JP2011105667A - Method for producing phenyl ester - Google Patents
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- JP2011105667A JP2011105667A JP2009263790A JP2009263790A JP2011105667A JP 2011105667 A JP2011105667 A JP 2011105667A JP 2009263790 A JP2009263790 A JP 2009263790A JP 2009263790 A JP2009263790 A JP 2009263790A JP 2011105667 A JP2011105667 A JP 2011105667A
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- -1 phenyl ester Chemical class 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 28
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 23
- 239000004327 boric acid Substances 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 230000032050 esterification Effects 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- CIBQKYNGEIFTDM-UHFFFAOYSA-N 2,2-di(propan-2-yl)propanedioic acid Chemical compound CC(C)C(C(C)C)(C(O)=O)C(O)=O CIBQKYNGEIFTDM-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000011964 heteropoly acid Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 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 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HRURMTZJRSHLAV-UHFFFAOYSA-N 1-n,4-n-bis(1,4-dimethylcyclohexa-2,4-dien-1-yl)benzene-1,4-diamine Chemical compound C1=CC(C)=CCC1(C)NC(C=C1)=CC=C1NC1(C)C=CC(C)=CC1 HRURMTZJRSHLAV-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 1
- DPFKMKWXWWRIDL-UHFFFAOYSA-N 2,2-dihexylpropanedioic acid Chemical compound CCCCCCC(C(O)=O)(C(O)=O)CCCCCC DPFKMKWXWWRIDL-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- JDFLIMZSDVQYRP-UHFFFAOYSA-N 4-n,4-n-di(propan-2-yl)benzene-1,4-diamine Chemical compound CC(C)N(C(C)C)C1=CC=C(N)C=C1 JDFLIMZSDVQYRP-UHFFFAOYSA-N 0.000 description 1
- KCSOBOZCMQBPFM-UHFFFAOYSA-N 4-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(C=CC=C2)C2=C1 KCSOBOZCMQBPFM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- UVPSETHCMCSCBE-UHFFFAOYSA-N C1(=CC=CC=C1)O.C(C)(CC)C1=C(C(=CC(=C1)[N+](=O)[O-])[N+](=O)[O-])O Chemical class C1(=CC=CC=C1)O.C(C)(CC)C1=C(C(=CC(=C1)[N+](=O)[O-])[N+](=O)[O-])O UVPSETHCMCSCBE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXPLGYBFGPYAHS-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 SXPLGYBFGPYAHS-UHFFFAOYSA-N 0.000 description 1
- ZXPNHQOWDWPUEH-UHFFFAOYSA-N boric acid;sulfuric acid Chemical compound OB(O)O.OS(O)(=O)=O ZXPNHQOWDWPUEH-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002363 hafnium compounds Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
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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、フェノールと特定のカルボン酸からエステル化反応により収率良くフェニルエステルを製造する方法に関するものである。 The present invention relates to a method for producing a phenyl ester from phenol and a specific carboxylic acid by an esterification reaction with high yield.
一般的に、アクリル酸やメタクリル酸などのカルボン酸とフェノールから直接フェニルエステルを製造する反応は、平衡定数≦０．０１であることから平衡が分解方向に偏っているため、収率を上げるのが困難である。このため、前記フェニルエステルを合成する場合には、１）特許文献１〜４などに開示されている酸クロリド、特許文献５に開示されている酸無水物などの活性アシル化剤を使用する方法、２）ＤＣＣ、ポリ燐酸などの脱水剤を使用する方法が望ましいとされている。しかし、これらの方法では高価な原料を用いているためにコスト高となる。そのため、触媒として硫酸、イオン交換樹脂など酸触媒を用い、脱水溶剤としてトルエン、キシレンなどを用いたエステル化法に関しても種々検討されてきた。 In general, the reaction for directly producing a phenyl ester from carboxylic acid such as acrylic acid or methacrylic acid and phenol has an equilibrium constant ≦ 0.01. Is difficult. For this reason, when synthesizing the phenyl ester, 1) a method using an active acylating agent such as an acid chloride disclosed in Patent Documents 1 to 4 and an acid anhydride disclosed in Patent Document 5 2) A method using a dehydrating agent such as DCC or polyphosphoric acid is considered desirable. However, these methods are expensive due to the use of expensive raw materials. For this reason, various studies have been made on esterification methods using an acid catalyst such as sulfuric acid or an ion exchange resin as a catalyst, and toluene or xylene as a dehydrating solvent.
特許文献６、７では反応触媒に強酸性イオン交換樹脂を用いたフェニルエステルの製造方法が開示されている。しかし、該方法では反応転化率が５０％前後と低く、選択率も８０％前後と満足できる成績ではない。このために、反応終了後、脱水溶剤であるトルエンを回収してから原料のメタクリル酸とフェノールを蒸留で回収する。次いで、粗メタクリル酸フェニルを留出させてからヘキサンなど炭化水素系溶剤に溶解し、弱アルカリでアクリル酸やフェノールを中和、洗浄する。その後、炭化水素系溶剤を留去し、精製フェニルエステルを蒸留して得る、という複雑な工程を取らざるを得ない。 Patent Documents 6 and 7 disclose a method for producing a phenyl ester using a strongly acidic ion exchange resin as a reaction catalyst. However, in this method, the reaction conversion rate is as low as about 50%, and the selectivity is not satisfactory as about 80%. For this purpose, after completion of the reaction, toluene as a dehydrating solvent is recovered, and then raw methacrylic acid and phenol are recovered by distillation. Next, after the crude phenyl methacrylate is distilled off, it is dissolved in a hydrocarbon solvent such as hexane, and acrylic acid and phenol are neutralized and washed with a weak alkali. Thereafter, a complicated process of distilling off the hydrocarbon solvent and obtaining the purified phenyl ester by distillation must be performed.
非特許文献１、２にはホウ酸と芳香族アルコールからホウ酸エステルを合成し、カルボン酸と置換することで芳香族アルコールのカルボン酸エステルを合成する方法が報告されている。しかし、この方法ではホウ酸を化学量論的に用いるために廃液中のホウ素の処理が問題となる。 Non-Patent Documents 1 and 2 report a method of synthesizing a boric acid ester from boric acid and an aromatic alcohol and synthesizing a carboxylic acid ester of an aromatic alcohol by substituting the carboxylic acid. However, in this method, since boric acid is used stoichiometrically, the treatment of boron in the waste liquid becomes a problem.
特許文献８、９、非特許文献３には、脂肪族又は芳香族カルボン酸とフェノールを脱水エステル化で反応させる際に硫酸／ホウ酸コンプレックスを用いる例が報告されている。この方法ではある種のカルボン酸フェニルエステルについては９０％以上の収率で得られるものもある。しかし、反応温度が高く、反応時間も長時間を要するため、一般的なフェニルエステルの合成方法とは言い難い。 Patent Documents 8 and 9 and Non-Patent Document 3 report examples in which a sulfuric acid / boric acid complex is used when an aliphatic or aromatic carboxylic acid is reacted with phenol by dehydration esterification. In this method, some carboxylic acid phenyl esters are obtained in a yield of 90% or more. However, since the reaction temperature is high and the reaction time is long, it is difficult to say that it is a general phenyl ester synthesis method.
酸以外の触媒として、特許文献１０には錫化合物、特許文献１１には鉛化合物、特許文献１２には錫化合物と鉛化合物を混合した触媒でフェニルエステルを合成する方法が開示されている。しかし、何れも収率は満足なレベルに達していない。 As catalysts other than acids, Patent Document 10 discloses a tin compound, Patent Document 11 discloses a lead compound, and Patent Document 12 discloses a method of synthesizing a phenyl ester using a catalyst in which a tin compound and a lead compound are mixed. However, none of the yields has reached a satisfactory level.
最近、特許文献１３に加水分解可能な４価のジルコニウム化合物及び／又は４価のハフニウム化合物と、スルホン酸、ヘテロポリ酸及び超強酸のうちのいずれか１種以上の酸性化合物とを触媒として併用することを特徴とする芳香族エステル化合物の製造方法が開示されている。また、特許文献１４にはヘテロポリ酸担持体又はヘテロポリ酸塩担持体であることを特徴とするフェノール類のエステル化方法が開示されている。さらに、特許文献１５には超強酸及び／又はヘテロポリ酸及び／又はヘテロポリ酸塩と、ボロン酸及び／又はボロン酸エステル及び／又は酸化ホウ素からなる触媒を用いるフェノール類のエステル化方法が開示されている。しかし、これらの方法は何れも収率が低く工業的なエステル化方法とは言い難い。 Recently, Patent Document 13 uses a hydrolyzable tetravalent zirconium compound and / or a tetravalent hafnium compound and any one or more acidic compounds of sulfonic acid, heteropolyacid and super strong acid as a catalyst. The manufacturing method of the aromatic ester compound characterized by this is disclosed. Patent Document 14 discloses a method for esterifying phenols, which is a heteropolyacid carrier or a heteropolyacid salt carrier. Further, Patent Document 15 discloses a method for esterifying phenols using a catalyst comprising a super strong acid and / or heteropoly acid and / or heteropoly acid salt and a boronic acid and / or boronic acid ester and / or boron oxide. Yes. However, none of these methods is an industrial esterification method with a low yield.
本発明は、フェノールと特定のカルボン酸からエステル化反応により収率良くフェニルエステルを製造する方法を提供することを目的とする。 An object of this invention is to provide the method of manufacturing a phenyl ester from a phenol and specific carboxylic acid with a sufficient yield by esterification reaction.
本発明に係るフェニルエステルの製造方法は、
水と共沸する溶剤中で、フェノールと下記一般式（Ｉ）
The method for producing a phenyl ester according to the present invention includes:
In a solvent azeotropic with water, phenol and the following general formula (I)
（式Ｉ中、Ｒ1は水素又はメチル基を表す）
で示されるカルボン酸とを酸触媒によりエステル化するフェニルエステルの製造方法であって、
前記エステル化反応の反応系内に、ホウ酸及び下記一般式（ＩＩ）
(In formula I, R 1 represents hydrogen or a methyl group)
A process for producing a phenyl ester, which is esterified with an acid catalyst,
In the reaction system of the esterification reaction, boric acid and the following general formula (II)
（式ＩＩ中、Ｒ2又はＲ3は直鎖又は分岐状の炭素数２〜１０のアルキル基を表す）
で示される２，２−ジアルキルマロン酸をそれぞれ前記一般式（Ｉ）で示されるカルボン酸に対して２〜５０モル％加えることを特徴とする。
(In Formula II, R 2 or R 3 represents a linear or branched alkyl group having 2 to 10 carbon atoms)
2 to 50 mol% of the 2,2-dialkylmalonic acid represented by the formula (I) is added to the carboxylic acid represented by the general formula (I).
本発明によれば、前記一般式（Ｉ）で示されるカルボン酸のフェニルエステルを収率良く製造することができる。 According to the present invention, the phenyl ester of the carboxylic acid represented by the general formula (I) can be produced with high yield.
本発明者らは、フェノールとカルボン酸から安価なエステル化という手法を用いてフェニルエステルを効率良く製造する方法について鋭意検討を行い、その過程で特許文献８に開示されたホウ酸硫酸コンプレックスを触媒として芳香族エステルを合成する方法に関して考察を行った。その結果、ホウ酸を用いるエステル化反応の機構は、ホウ酸とカルボン酸が硫酸触媒で無水物となり、その酸無水物が芳香族アルコール類と反応してエステルが合成され、使用されたカルボン酸を補うためにフリーのカルボン酸が以下のようにホウ酸と反応すると仮定した。 The present inventors diligently studied a method for efficiently producing a phenyl ester from a phenol and a carboxylic acid by using a method of inexpensive esterification, and in the process, the boric acid-sulfuric acid complex disclosed in Patent Document 8 was catalyzed. The method for synthesizing aromatic esters was discussed. As a result, the mechanism of the esterification reaction using boric acid is that boric acid and carboxylic acid are converted into anhydrides with a sulfuric acid catalyst, and the acid anhydride reacts with aromatic alcohols to synthesize esters, and the carboxylic acid used. It was assumed that free carboxylic acid would react with boric acid as follows:
この仮定に従って、計算化学の手法を用いて反応中間体のエネルギー状態、活性化エネルギーを計算すると、ホウ酸をそのまま用いる方法では活性化エネルギーが大きく、原料系に比べて反応系のエネルギー状態が高いため収率を上げるのは困難であることが判明した。 According to this assumption, when the energy state and activation energy of the reaction intermediate are calculated using the computational chemistry method, the activation energy is large in the method using boric acid as it is, and the energy state of the reaction system is higher than the raw material system. Therefore, it was proved difficult to increase the yield.
そこで、フェニルエステルを効率良く得るためにホウ酸とカルボン酸の中間体モデルに関して詳細な量子化学計算を用いた検討を行った。その結果、ホウ酸の一部をエステル化反応に関与しにくいカルボン酸類で環状酸無水物の形でブロックしたホウ酸誘導体を用いることにより、原料系より反応系のエネルギー状態が低くなり、更に中間体への活性化エネルギーもホウ酸単独を用いた系に比べると低くなることを見出し、本発明に至った。 Therefore, in order to obtain phenyl esters efficiently, we investigated the intermediate model of boric acid and carboxylic acid using detailed quantum chemical calculations. As a result, by using a boric acid derivative in which a part of boric acid is blocked in the form of a cyclic acid anhydride with a carboxylic acid that is not easily involved in the esterification reaction, the energy state of the reaction system is lower than that of the raw material system, and further It has been found that the activation energy to the body is lower than that of the system using boric acid alone, and the present invention has been achieved.
即ち、本発明に係るフェニルエステルの製造方法は、水と共沸する溶剤中で、フェノールと前記一般式（Ｉ）で示されるカルボン酸とを酸触媒によりエステル化するフェニルエステルの製造方法であって、前記エステル化の反応系内にホウ酸及び前記一般式（ＩＩ）で示される２，２−ジアルキルマロン酸をそれぞれ前記一般式（Ｉ）で示されるカルボン酸に対して２〜５０モル％加えることを特徴とする。 That is, the method for producing a phenyl ester according to the present invention is a method for producing a phenyl ester in which a phenol and a carboxylic acid represented by the general formula (I) are esterified with an acid catalyst in a solvent azeotropic with water. In the esterification reaction system, boric acid and the 2,2-dialkylmalonic acid represented by the general formula (II) are each 2 to 50 mol% based on the carboxylic acid represented by the general formula (I). It is characterized by adding.
以下、本発明について詳しく説明する。 The present invention will be described in detail below.
前記一般式（Ｉ）で示されるカルボン酸において、Ｒ1は水素又はメチル基を表す。 In the carboxylic acid represented by the general formula (I), R 1 represents hydrogen or a methyl group.
前記一般式（ＩＩ）で示される２，２−ジアルキルマロン酸において、Ｒ2又はＲ3は、直鎖又は分岐状の炭素数２〜１０のアルキル基を表す。直鎖又は分岐状の炭素数２〜１０のアルキル基としては、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基等が挙げられる。実用的に考えると、炭素数３〜５であることが好ましい。また、Ｒ2又はＲ3としては分岐アルキル基が好ましい。Ｒ2又はＲ3が分岐アルキル基である場合に、２，２−ジアルキルマロン酸でブロック化されたホウ酸誘導体が加水分解されにくく、触媒としての中間体の安定性が良好となる傾向にある。分岐アルキル鎖としては、イソプロピル基、イソブチル基がより好ましい。 In the 2,2-dialkylmalonic acid represented by the general formula (II), R 2 or R 3 represents a linear or branched alkyl group having 2 to 10 carbon atoms. Examples of the linear or branched alkyl group having 2 to 10 carbon atoms include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, octyl group, nonyl group, decyl group, etc. Is mentioned. Considering practically, it is preferable that it is C3-C5. R 2 or R 3 is preferably a branched alkyl group. When R 2 or R 3 is a branched alkyl group, the boric acid derivative blocked with 2,2-dialkylmalonic acid is difficult to be hydrolyzed, and the stability of the intermediate as a catalyst tends to be good. . As the branched alkyl chain, an isopropyl group and an isobutyl group are more preferable.
また、Ｒ2又はＲ3は同じ基であってもよく、異なる基であってもよい。２，２−ジアルキルマロン酸の合成の面からは、Ｒ2又はＲ3は同じ基であることが好ましい。 R 2 or R 3 may be the same group or different groups. From the viewpoint of the synthesis of 2,2-dialkylmalonic acid, R 2 or R 3 are preferably the same group.
前記溶剤としては、水と共沸し得る溶剤であれば何れの溶剤も使用可能である。しかし、フェニルエステルを製造するには反応温度を１００℃以上にすることが好ましいため、加圧系反応器を用いるのでなければ一般的には共沸点が高い方が好ましい。例えば、トルエン、キシレン、エチルベンゼン、クメンなど芳香族系溶剤を使用することが好ましい。コスト面で考えると、トルエン、キシレンがより好ましい。 As the solvent, any solvent can be used as long as it can be azeotroped with water. However, since it is preferable to set the reaction temperature to 100 ° C. or higher for producing the phenyl ester, generally a higher azeotropic point is preferable unless a pressurized reactor is used. For example, it is preferable to use an aromatic solvent such as toluene, xylene, ethylbenzene or cumene. From the viewpoint of cost, toluene and xylene are more preferable.
前記酸触媒としては、エステル化反応に使用できる酸であれば何れの酸を用いても良いが、フェノールのエステル化に用いるのは硫酸、強酸性イオン交換樹脂が好ましい。酸触媒の使用量は、前記一般式（Ｉ）で示されるカルボン酸に対して、０．１〜２０モル％の間で任意に設定できる。しかし、少なすぎると反応時間が長くなり、多すぎると副反応が多くなるため、１〜１０モル％が好ましく、３〜７モル％がより好ましい。 As the acid catalyst, any acid may be used as long as it can be used for the esterification reaction. However, sulfuric acid and strong acid ion exchange resin are preferable for the esterification of phenol. The usage-amount of an acid catalyst can be arbitrarily set between 0.1-20 mol% with respect to the carboxylic acid shown by the said general formula (I). However, if the amount is too small, the reaction time becomes long, and if the amount is too large, side reactions increase, so 1 to 10 mol% is preferable, and 3 to 7 mol% is more preferable.
本発明においては、前記エステル化の反応系内に前記一般式（ＩＩ）で示される２，２−ジアルキルマロン酸を前記一般式（Ｉ）で示されるカルボン酸に対して２〜５０モル％加える。２モル％未満では反応速度が遅くなるため副反応が起きる。一方、５０モル％をこえると、一般的に前記一般式（ＩＩ）で示される２，２−ジアルキルマロン酸は高価でありコストが高くなるため、２，２−ジアルキルマロン酸とホウ酸の無水物を回収するなどコストを下げる策を練る必要がある。しかし、斯様な工程を入れることは工程が複雑になりコスト高となる。好ましくは、３〜７モル％である。 In the present invention, 2,2-dialkylmalonic acid represented by the general formula (II) is added to the esterification reaction system in an amount of 2 to 50 mol% based on the carboxylic acid represented by the general formula (I). . If it is less than 2 mol%, the reaction rate becomes slow and side reactions occur. On the other hand, if the amount exceeds 50 mol%, 2,2-dialkylmalonic acid represented by the general formula (II) is generally expensive and expensive, so that anhydrous 2,2-dialkylmalonic acid and boric acid are anhydrous. It is necessary to devise measures to reduce costs, such as collecting things. However, adding such a process complicates the process and increases the cost. Preferably, it is 3-7 mol%.
また、本発明においては前記ホウ酸についても、前記エステル化の反応系内に前記一般式（Ｉ）で示されるカルボン酸に対して２〜５０モル％加える。２モル％未満では反応速度が遅くなるため副反応が起きる。一方、５０モル％をこえると、２，２−ジアルキルマロン酸とホウ酸の無水物を回収するなどコストを下げる策を練る必要がある。しかし、斯様な工程を入れることは工程が複雑になりコスト高となる。好ましくは、３〜７モル％である。 In the present invention, boric acid is also added in an amount of 2 to 50 mol% with respect to the carboxylic acid represented by the general formula (I) in the esterification reaction system. If it is less than 2 mol%, the reaction rate becomes slow and side reactions occur. On the other hand, if it exceeds 50 mol%, it is necessary to devise measures to reduce the cost, such as recovering 2,2-dialkylmalonic acid and boric anhydride. However, adding such a process complicates the process and increases the cost. Preferably, it is 3-7 mol%.
２，２−ジアルキルマロン酸とホウ酸は、上述したように、それぞれ２〜５０モル％の範囲内で使用すれば、いずれの割合で用いても本発明の効果は得られるが、等モルで用いることが好ましい。 As described above, if 2,2-dialkylmalonic acid and boric acid are used within the range of 2 to 50 mol%, the effects of the present invention can be obtained even if used in any proportion. It is preferable to use it.
前記フェノールの使用量は、前記一般式（Ｉ）で示されるカルボン酸に対して当量より多くても少なくても反応上は差し支えない。しかし、反応の効率、反応後の精製工程などを考えると、フェノールの量は前記一般式（Ｉ）で示されるカルボン酸の仕込み量に対して８０〜９９モル％の間であることが好ましく、８５モル％から９５モル％であることがより好ましい。 The amount of the phenol used may be more or less than the equivalent amount with respect to the carboxylic acid represented by the general formula (I). However, considering the efficiency of the reaction, the purification step after the reaction, etc., the amount of phenol is preferably between 80 and 99 mol% with respect to the charged amount of the carboxylic acid represented by the general formula (I), More preferably, it is 85 mol% to 95 mol%.
反応温度は、酸濃度にも依存するが、反応時間を１０〜２４時間程度に設定するには１００℃以上で実施するのが好ましい。反応温度が１００℃未満では反応速度が極端に遅くなり、実用的な反応条件とは言いがたい。しかし、前記一般式（Ｉ）のカルボン酸は高温で反応すると重合する可能性があるため、１４０℃以下でエステル化反応を行うことが好ましい。 Although the reaction temperature depends on the acid concentration, it is preferably carried out at 100 ° C. or higher in order to set the reaction time to about 10 to 24 hours. If the reaction temperature is less than 100 ° C., the reaction rate becomes extremely slow, which is not practical reaction conditions. However, since the carboxylic acid of the general formula (I) may be polymerized when reacted at a high temperature, it is preferable to perform the esterification reaction at 140 ° C. or lower.
前記一般式（Ｉ）で示されるカルボン酸や合成されるフェニルエステルの重合を防止するために、反応系内に重合防止剤を添加することが好ましい。重合防止剤の種類は特に限定されず、その１種類を用いても２種類以上を用いても良い。重合防止剤としては、例えば、ハイドロキノン、ｐ−メトキシフェノール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、ｔｅｒｔ−ブチル−カテコール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、ペンタエリスリトール、テトラキス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシヒドロシンナメイト）、２−ｓｅｃ−ブチル−４，６−ジニトロフェノールなどのフェノール系化合物、Ｎ，Ｎ−ジイソプロピルパラフェニレンジアミン、Ｎ，Ｎ−ジ−２−ナフチルパラフェニレンジアミン、Ｎ−フェニレン−Ｎ−（１，３−ジメチルブチル）パラフェニレンジアミン、Ｎ，Ｎ’−ビス（１，４−ジメチルフェニル）−パラフェニレンジアミン、Ｎ−（１，４−ジメチルフェニル）−Ｎ’−フェニル−パラフェニレンジアミンなどのアミン系化合物、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、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシル、ビス（１−オキシル−２，２，６，６−テトラメチルピペリジン−４−イル）セバケイトなどのＮ−オキシル系化合物、銅、塩化銅（ＩＩ）、塩化鉄（ＩＩＩ）などの金属化合物などが挙げられる。重合防止剤の使用量は、適宜決めれば良いが、使用する前記一般式（Ｉ）で示されるカルボン酸に対して１００ｐｐｍ以上が好ましく、十分な重合防止効果を得るには５００ｐｐｍ以上がより好ましい。一方、コスト面から考えると重合防止剤の使用量は、１００００ｐｐｍ以下であることが好ましく、製品の着色、使用場面での便宜性などを考えると、５０００ｐｐｍ以下であることがより好ましい。 In order to prevent polymerization of the carboxylic acid represented by the general formula (I) or the synthesized phenyl ester, it is preferable to add a polymerization inhibitor in the reaction system. The kind of polymerization inhibitor is not specifically limited, The 1 type may be used or 2 or more types may be used. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, tert-butyl-catechol, 2, Such as 6-di-tert-butyl-4-methylphenol, pentaerythritol, tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 2-sec-butyl-4,6-dinitrophenol Phenol compounds, N, N-diisopropylparaphenylenediamine, N, N-di-2-naphthylparaphenylenediamine, N-phenylene-N- (1,3-dimethylbutyl) paraphenylenediamine, N, N′-bis (1,4-Dimethylphenyl) -paraphenylenediamine, N- (1, Amine compounds such as -dimethylphenyl) -N'-phenyl-paraphenylenediamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6, N-oxyl compounds such as 6-tetramethylpiperidine-N-oxyl and bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, copper, copper (II) chloride, chloride Examples thereof include metal compounds such as iron (III). Although the usage-amount of a polymerization inhibitor should just be determined suitably, 100 ppm or more is preferable with respect to the carboxylic acid shown by the said general formula (I) to be used, and 500 ppm or more is more preferable in order to acquire sufficient polymerization prevention effect. On the other hand, from the viewpoint of cost, the amount of the polymerization inhibitor used is preferably 10,000 ppm or less, and more preferably 5000 ppm or less in consideration of product coloring, convenience in use, and the like.
また、重合を防止するためにエステル化反応液中に空気などの酸素含有ガスをバブリングすることも好ましい。導入する空気などの酸素含有ガスの量は、所望の重合防止効果が得られるように適時設定できる。例えば、酸素含有ガスとして空気を用いる場合、使用する前記一般式（Ｉ）で示されるカルボン酸１モルに対して０．５〜３．０ｍｌ／ｍｉｎでバブリングすることが好ましい。エステル化反応液に重合防止剤を添加し、併せて反応液中に空気などの酸素含有ガスを導入しながら反応を行うことは、重合防止効果の増幅という観点から特に好ましい。 It is also preferable to bubble an oxygen-containing gas such as air in the esterification reaction liquid in order to prevent polymerization. The amount of oxygen-containing gas such as air to be introduced can be set in a timely manner so as to obtain a desired polymerization preventing effect. For example, when air is used as the oxygen-containing gas, it is preferably bubbled at 0.5 to 3.0 ml / min with respect to 1 mol of the carboxylic acid represented by the general formula (I) used. It is particularly preferable to add a polymerization inhibitor to the esterification reaction liquid and perform the reaction while introducing an oxygen-containing gas such as air into the reaction liquid from the viewpoint of amplification of the polymerization prevention effect.
エステル化反応の後は、反応液をそのまま蒸留精製する、又は、反応液に水を加えて二相系にしてからフェニルエステルを抽出した後に蒸留して精製するなど、通常の後処理方法により処理することで精製フェニルエステルを得ることができる。 After the esterification reaction, the reaction solution is distilled and purified as it is, or the reaction solution is treated by a usual post-treatment method, such as adding water to the two-phase system and then extracting and purifying the phenyl ester. By doing so, a purified phenyl ester can be obtained.
以下、実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（実施例１）
ディーンスターク付きの四つ口フラスコにメタクリル酸０．２４モル、フェノール０．２０モルをキシレン１０モルに溶解して添加した。また、重合防止剤として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０．３ミリモル、ヒドロキノン０．４５ミリモルを添加した。さらに、エステル化触媒として硫酸０．０１モル、更に添加剤としてホウ酸０．０１モル、ジイソプロピルマロン酸０．０１モルを添加して、エアレーションしながらバス温を１４０℃まで昇温させた。反応温度を１３０℃に保つように反応系の減圧度をコントロールし、還流脱水しながら反応を行った。
Example 1
To a four-necked flask with Dean Stark, 0.24 mol of methacrylic acid and 0.20 mol of phenol were dissolved in 10 mol of xylene and added. Further, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl 0.3 mmol and hydroquinone 0.45 mmol were added as polymerization inhibitors. Furthermore, 0.01 mol of sulfuric acid was added as an esterification catalyst, 0.01 mol of boric acid and 0.01 mol of diisopropylmalonic acid were added as additives, and the bath temperature was raised to 140 ° C. while aeration. The reaction was carried out while controlling the degree of vacuum of the reaction system so as to keep the reaction temperature at 130 ° C. and refluxing dehydration.
生成物の分析は、ＧＬＣ（ＧＣ、ガスクロマトグラフィー）でメタクリル酸、フェノール、フェニルメタクリレートのピーク面積を測定し、便宜的に、転化率＝１００×（フェニルメタクリレートの面積）／（フェノールの面積＋フェニルメタクリレートの面積）（％）で算出した。 For analysis of the product, the peak areas of methacrylic acid, phenol, and phenyl methacrylate were measured by GLC (GC, gas chromatography). For convenience, conversion rate = 100 × (area of phenyl methacrylate) / (area of phenol + It was calculated by the area (%) of phenyl methacrylate.
ＧＬＣの分析条件は以下の通りである。
カラム ＤＢ−１×３０ｍ
キャリアガス ヘリウム
検出器 ＦＩＤ
カラム温度 ５０℃×５分、昇温１０℃／分、２２０℃×１０分
注入口温度 ２５０℃
検出器温度 ２５０℃。
The analysis conditions of GLC are as follows.
Column DB-1 × 30m
Carrier gas Helium detector FID
Column temperature 50 ° C. × 5 minutes, temperature increase 10 ° C./minute, 220 ° C. × 10 minutes inlet temperature 250 ° C.
Detector temperature 250 ° C.
１７時間の反応で、転化率は８５％に達した。 The conversion reached 85% after 17 hours of reaction.
（比較例１）
前記エステル化触媒として硫酸０．０１５モル、添加剤としてホウ酸０．０１５モルを添加し、ジイソプロピルマロン酸を添加しなかったこと以外は、実施例１と同様に行った。９時間の反応で転化率は７５％であった。
(Comparative Example 1)
The same procedure as in Example 1 was conducted except that 0.015 mol of sulfuric acid was added as the esterification catalyst, 0.015 mol of boric acid was added as an additive, and diisopropylmalonic acid was not added. The conversion was 75% after 9 hours of reaction.
（比較例２）
前記添加剤としてホウ酸０．００４モルを添加し、ジイソプロピルマロン酸を添加しなかったこと以外は、実施例１と同様に行った。１７時間の反応で転化率は６４％であった。
(Comparative Example 2)
The same procedure as in Example 1 was performed except that 0.004 mol of boric acid was added as the additive and diisopropylmalonic acid was not added. The conversion for 17 hours was 64%.
（実施例２）
前記ジイソプロピルマロン酸０．０１モルに代えて、ジエチルマロン酸０．０１モルを添加したこと以外は、実施例１と同様に行った。１８時間の反応で、転化率は８３％に達した。
(Example 2)
The same procedure as in Example 1 was performed except that 0.01 mol of diethylmalonic acid was added instead of 0.01 mol of diisopropylmalonic acid. After 18 hours of reaction, the conversion reached 83%.
（実施例３）
前記ジイソプロピルマロン酸０．０１モルに代えて、ジヘキシルマロン酸０．０１モルを添加したこと以外は、実施例１と同様に行った。１７時間の反応で、転化率は８０％に達した。
(Example 3)
The same procedure as in Example 1 was performed except that 0.01 mol of dihexylmalonic acid was added instead of 0.01 mol of diisopropylmalonic acid. The conversion reached 80% after 17 hours of reaction.
（実施例４）
前記メタクリル酸０．２４モルに代えて、アクリル酸０．２４モルを添加し、バス温を１３０℃まで昇温させ、反応温度を１２０℃に保つように反応系の減圧度をコントロールし、還流脱水しながら反応を行ったこと以外は、実施例１と同様に行った。１８時間の反応で、転化率は８０％に達した。
Example 4
Instead of 0.24 mol of methacrylic acid, 0.24 mol of acrylic acid was added, the bath temperature was raised to 130 ° C., and the pressure reduction of the reaction system was controlled to maintain the reaction temperature at 120 ° C. The reaction was performed in the same manner as in Example 1 except that the reaction was performed while dehydrating. The conversion reached 80% after 18 hours of reaction.
（比較例３）
前記添加剤としてホウ酸０．００２モルを添加し、ジイソプロピルマロン酸０．００２モルを添加したこと以外は、実施例１と同様に行った。１９時間の反応で転化率は６５％であった。
(Comparative Example 3)
The same procedure as in Example 1 was performed except that 0.002 mol of boric acid was added as the additive and 0.002 mol of diisopropylmalonic acid was added. The conversion for 19 hours was 65%.
前記実施例及び比較例の結果を表１に示す。 The results of the examples and comparative examples are shown in Table 1.
Claims (1)
で示されるカルボン酸とを酸触媒によりエステル化するフェニルエステルの製造方法であって、
前記エステル化反応の反応系内に、ホウ酸及び下記一般式（ＩＩ）
で示される２，２−ジアルキルマロン酸をそれぞれ前記一般式（Ｉ）で示されるカルボン酸に対して２〜５０モル％加えることを特徴とするフェニルエステルの製造方法。 In a solvent azeotropic with water, phenol and the following general formula (I)
A process for producing a phenyl ester, which is esterified with an acid catalyst,
In the reaction system of the esterification reaction, boric acid and the following general formula (II)
A method for producing a phenyl ester, wherein 2 to 50 mol% of a 2,2-dialkylmalonic acid represented by the formula (I) is added to the carboxylic acid represented by the general formula (I).
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| WO2015064498A1 (en) | 2013-10-30 | 2015-05-07 | 三菱レイヨン株式会社 | Phenyl(meta)acrylate production method and phenyl(meta)acrylate composition |
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| KR20160135275A (en) | 2014-06-12 | 2016-11-25 | 미쯔비시 레이온 가부시끼가이샤 | (meth)acrylic acid ester manufacturing method and aromatic carboxylic acid ester manufacturing method |
| US9796652B2 (en) | 2014-06-12 | 2017-10-24 | Mitsubishi Chemical Corporation | Method for manufacturing (meth) acrylic acid ester and method for manufacturing aromatic carboxylic acid ester |
| WO2022163360A1 (en) | 2021-01-27 | 2022-08-04 | 三菱瓦斯化学株式会社 | Method for producing (meth)acyrlic acid ester compound |
| KR20230133876A (en) | 2021-01-27 | 2023-09-19 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method for producing (meth)acrylic acid ester compound |
| KR20240136237A (en) | 2023-03-06 | 2024-09-13 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Method of producing vinyl resin |
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