversion rate is shown in Figure 1.
実施例 ２
調整温度及び時間を190℃で30分とする以外は
実施例１における粗エステル溶液Ａの調整と同様
にして溶存アルミニウムイオン870ppmを含有す
る粗エステル溶液Ｂを調整した。このときの無水
フタル酸の反応転化率は35％であつた。Example 2 A crude ester solution B containing 870 ppm of dissolved aluminum ions was prepared in the same manner as the preparation of the crude ester solution A in Example 1, except that the adjustment temperature and time were 190° C. for 30 minutes. The reaction conversion rate of phthalic anhydride at this time was 35%.
実施例１と同様にして、反応器に粗エステル溶
液B291部及び２−エチルヘキシルアルコール
156.2部を加え190℃で反応させた、反応開始後45
分で水５ｇを加え（このときの無水フタル酸の反
応転化率は92.5％であつた。）さらに１時間30分
後に水５ｇを加えて190℃に保つて、反応開始後
２時間15分反応させた。その後、反応系に析出し
た触媒をフイルターで過し組エステルを得た。
このエステルの反応転化率は99.8％でアルミニウ
ムイオン濃度は55ppmであつた。ついで中和、水
洗し、水、アルコール、触媒を除去して得られた
エステルの酸価は0.007、色相ハーゼン値は10、
体積固有抵抗値は２×1012Ωcmであつた。 In the same manner as in Example 1, 291 parts of crude ester solution B and 2-ethylhexyl alcohol were added to the reactor.
156.2 parts was added and reacted at 190℃, 45 minutes after the start of the reaction.
After 1 hour and 30 minutes, 5 g of water was added (the reaction conversion rate of phthalic anhydride was 92.5%). After 1 hour and 30 minutes, 5 g of water was added, and the temperature was kept at 190°C, and the reaction was carried out for 2 hours and 15 minutes after the reaction started. I let it happen. Thereafter, the catalyst precipitated in the reaction system was filtered to obtain an ester.
The reaction conversion rate of this ester was 99.8%, and the aluminum ion concentration was 55 ppm. Then, the acid value of the ester obtained by neutralizing and washing with water to remove water, alcohol, and catalyst was 0.007, the hue Hazen value was 10,
The volume resistivity value was 2×10 12 Ωcm.
比較例 ２
反応系への水の添加を反応開始後15分後（この
ときの無水フタル酸の反応転化率は67％であつ
た）に５ｇを１回加えることに変更する以外は実
施例２と同様の方法で、190℃で２時間反応させ
て粗エステルを得た。粗エステルの反応転化率は
98.8％でアルミニウムイオン濃度は490ppmであ
つた。この状態からさらに継続して２時間反応さ
せたが反応転化率は99.4％であつた。即ち、反応
開始後２時間以後の反応速度が著しく低下し所定
の転化率に達しなかつた。Comparative Example 2 Example 2 except that the addition of water to the reaction system was changed to adding 5 g once 15 minutes after the start of the reaction (the reaction conversion rate of phthalic anhydride at this time was 67%). A crude ester was obtained by reacting at 190°C for 2 hours in the same manner as above. The reaction conversion rate of crude ester is
The aluminum ion concentration was 490 ppm at 98.8%. From this state, the reaction was continued for 2 hours, and the reaction conversion rate was 99.4%. That is, the reaction rate after 2 hours from the start of the reaction decreased significantly and did not reach the predetermined conversion rate.
実施例 ３
活性アルミナの替りにトリエトキシアルミニウ
ム2.1ｇを用いる以外は実施例１における粗エス
テル溶液Ａの調整と同様にして、溶存アルミニウ
ムイオン410ppmを含有する粗エステル溶液Ｃを
得た。このときの無水フタル酸の反応転化率は
27.0％であつた。Example 3 A crude ester solution C containing 410 ppm of dissolved aluminum ions was obtained in the same manner as the preparation of the crude ester solution A in Example 1, except that 2.1 g of triethoxyaluminum was used instead of activated alumina. The reaction conversion rate of phthalic anhydride at this time is
It was 27.0%.
反応器に、上記粗エステル溶液C291部及び２
−エチルヘキシルアルコール156.2部を加え、190
℃に昇温して反応させた。 Add 291 parts of the above crude ester solution C and 2 parts to the reactor.
- Add 156.2 parts of ethylhexyl alcohol to 190
The temperature was raised to ℃ to cause a reaction.
190℃に昇温後40分で水５ｇを加え（このとき
の無水フタル酸の反応転化率は91.2％であつた。）
さらに１時間30分後に水５ｇを加え190℃に保つ
て反応開始後２時間10分反応させた。その後不溶
触媒をフイルターで過し粗エステルを得た。こ
のエステルの反応転化率は99.7％、アルミニウム
イオン濃度は、74ppmであつた。ついで中和、水
洗し、水、アルコール、触媒を除去して得られた
エステルの酸価は0.01、色相ハーゼン値は10、体
積固有抵抗値は、3.5×1012Ωcmであつた。 5 g of water was added 40 minutes after the temperature was raised to 190°C (the reaction conversion rate of phthalic anhydride at this time was 91.2%).
After a further 1 hour and 30 minutes, 5 g of water was added and the temperature was maintained at 190°C, and the reaction was continued for 2 hours and 10 minutes after the start of the reaction. Thereafter, the insoluble catalyst was filtered to obtain a crude ester. The reaction conversion rate of this ester was 99.7%, and the aluminum ion concentration was 74 ppm. The ester obtained by neutralization and washing with water to remove water, alcohol, and catalyst had an acid value of 0.01, a hue Hazen value of 10, and a volume resistivity value of 3.5×10 12 Ωcm.
第１図は本発明方法及び従来方法におけるエス
テル化反応時間と反応転化率の関係の一例を示す
図である。
FIG. 1 is a diagram showing an example of the relationship between esterification reaction time and reaction conversion rate in the method of the present invention and the conventional method.
Claims (1)
ルからエステルを製造するに際して、アルミニウ
ムイオン及びアルカリ金属イオンの存在下でカル
ボン酸又はカルボン酸無水物とアルコールを反応
させ、カルボン酸又はカルボン酸無水物の反応転
化率が約70重量％以上に到達したのちに反応系に
水を加えることを特徴とするカルボン酸エステル
の製造方法。 ２ カルボン酸無水物が無水フタル酸である第１
項記載の製造方法。 ３ アルミニウムイオンの初期濃度が20〜
10000ppmである第１項又は第２項記載の製造方
法。 ４ 反応系に加える水の量が仕込んだカルボン酸
又はカルボン酸無水物100重量部に対し、約0.01
〜20重量部である第１項〜第３項何れか１項に記
載の製造方法。[Scope of Claims] 1. When producing an ester from a carboxylic acid or carboxylic acid anhydride and an alcohol, the carboxylic acid or carboxylic anhydride is reacted with the alcohol in the presence of aluminum ions and alkali metal ions, and the carboxylic acid or carboxylic acid anhydride is reacted with the alcohol. A method for producing a carboxylic acid ester, characterized in that water is added to the reaction system after the reaction conversion rate of the acid anhydride reaches about 70% by weight or more. 2 The first carboxylic acid anhydride is phthalic anhydride
Manufacturing method described in section. 3 The initial concentration of aluminum ions is 20~
The manufacturing method according to item 1 or 2, wherein the amount is 10000 ppm. 4 The amount of water added to the reaction system is approximately 0.01 parts by weight per 100 parts by weight of the charged carboxylic acid or carboxylic acid anhydride.
The manufacturing method according to any one of Items 1 to 3, wherein the amount is 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56189495A JPS5890528A (en) | 1981-11-25 | 1981-11-25 | Preparation of carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56189495A JPS5890528A (en) | 1981-11-25 | 1981-11-25 | Preparation of carboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5890528A JPS5890528A (en) | 1983-05-30 |
| JPS649975B2 true JPS649975B2 (en) | 1989-02-21 |
Family
ID=16242218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56189495A Granted JPS5890528A (en) | 1981-11-25 | 1981-11-25 | Preparation of carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5890528A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426484A (en) * | 2022-01-21 | 2022-05-03 | 中国石油化工股份有限公司 | Synthetic method of pentaerythritol ester |
-
1981
- 1981-11-25 JP JP56189495A patent/JPS5890528A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5890528A (en) | 1983-05-30 |
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