JPS63218653A - Production of diaryl sulfones - Google Patents
Production of diaryl sulfonesInfo
- Publication number
- JPS63218653A JPS63218653A JP62053740A JP5374087A JPS63218653A JP S63218653 A JPS63218653 A JP S63218653A JP 62053740 A JP62053740 A JP 62053740A JP 5374087 A JP5374087 A JP 5374087A JP S63218653 A JPS63218653 A JP S63218653A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- catalyst
- aromatic sulfonic
- sulfonic acid
- aromatic
- 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.)
- Granted
Links
- -1 diaryl sulfones Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 5
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 7
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 abstract description 9
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract description 8
- 229940092714 benzenesulfonic acid Drugs 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 10
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 1
- YTCDCQWZOGUBQQ-UHFFFAOYSA-N 2,3-dibromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(Br)=C1Br YTCDCQWZOGUBQQ-UHFFFAOYSA-N 0.000 description 1
- ZGZXYZZHXXTTJN-UHFFFAOYSA-N 2,3-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(Cl)=C1Cl ZGZXYZZHXXTTJN-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- JIFAWAXKXDTUHW-UHFFFAOYSA-N 2-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1F JIFAWAXKXDTUHW-UHFFFAOYSA-N 0.000 description 1
- SGBQUMZTGSQNAO-UHFFFAOYSA-N 2-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(O)=CC=C21 SGBQUMZTGSQNAO-UHFFFAOYSA-N 0.000 description 1
- ZJTNYBYLBTVLRD-UHFFFAOYSA-N 2-iodobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1I ZJTNYBYLBTVLRD-UHFFFAOYSA-N 0.000 description 1
- FQBAMYDJEQUGNV-UHFFFAOYSA-N 2-methoxybenzenesulfonic acid Chemical compound COC1=CC=CC=C1S(O)(=O)=O FQBAMYDJEQUGNV-UHFFFAOYSA-N 0.000 description 1
- WRZDSZXJYGDDBE-UHFFFAOYSA-N 2-phenoxybenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1OC1=CC=CC=C1 WRZDSZXJYGDDBE-UHFFFAOYSA-N 0.000 description 1
- RIOSJKSGNLGONI-UHFFFAOYSA-N 2-phenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C1=CC=CC=C1 RIOSJKSGNLGONI-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- ZGHKRWVZYZMUOS-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)O.[Br] Chemical compound C1(=CC=CC=C1)S(=O)(=O)O.[Br] ZGHKRWVZYZMUOS-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—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)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、ジアリールスルホン類の改良された製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved method for producing diarylsulfones.
本発明により得られるジアリールスルホン類は、ポリエ
ステル、ポリアミド、ポリイミド、ポリスルホン等の耐
熱性樹脂の原料又は原料中間体として有用な化合物であ
る。The diarylsulfones obtained by the present invention are useful compounds as raw materials or raw material intermediates for heat-resistant resins such as polyesters, polyamides, polyimides, and polysulfones.
[従来の技術]
ジアリールスルホン類の製造方法として、これまでに芳
香族化合物と硫酸とから芳香族スルホン酸を合成し、こ
の芳香族スルホン酸と芳香族化合物とを五酸化リン等の
脱水剤を用いて反応させる方法が提案されている(米国
特許第3,501゜532号、米国特許第3,729,
517号、特開昭60−92256@)。[Prior art] As a method for producing diarylsulfones, aromatic sulfonic acid is synthesized from an aromatic compound and sulfuric acid, and the aromatic sulfonic acid and aromatic compound are mixed with a dehydrating agent such as phosphorus pentoxide. (U.S. Pat. No. 3,501゜532, U.S. Pat. No. 3,729,
No. 517, JP-A-60-92256@).
しかし、この方法において脱水剤の使用量が触媒聞では
ジアリールスルホン類の収率が高々30%と低く、収率
を向上させるためには更に多量の脱水剤を使用する必要
がある。このため大量のリン酸を含む廃水の処理を必要
とし、工業上のみならず環境上も好ましくない。However, in this method, if the amount of dehydrating agent used is catalytic, the yield of diarylsulfones is as low as 30% at most, and in order to improve the yield, it is necessary to use a larger amount of dehydrating agent. Therefore, it is necessary to treat a large amount of wastewater containing phosphoric acid, which is unfavorable not only industrially but also environmentally.
又、上記の脱水剤は一般に高価なため、経済的にも不利
となる。Furthermore, since the above-mentioned dehydrating agents are generally expensive, they are economically disadvantageous.
一方、本発明者らはジアリールスルホン類の製造方法に
ついて検討するなかで、タングステン酸、モリブデン酸
及びそれらのヘテロポリ酸が優れた触媒効果を有するこ
とを見い出し、先に提案したところである(特願昭61
−168597号、特願昭61−213368号)。On the other hand, while studying methods for producing diarylsulfones, the present inventors discovered that tungstic acid, molybdic acid, and their heteropolyacids have excellent catalytic effects, and have previously proposed this (patent application 61
-168597, Japanese Patent Application No. 61-213368).
当該製造方法は、含リン廃水を出さず経済的にも有利で
あるが、引続く検討の中で、特にベンゼン、クロルベン
ゼン等のアルキル置換基をもたない芳香族化合物を原料
とする場合には反応が完結するまでに長時間を要する等
、尚、改善の余地が認められた。This production method does not produce phosphorus-containing wastewater and is economically advantageous, but in subsequent studies, we found that it is difficult to use aromatic compounds that do not have alkyl substituents, such as benzene and chlorobenzene, as raw materials. However, there was still room for improvement, such as the fact that it took a long time for the reaction to complete.
[発明が解決しようとする問題点]
本発明者らは、芳香族スルホン酸と芳香族化合物とを反
応させ、安価に高収率でジアリールスルホン類を生産す
る方法を確立すべく鋭意検討した結果、脱水剤を反応初
期から添加せずに、一定反応が進行した段階において添
加すれば、必要とする脱水剤の量を大幅に低減できるこ
とを見い出し、この知見に基づいて本発明を完成するに
至った。[Problems to be Solved by the Invention] The present inventors have conducted intensive studies to establish a method for producing diarylsulfones at low cost and in high yield by reacting aromatic sulfonic acids with aromatic compounds. discovered that the amount of dehydrating agent required could be significantly reduced if the dehydrating agent was not added from the initial stage of the reaction, but was added at a stage when the reaction had progressed to a certain extent, and based on this knowledge, the present invention was completed. Ta.
即ち、本発明は、ジアリールスルホン類の改良された製
造方法を提供することを目的とする。That is, an object of the present invention is to provide an improved method for producing diarylsulfones.
[問題点を解決するための手段]
本発明は、芳香族化合物と芳香族スルホン酸とを触媒の
存在下又は非存在下に反応させてジアリールスルホン類
を製造する方法において、芳香族スルホン酸の転化率が
40〜95%の時点で、原料の芳香族スルホン酸に対し
、リン酸換算で0゜025〜0.5倍モル量のリン酸化
物及び/又は縮合リンM(以下、「リン系化合物」と称
する。)を添加することを特徴とする。[Means for Solving the Problems] The present invention provides a method for producing diarylsulfones by reacting an aromatic compound and an aromatic sulfonic acid in the presence or absence of a catalyst. When the conversion rate is 40 to 95%, 0.025 to 0.5 times the molar amount of phosphorus oxide and/or condensed phosphorus M (hereinafter referred to as "phosphorus-based It is characterized by the addition of a chemical compound (referred to as "compound").
本発明方法において用いられる芳香族化合物としては、
ベンゼン、ナフタレン、及びそれらのアルキル基(炭素
数1〜20)、フェニル基、ヒドロキシル基、アルコキ
シ基、フェノキシ基又はハロゲン原子による各置換体が
例示され、具体的には、ベンゼン、トルエン、エチルベ
ンゼン、ドデシルベンゼン、フェノール、ビフェニル、
アニソール、ジフェニルエーテル、キシレン、トリメチ
ルベンゼン、β−ハロエチルベンゼン、ナフタレン、メ
チルナフタレン、ナフトール、フルオロベンゼン、クロ
ルベンゼン、ブロムベンゼン、ヨードベンゼン等が掲げ
られる。Aromatic compounds used in the method of the present invention include:
Benzene, naphthalene, and substituted products thereof with alkyl groups (1 to 20 carbon atoms), phenyl groups, hydroxyl groups, alkoxy groups, phenoxy groups, or halogen atoms are exemplified, and specifically, benzene, toluene, ethylbenzene, dodecylbenzene, phenol, biphenyl,
Examples include anisole, diphenyl ether, xylene, trimethylbenzene, β-haloethylbenzene, naphthalene, methylnaphthalene, naphthol, fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene.
本発明方法において用いられる芳香族スルホン酸は、上
記芳香族化合物を硫酸等に例示されるスルホン化剤によ
りスルホン化して得られるモノスルホン化物であって、
具体的には、ベンゼンスルホン酸、トルエンスルホン酸
、エチルベンゼンスルホン酸、β−ハロエチルベンゼン
スルホン酸、ドデシルベンゼンスルホン酸、ヒドロキシ
ベンゼンスルホン酸、フェニルベンゼンスルホン酸、フ
ルオロベンゼンスルホン酸、クロルベンゼンスルホン酸
、ブロムベンゼンスルホン酸、ヨードベンゼンスルホン
酸、ニトロベンゼンスルホン酸、メトキシベンゼンスル
ホン酸、フェノキシベンゼンスルホン酸、キシレンスル
ホン酸、ジクロルベンゼンスルホン酸、ジブロモベンゼ
ンスルホン酸、トリメデルベンゼンスルホン酸、ナフタ
レンスルホン酸、メチルナフタレンスルホン酸、ヒドロ
キシナフタレンスルホン酸、4,4°−ジフェニルジス
ルホン酸、4,4゛−ジフェニルエーテルジスルホン酸
等が例示される。The aromatic sulfonic acid used in the method of the present invention is a monosulfonated product obtained by sulfonating the above-mentioned aromatic compound with a sulfonating agent such as sulfuric acid, and
Specifically, benzenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, β-haloethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, hydroxybenzenesulfonic acid, phenylbenzenesulfonic acid, fluorobenzenesulfonic acid, chlorobenzenesulfonic acid, bromine Benzenesulfonic acid, iodobenzenesulfonic acid, nitrobenzenesulfonic acid, methoxybenzenesulfonic acid, phenoxybenzenesulfonic acid, xylene sulfonic acid, dichlorobenzenesulfonic acid, dibromobenzenesulfonic acid, trimedelbenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalene Examples include sulfonic acid, hydroxynaphthalenesulfonic acid, 4,4°-diphenyldisulfonic acid, and 4,4′-diphenyl ether disulfonic acid.
但し、芳香族化合物及び芳香族スルホン酸は上記例示に
限定されるものではない。However, the aromatic compounds and aromatic sulfonic acids are not limited to the above examples.
芳香族化合物を硫酸等によりスルホン化してモノスルホ
ン化物を得、引き続き脱水反応してジアリールスルホン
類を製造する場合にはスルホン基の両端に同一のアリー
ル基を有する対称型のスルホン類が得られ、又、予め調
製した芳香族スルホン酸と芳香族化合物とを脱水反応す
る方法にあっては、芳香族化合物を適宜選択することに
より非対称型のスルホン類を得ることができ、本発明は
上記いずれの方法においても適用できる。When an aromatic compound is sulfonated with sulfuric acid or the like to obtain a monosulfonated product, followed by a dehydration reaction to produce diarylsulfones, symmetrical sulfones having the same aryl group at both ends of the sulfone group are obtained. In addition, in the method of dehydrating a pre-prepared aromatic sulfonic acid and an aromatic compound, asymmetric sulfones can be obtained by appropriately selecting the aromatic compound, and the present invention is applicable to any of the above methods. It can also be applied to methods.
リン酸化物としては、例えば五酸化リン、三二酸化リン
等が挙げられ、縮合リン酸としては、メタリン酸、ピロ
リン酸、トリポリリン酸及びポリリン酸等が例示される
。Examples of phosphoric oxides include phosphorus pentoxide and phosphorus sesquioxide, and examples of condensed phosphoric acids include metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and polyphosphoric acid.
本発明方法に係るリン系化合物の添加量は、具体的には
原料の芳香族スルホン酸に対し、リン酸換算で0.02
5〜0.5倍モルが好ましい。これより少ないと収率が
低く、多いと廃水を処理する上での負担が大きく、又、
経済的にも不利となる。Specifically, the amount of the phosphorus-based compound added in the method of the present invention is 0.02 in terms of phosphoric acid based on the raw material aromatic sulfonic acid.
5 to 0.5 times the mole is preferable. If it is less than this, the yield will be low, if it is more than this, the burden of treating wastewater will be large, and
It is also economically disadvantageous.
リン系化合物の添加は、芳香族スルホン酸の転化率が4
0〜95%の時点がなされることが好ましい。The addition of phosphorus compounds increases the conversion rate of aromatic sulfonic acids to 4.
Preferably, a time point between 0 and 95% is taken.
上記時点は反応条件により適宜選択され、具体的には、
触媒の存在下に反応を進行させる場合には芳香族スルホ
ン酸の転化率が70〜95%の時点で、又、触媒を用い
ない場合には40〜70%の時点で夫々所定量のリン系
化合物を添加することが望ましい。これより低い転化率
において添加した場合には目的物の収率が低くなる傾向
にあり、又、より高い転化率にあっては反応時間が長く
なって工業上不利となる。The above time points are appropriately selected depending on the reaction conditions, and specifically,
When the reaction proceeds in the presence of a catalyst, a predetermined amount of phosphorus is added when the conversion rate of aromatic sulfonic acid is 70 to 95%, and when the conversion rate is 40 to 70% when no catalyst is used. It is desirable to add compounds. When added at a conversion rate lower than this, the yield of the target product tends to be low, and at a higher conversion rate, the reaction time becomes longer, which is industrially disadvantageous.
本発明に係る製造方法は無触媒であっても適用できるも
のの、触媒を使用すれば収率及び生産性を高めることが
でき、工業的に有利でおる。Although the production method according to the present invention can be applied without a catalyst, the use of a catalyst can increase the yield and productivity, which is industrially advantageous.
触媒としては、例えばタングステン酸、モリブデン酸、
あるいはこれらのヘテロポリ酸が掲げられる。ここにい
うヘテロポリ酸とは、2種以上の酸素酸からなる縮合酸
である。Examples of catalysts include tungstic acid, molybdic acid,
Alternatively, these heteropolyacids can be mentioned. The heteropolyacid referred to herein is a condensed acid consisting of two or more types of oxyacids.
ポリ酸原子としては、W及びMOであり、ヘテロ原子と
しては、例えばタングステン酸のヘテロポリ酸における
ヘテロ原子としては、P、AS。Examples of polyacid atoms include W and MO, and examples of heteroatoms in heteropolyacids such as tungstic acid include P and AS.
Si、Ti、Co、Fe、B、V、Be、■、N’ s
G a等が例示される。Si, Ti, Co, Fe, B, V, Be, ■, N's
Examples include G a and the like.
又、モリブデン酸のヘテロポリ酸におけるヘテロ原子と
しては、PSAs、Si、Ge、Ti。Further, examples of the heteroatom in the heteropolyacid of molybdic acid include PSAs, Si, Ge, and Ti.
Ce、Th、Mn、N i 、Te、I 、Co、Cr
、Fe、 Ga等が例示される。Ce, Th, Mn, Ni, Te, I, Co, Cr
, Fe, Ga, etc.
上記の例示した触媒は、東独で使用しても2種以上を併
用してもよい。The catalysts exemplified above may be used in East Germany or two or more thereof may be used in combination.
好ましいヘテロポリ酸として12−タンゲス1〜リン酸
、12−タングストケイ酸、12−モリブドリン酸等が
例示される。Examples of preferred heteropolyacids include 12-tunges 1-phosphoric acid, 12-tungstosilicic acid, and 12-molybdophosphoric acid.
触媒の使用量は触媒の種類により異なるものの、触媒活
性が発揮されるのに有効な但である限り特に限定はされ
ない。しかし、反応速度及び経済性の観点からは、原料
の芳香族スルホン酸1ooi量部に対して0.01〜3
0重量部程度置部ましくは0.1〜10重量部重量部首
利C必る。The amount of catalyst used varies depending on the type of catalyst, but is not particularly limited as long as it is effective for exhibiting catalytic activity. However, from the viewpoint of reaction rate and economic efficiency, 0.01 to 3 parts per 100 parts of aromatic sulfonic acid as the raw material
It must be about 0 parts by weight or 0.1 to 10 parts by weight.
本発明に係る製造方法は、一般に次の如くして行なわれ
る。The manufacturing method according to the present invention is generally carried out as follows.
芳香族化合物とWIt酸、又は芳香族化合物と芳香族ス
ルホン酸、並びに好ましくは触媒が夫々所定量存在する
系において、所定の温度条件下で、生成する水を除去し
ながら反応を進行する。In a system in which an aromatic compound and a WIt acid, or an aromatic compound and an aromatic sulfonic acid, and preferably a catalyst are present in predetermined amounts, the reaction proceeds under predetermined temperature conditions while removing produced water.
芳香族スルホン酸が所定の転化率に到達した段階で所定
量のリン系化合物を添加し、反応を完結させる。When the aromatic sulfonic acid reaches a predetermined conversion rate, a predetermined amount of a phosphorus compound is added to complete the reaction.
反応により生成する水を除去する方法としては、具体的
には、芳香族化合物を還流し共沸する水を相分離する方
法、窒素ガス等のキャリヤーガスを反応液に導入する方
法、減圧下に反応する方法等が例示できる。Specifically, methods for removing the water produced by the reaction include a method of refluxing the aromatic compound and phase separation of the azeotropic water, a method of introducing a carrier gas such as nitrogen gas into the reaction solution, a method of introducing a carrier gas such as nitrogen gas into the reaction liquid, and a method of removing the water under reduced pressure. Examples include methods of reaction.
芳香族化合物の使用量は、硫酸を原料とする場合には硫
酸に対して2.0〜40倍モル量、芳香族スルホン酸を
原料とする場合には芳香族スルホン酸に対して1.0〜
20倍モル量が適している。The amount of aromatic compound used is 2.0 to 40 times the molar amount of sulfuric acid when sulfuric acid is used as a raw material, and 1.0 times the molar amount of aromatic sulfonic acid when aromatic sulfonic acid is used as a raw material. ~
A 20-fold molar amount is suitable.
芳香族化合物が上記の範囲以下ではジアリールスルホン
類の収率が低く、逆に範囲を越えて使用しても特に利点
は認められず、経済的に不利である。If the amount of the aromatic compound is below the above range, the yield of diarylsulfones will be low, and on the other hand, if it is used beyond the range, no particular advantage will be recognized and it will be economically disadvantageous.
反応温度は、芳香族スルホン酸及び芳香族化合物の種類
、所望する反応時間等により適宜選択できるが、通常6
0〜280℃、好ましくは100〜230℃である。反
応温度が60℃以下では実用的な反応速度が得られにく
く、280℃以上では重合等の副反応が起こり、ジアリ
ールスルホン類の収率が低下する傾向にある。The reaction temperature can be appropriately selected depending on the type of aromatic sulfonic acid and aromatic compound, the desired reaction time, etc.
The temperature is 0 to 280°C, preferably 100 to 230°C. If the reaction temperature is 60°C or lower, it is difficult to obtain a practical reaction rate, and if the reaction temperature is 280°C or higher, side reactions such as polymerization occur, and the yield of diarylsulfones tends to decrease.
リン系化合物を添加後、1〜10時間でスルホン化は完
結する。Sulfonation is completed in 1 to 10 hours after adding the phosphorus compound.
このようにして得られた反応液を必要に応じて当該反応
の、原料である芳香族化合物又は低級アルコール、エー
テル、ケl〜ン等の有機溶剤で希釈し、触媒を濾別した
債、母液を冷却して晶析させるか、あるいは母液から希
釈媒体を留去してジアリールスルホン類を得る。上記工
程においては必要に応じて水洗してもよく、その順序は
問わない。回収した触媒及び希釈媒体等は、そのまま再
使用が可能である。The reaction solution thus obtained is diluted with an aromatic compound as a raw material for the reaction or an organic solvent such as a lower alcohol, ether, or cologne as necessary, and the catalyst is filtered off. The diarylsulfones are obtained either by cooling and crystallizing or by distilling off the diluting medium from the mother liquor. In the above steps, washing with water may be performed as necessary, and the order is not limited. The recovered catalyst, diluent medium, etc. can be reused as they are.
又、メタノール、エタノール等の脂肪族低級アルコール
、トルエン、キシレン等の芳香族化合物により再結晶す
ることにより更に高純度のジアリールスルホン類が得ら
れる。Moreover, even higher purity diarylsulfones can be obtained by recrystallizing with an aliphatic lower alcohol such as methanol or ethanol, or an aromatic compound such as toluene or xylene.
[実 施 例コ
以下、実施例及び比較例を掲げ、本発明の詳細な説明す
る。[Example] The present invention will be explained in detail below by giving Examples and Comparative Examples.
実施例1
98%硫酸10(1(1,0モル)とベンゼン187g
(2,4モル)とを還流上加熱撹拌しながら10時間反
応した。この時点で硫酸は検出されず、反応液を高速液
体クロマトグラフにより分析し、未反応の芳香族スルホ
ン酌量より芳香族スルボン酸の転化率を求めたところ6
0%であった。Example 1 98% sulfuric acid 10 (1 (1,0 mol) and benzene 187 g
(2.4 mol) was reacted for 10 hours under reflux with heating and stirring. At this point, no sulfuric acid was detected, and the reaction solution was analyzed using high-performance liquid chromatography, and the conversion rate of aromatic sulfonic acid was determined from the amount of unreacted aromatic sulfonic acid.6
It was 0%.
反応液に五酸化リンを23g(原料となる芳香族スルホ
ン酸に対しリン酸換算で0.32倍モル、以下同様)加
え、更に3時間還流させた。次に、反応液にベンゼン2
00gを加えて希釈し、水洗を行なった。次いでベンゼ
ンを減圧下留去して、ジフェニルスルホン196g(収
率90%、融点124〜128℃)を得た。23 g of phosphorus pentoxide (0.32 times the mole of aromatic sulfonic acid as a raw material in terms of phosphoric acid, the same applies hereinafter) was added to the reaction solution, and the mixture was further refluxed for 3 hours. Next, add benzene 2 to the reaction solution.
00g was added to dilute the solution and washed with water. Benzene was then distilled off under reduced pressure to obtain 196 g of diphenylsulfone (yield 90%, melting point 124-128°C).
実施例2
ベンゼンスルホン酸158g’(1,0モル)、ベンゼ
ン94g(1,2モル)とを還流下に加熱撹拌して9時
間反応した。反応液を高速液体クロマトグラフで分析し
たところ、ベンゼンスルホン酸の転化率は70%であっ
た。反応液に五酸化リンを11 (0,24倍モル)加
え、更に3時間還流させた。次に、反応液にベンゼン2
00gを加えて希釈し、水洗を行なった。次いで反応液
からベンゼンを減圧下留去し、得られた固体を水洗俊乾
燥し、ジフェニルスルホン203g(収率93%、融点
124〜128℃)を得た。Example 2 158 g' (1.0 mol) of benzenesulfonic acid and 94 g (1.2 mol) of benzene were heated and stirred under reflux and reacted for 9 hours. When the reaction solution was analyzed by high performance liquid chromatography, the conversion rate of benzenesulfonic acid was 70%. 11 (0.24 times the mole) of phosphorus pentoxide was added to the reaction solution, and the mixture was further refluxed for 3 hours. Next, add benzene 2 to the reaction solution.
00g was added to dilute the solution and washed with water. Benzene was then distilled off from the reaction solution under reduced pressure, and the resulting solid was washed with water and dried to obtain 203 g of diphenylsulfone (yield 93%, melting point 124-128°C).
実施例3
p−トルエンスルホン酸・−水和物190g(1,0モ
ル)、トルエン111g(1,2モル)を還流下に加熱
撹拌して8時間反応した。反応液を高速液体クロマトグ
ラフで分析したところ、p−トルエンスルホン酸の転化
率は70%であった。Example 3 190 g (1.0 mol) of p-toluenesulfonic acid-hydrate and 111 g (1.2 mol) of toluene were heated and stirred under reflux and reacted for 8 hours. When the reaction solution was analyzed by high performance liquid chromatography, the conversion rate of p-toluenesulfonic acid was 70%.
反応液に五酸化リンを21g(0,3倍モル)加え、更
に3時間還流させた。次に、反応液にトルエン300g
を加えて希釈し、水洗を行なった。21 g (0.3 times the mole) of phosphorus pentoxide was added to the reaction solution, and the mixture was further refluxed for 3 hours. Next, add 300 g of toluene to the reaction solution.
was added to dilute it and washed with water.
トルエンを減圧下留去して、4,4°−ジメチルジフェ
ニルスルホン236g (収率96%、融点153〜1
56℃ ) を1野lこ。Toluene was distilled off under reduced pressure to obtain 236 g of 4,4°-dimethyldiphenylsulfone (yield 96%, melting point 153-1
56℃) in one field.
実施例4
ベンゼンスルホン酸158g(1,0モル)、ベンゼン
94g(1,2モル)及び12−タンクストリンM (
H3PW12040−29H20)5’;tを還流下に
加熱撹拌して4時間反応した。反応液を高速液体クロマ
トグラフで分析したところ、ベンゼンスルホン酸の転化
率は85%でおった。反応液にポリリン110g(0,
11倍モル)加え、更に2時間還流させた。以下、実施
例1と同様にして、ジフェニルスルホン210g(収率
96%)を191ご。Example 4 158 g (1.0 mol) of benzenesulfonic acid, 94 g (1.2 mol) of benzene and 12-tanxtrine M (
H3PW12040-29H20)5';t was heated and stirred under reflux and reacted for 4 hours. When the reaction solution was analyzed by high performance liquid chromatography, the conversion rate of benzenesulfonic acid was 85%. Add 110 g of polyphosphorus (0,
11 times the mole) and further refluxed for 2 hours. Thereafter, in the same manner as in Example 1, 210 g (yield 96%) of diphenyl sulfone was added to 191 g.
実施例5
98%硫酸100y (1,0モル)、O−キシレン1
27g(1,2モル)及び12−タングストケイM (
H4S i W18O49” 24H20>5゜0gを
還流下に加熱撹拌し、O−キシレン107g(1,0モ
ル)を徐々に滴下した。6時間反応した後、実施例1と
同様に反応液を高速液体クロマトグラフで分析したとこ
ろ、0−キシレンスルホン酸の転化率は90%でめった
。反応液に五酸化リンを5.1 (0,08倍モル)加
え、更に2時間還流させた。次に、反応液に0−キシレ
ン300ffを加えて希釈し、水洗を行なった。キシレ
ンを減圧上留去して、3,3°、4,4−テトラメチル
ジフェニルスルホン26,1(収率96%、融点164
〜165℃)を得た。Example 5 98% sulfuric acid 100y (1.0 mol), O-xylene 1
27 g (1,2 mol) and 12-Tungstosilica M (
H4S i W18O49''24H20>5゜0g was heated and stirred under reflux, and 107g (1.0 mol) of O-xylene was gradually added dropwise.After reacting for 6 hours, the reaction solution was heated to high speed liquid in the same manner as in Example 1. When analyzed by chromatography, the conversion rate of 0-xylene sulfonic acid was 90%. 5.1 (0.08 times mole) of phosphorus pentoxide was added to the reaction solution, and the mixture was further refluxed for 2 hours. Next, The reaction solution was diluted with 300 ff of 0-xylene and washed with water.The xylene was distilled off under reduced pressure to obtain 3,3°,4,4-tetramethyldiphenylsulfone 26,1 (yield 96%, melting point 164
~165°C) was obtained.
実施例6
p−トルエンスルホン酸・−水和物190g(1,0モ
ル)、0−キシレン127g(1,2モル)及び12−
タングストリン酸(H3PW12040・30H20)
3gを還流下に加熱撹拌して8時間反応した。反応液を
高速液体クロマトグラフで分析したところ、p−トルエ
ンスルホン酸の転化率は82%であった。反応液に五酸
化リンを10tj(0,14倍モル)加え、更に3時間
速流させた。次に、反応液に0−キシレン300gを加
えて希釈し、水洗を行なった。0−キシレンを減圧上留
去して、3,4.4’−トリメチルジフェニルスルホン
247g(収率95%、融点128〜131℃)を得た
。Example 6 190 g (1.0 mol) of p-toluenesulfonic acid-hydrate, 127 g (1.2 mol) of 0-xylene and 12-
Tungstophosphoric acid (H3PW12040/30H20)
3 g was heated and stirred under reflux and reacted for 8 hours. When the reaction solution was analyzed by high performance liquid chromatography, the conversion rate of p-toluenesulfonic acid was 82%. 10 tj (0.14 times mole) of phosphorus pentoxide was added to the reaction solution, and the mixture was allowed to flow at high speed for an additional 3 hours. Next, 300 g of 0-xylene was added to the reaction solution to dilute it, and the solution was washed with water. 0-xylene was distilled off under reduced pressure to obtain 247 g of 3,4.4'-trimethyldiphenylsulfone (yield 95%, melting point 128-131°C).
比較例1
98%5A酸100g(1,0モル)、ベンゼン187
g(2,4モル)を還流下に加熱撹拌して1時間反応し
た。反応液を高速液体クロマトグラフで分析したところ
、ベンゼンスルホン酸の転化率は15%であった。反応
液に五酸化リンを実施例1と同量の23y (0,32
倍モル)加え、更に12時間遠速させた。次に、反応液
にベンゼン200gを加えて希釈し、水洗を行なった。Comparative Example 1 98% 5A acid 100g (1.0 mol), benzene 187
g (2.4 mol) was heated and stirred under reflux and reacted for 1 hour. When the reaction solution was analyzed by high performance liquid chromatography, the conversion rate of benzenesulfonic acid was 15%. The same amount of 23y (0,32
twice the molar amount) and further centrifuged for 12 hours. Next, 200 g of benzene was added to the reaction solution to dilute it, and the solution was washed with water.
ベンゼンを減圧上留去して得られたジフェニルスルホン
は153g(収率70%)であった。Diphenylsulfone obtained by distilling off benzene under reduced pressure was 153 g (yield 70%).
比較例2
98%硫酸100g(1,0モル)、ベンゼン187g
(2,4モル)及び12−タングストリン酸5gを還流
下に加熱撹拌して反応液中のベンゼンスルホン酸の転化
率が99%になるまで反応させた。反応所要時間は15
時間であった。反応液に五酸化リンを2g(0,028
倍モル)加え、更に3時間速流させた。次に、反応液に
ベンゼン2009を加えて希釈したところ、過反応によ
る不溶物を認めたのでこれを濾別後、水洗を行なった。Comparative example 2 98% sulfuric acid 100g (1.0 mol), benzene 187g
(2.4 mol) and 5 g of 12-tungstophosphoric acid were heated and stirred under reflux to react until the conversion rate of benzenesulfonic acid in the reaction solution reached 99%. The reaction time is 15
It was time. Add 2g of phosphorus pentoxide (0,028
2 times the mole) and the mixture was further allowed to flow at high speed for 3 hours. Next, when benzene 2009 was added to the reaction solution to dilute it, insoluble matter due to overreaction was found, so this was filtered off and washed with water.
ベンゼンを減圧上留去して得られたジフェニルスルホン
は190g(収率87%)であった。Diphenylsulfone obtained by distilling off benzene under reduced pressure was 190 g (yield: 87%).
比較例3
実施例3において、五酸化リンを1.49 (0゜02
倍モル)用いること以外はすべて同様に行なったところ
、4,4−ジメチルジフェニルスルホンが2017 (
収率83%)得られた。Comparative Example 3 In Example 3, phosphorus pentoxide was added at 1.49 (0°02
When the same procedure was repeated except that 4,4-dimethyldiphenylsulfone was used (2017 times the mole), 4,4-dimethyldiphenylsulfone was
Yield: 83%).
「発明の効果」
本発明によれば硫酸又は芳香族スルホン酸と芳香族化合
物からジアリールスルホン類を効率よく高収率で得るこ
とができる。又、高価な脱水剤の使用量が少ないため安
価ですみ、更に聞リン酸が少ないため量水処理が大幅に
軽減される。従って、本発明に係る方法により工業的に
極めて有利にジアリールスルホン類を製造することが可
能でおる。"Effects of the Invention" According to the present invention, diarylsulfones can be obtained efficiently and in high yield from sulfuric acid or aromatic sulfonic acid and an aromatic compound. Moreover, since the amount of expensive dehydrating agent used is small, it is inexpensive, and furthermore, since the amount of phosphoric acid is small, the amount of water treatment is significantly reduced. Therefore, it is possible to industrially produce diarylsulfones very advantageously by the method according to the present invention.
(以下余白)(Margin below)
Claims (4)
下又は非存在下に反応させてジアリールスルホン類を製
造する方法において、芳香族スルホン酸の転化率が40
〜95%の時点で、原料の芳香族スルホン酸に対し、リ
ン酸換算で0.025〜0.5倍モル量のリン酸化物及
び/又は縮合リン酸を添加することを特徴とするジアリ
ールスルホン類の製造方法。(1) In a method for producing diarylsulfones by reacting an aromatic compound and an aromatic sulfonic acid in the presence or absence of a catalyst, the conversion rate of the aromatic sulfonic acid is 40%.
A diaryl sulfone characterized by adding 0.025 to 0.5 times the molar amount of phosphoric oxide and/or condensed phosphoric acid in terms of phosphoric acid to the aromatic sulfonic acid as a raw material at a point of ~95%. Methods of manufacturing products.
にあたり、芳香族スルホン酸の転化率が70〜95%の
時点でリン酸化物及び/又は縮合リン酸を添加すること
を特徴とする特許請求の範囲第1項記載のジアリールス
ルホン類の製造方法。(2) A patent claim characterized in that in producing diarylsulfones in the presence of a catalyst, phosphorus oxide and/or condensed phosphoric acid is added when the conversion rate of aromatic sulfonic acid is 70 to 95%. A method for producing diarylsulfones according to item 1.
らのヘテロポリ酸からなる群から選ばれる1種又は2種
以上の混合物であることを特徴とする特許請求の範囲第
1項又は第2項記載のジアリールスルホン類の製造方法
。(3) The catalyst according to claim 1 or 2, wherein the catalyst is one or a mixture of two or more selected from the group consisting of tungstic acid, molybdic acid, and their heteropolyacids. Method for producing diarylsulfones.
るにあたり、芳香族スルホン酸の転化率が40〜70%
の時点でリン酸化物及び/又は縮合リン酸を添加するこ
とを特徴とする特許請求の範囲第1項記載のジアリール
スルホン類の製造方法。(4) When producing diarylsulfones in the absence of a catalyst, the conversion rate of aromatic sulfonic acid is 40 to 70%.
The method for producing diarylsulfones according to claim 1, characterized in that phosphoric oxide and/or condensed phosphoric acid are added at the point of .
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62053740A JPS63218653A (en) | 1987-03-09 | 1987-03-09 | Production of diaryl sulfones |
US07/070,576 US4778932A (en) | 1986-07-16 | 1987-07-07 | Process for preparing diarylsulfones |
DE3723401A DE3723401C2 (en) | 1986-07-16 | 1987-07-15 | Process for the preparation of diarylsulfones |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62053740A JPS63218653A (en) | 1987-03-09 | 1987-03-09 | Production of diaryl sulfones |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63218653A true JPS63218653A (en) | 1988-09-12 |
JPH0460595B2 JPH0460595B2 (en) | 1992-09-28 |
Family
ID=12951218
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62053740A Granted JPS63218653A (en) | 1986-07-16 | 1987-03-09 | Production of diaryl sulfones |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63218653A (en) |
-
1987
- 1987-03-09 JP JP62053740A patent/JPS63218653A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH0460595B2 (en) | 1992-09-28 |
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