JPH05123579A - Catalyst for ester exchange reaction and manufacture of aromatic carbonic acid diester using catalyst the same - Google Patents
Catalyst for ester exchange reaction and manufacture of aromatic carbonic acid diester using catalyst the sameInfo
- Publication number
- JPH05123579A JPH05123579A JP3293035A JP29303591A JPH05123579A JP H05123579 A JPH05123579 A JP H05123579A JP 3293035 A JP3293035 A JP 3293035A JP 29303591 A JP29303591 A JP 29303591A JP H05123579 A JPH05123579 A JP H05123579A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carbonic acid
- acid diester
- reaction
- ester exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 aromatic carbonic acid diester Chemical class 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 title abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 150000002148 esters Chemical group 0.000 title abstract 7
- 238000005809 transesterification reaction Methods 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 150000005690 diesters Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- DOBSQSLSWMMIEM-UHFFFAOYSA-N butoxytin Chemical compound CCCCO[Sn] DOBSQSLSWMMIEM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 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 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZZNBQSXWJOSEBF-UHFFFAOYSA-N (2-butylphenyl) hydrogen carbonate Chemical compound CCCCC1=CC=CC=C1OC(O)=O ZZNBQSXWJOSEBF-UHFFFAOYSA-N 0.000 description 1
- JJDRUQXMTFFWGM-UHFFFAOYSA-N (2-propan-2-ylphenyl) hydrogen carbonate Chemical compound CC(C)C1=CC=CC=C1OC(O)=O JJDRUQXMTFFWGM-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- RZZUDEFKEKBEQL-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-2,4-diene-1,6-diol Chemical compound OC12C(C=CC=C1)(O)O2 RZZUDEFKEKBEQL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000001987 diarylethers Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- OKQDSOXFNBWWJL-UHFFFAOYSA-N dihexyl carbonate Chemical compound CCCCCCOC(=O)OCCCCCC OKQDSOXFNBWWJL-UHFFFAOYSA-N 0.000 description 1
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003606 tin 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルキル炭酸ジエステ
ルとフェノール化合物などとのエステル交換反応によ
り、芳香族炭酸ジエステルを得る上で有用なエステル交
換反応用触媒とそれを用いた芳香族炭酸ジエステルの製
造方法に関する。FIELD OF THE INVENTION The present invention relates to a transesterification catalyst useful for obtaining an aromatic carbonic acid diester by a transesterification reaction between an alkyl carbonic acid diester and a phenolic compound, and an aromatic carbonic acid diester using the same. It relates to a manufacturing method.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】ポリカー
ボネートやイソシアネート化合物などの合成樹脂の原料
として芳香族炭酸ジエステルが、使用されている。この
芳香族炭酸ジエステルは、アルキル炭酸ジエステルなど
とフェノール化合物などとのエステル交換反応により得
られる。この反応で使用されるエステル交換反応触媒に
ついては種々の触媒系が、提案されている。例えば特公
昭56-40708号広報には、トリアルキルスズ化合物などが
開示され、特開昭56-123948 号広報には、Ｔｉ系、Ａｌ
系触媒が、提案されている。BACKGROUND OF THE INVENTION Aromatic carbonic acid diesters are used as raw materials for synthetic resins such as polycarbonate and isocyanate compounds. This aromatic carbonic acid diester is obtained by transesterification reaction of an alkyl carbonic acid diester or the like with a phenol compound or the like. Various catalyst systems have been proposed for transesterification catalysts used in this reaction. For example, Japanese Patent Publication No. 56-40708 discloses a trialkyl tin compound and the like, and Japanese Patent Publication No. 56-123948 discloses a Ti-based compound and an Al compound.
Based catalysts have been proposed.
【０００３】しかしながら、これらの触媒は、いずれも
触媒活性および選択性が未だ十分ではなく、副反応を伴
い易い。従って、上記触媒を用いるエステル交換反応で
は、ジアルキルエーテル、ジアリールエーテル、アルキ
ルアリールエーテルなどの副反応物が生成しやすく、芳
香族炭酸ジエステルの収率が低下する。However, these catalysts are still insufficient in catalytic activity and selectivity, and are likely to cause side reactions. Therefore, in the transesterification reaction using the above catalyst, a side reaction product such as a dialkyl ether, a diaryl ether, or an alkylaryl ether is likely to be produced, and the yield of the aromatic carbonic acid diester is lowered.
【０００４】従って、本発明の目的は、アルキル炭酸ジ
エステルまたはアリールーアルキル炭酸ジエステルを、
フェノール化合物またはそのアシルエステルで、エステ
ル交換するエステル交換反応において、触媒活性および
選択性が高く、芳香族炭酸ジエステルを収率良く得るこ
とができるエステル交換反応用触媒を提供することにあ
る。Therefore, an object of the present invention is to provide an alkyl carbonic acid diester or an aryl-alkyl carbonic acid diester,
It is an object of the present invention to provide a transesterification catalyst having a high catalytic activity and selectivity in the transesterification reaction of a phenolic compound or an acyl ester thereof with which a phenolic compound or an acyl ester thereof can be obtained, and capable of obtaining an aromatic carbonic acid diester in a high yield.
【０００５】また、本発明の目的は、芳香族炭酸ジエス
テルを効率良く得ることができる製造方法を提供するこ
とにある。Another object of the present invention is to provide a process for producing aromatic carbonic acid diesters efficiently.
【０００６】[0006]
【発明の構成】上記目的を達成するため、本発明は少な
くともジアルキル錫から合成されたエステル交換反応用
触媒を提供する。To achieve the above object, the present invention provides a transesterification catalyst synthesized from at least dialkyltin.
【０００７】また、本発明はアルキル炭酸ジエステルま
たはアリールーアルキル炭酸ジエステルと、フェノール
化合物またはそのアシルエステルとのエステル交換反応
を上記エステル交換反応用触媒の存在下で行なう芳香族
炭酸ジエステルの製造方法を提供する。The present invention also provides a method for producing an aromatic carbonic acid diester, which comprises transesterifying an alkyl carbonic acid diester or an aryl-alkyl carbonic acid diester with a phenol compound or an acyl ester thereof in the presence of the above transesterification catalyst. provide.
【０００８】本発明のエステル交換反応用触媒は、アル
キル炭酸ジエステルまたはアリールーアルキル炭酸ジエ
ステルを、フェノール化合物またはそのアシルエステル
でエステル交換して芳香族炭酸ジエステルを得る反応に
好適に使用される。The catalyst for the transesterification reaction of the present invention is suitably used for a reaction to obtain an aromatic carbonic acid diester by transesterifying an alkyl carbonic acid diester or an aryl-alkyl carbonic acid diester with a phenol compound or an acyl ester thereof.
【０００９】式１で表わされる触媒のＲとしては、メチ
ル、エチル、プロピル、イソプロピル、ｔ−ブチル、ペ
ンチル、ヘキシル、ヘプチル、オクチル基などの直鎖ま
たは分岐鎖状のアルキル基である。R of the catalyst represented by the formula 1 is a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, t-butyl, pentyl, hexyl, heptyl and octyl groups.
【００１０】また、Ｙは、カテコールなどの芳香族ジオ
ール類や１、２ーシクロヘキサンジオール、２、３ーブ
タンジオールや１、２ープロパンジオールなどのような
脂肪族ジオール類である。Further, Y is an aromatic diol such as catechol or an aliphatic diol such as 1,2-cyclohexanediol, 2,3-butanediol or 1,2-propanediol.
【００１１】これらの合成は、P.J.Smith によりJ.Orug
ano.Chem．（ジャーナル．オブ．オーガニック．ケミス
トリー）,40(1972)341に報告されている。These syntheses are described by PJ Smith in J. Orug.
ano.Chem. (Journal of Organic Chemistry), 40 (1972) 341.
【００１２】式４で表わされる芳香族炭酸ジエステル
は、式２で、表わされるアルキル炭酸ジエステルまたは
アリールーアルキル炭酸ジエステルと式３で表わされる
フェノール化合物またはそのアシルエステルとのエステ
ル交換反応により得られる。The aromatic carbonic acid diester represented by the formula 4 is obtained by a transesterification reaction between the alkyl carbonate diester represented by the formula 2 or the aryl-alkyl carbonic acid diester and the phenol compound represented by the formula 3 or an acyl ester thereof.
【００１３】[0013]
【化１】 [Chemical 1]
【００１４】（式中Ｒ１およびＲ２は、同一または異な
って、炭素数１〜１０のアルキル基、または置換基を有
していてもよいアリール基を示す。Ａｒは置換基を有し
ていてもよいアリール基を示す。Ｒ３は水素原子または
アシル基を示す。但し、Ｒ１とＲ２は同時に置換基を有
していてもよいアリール基ではない。）前記式２で表さ
れる化合物のアルキル基としては、例えばメチル、エチ
ル、ピロピル、イソピロピル、ｔ−ブチル、ペンチル、
ヘキシル、ヘプチル、オクチル基などの直鎖または分岐
鎖状のアルキ基Ｒ１及びＲ２は、互いに異なっていても
よい。(In the formula, R1 and R2 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an aryl group which may have a substituent. Ar may have a substituent. R3 represents a hydrogen atom or an acyl group, provided that R1 and R2 are not an aryl group which may have a substituent at the same time.) As an alkyl group of the compound represented by Formula 2 above Is, for example, methyl, ethyl, pillopyr, isopyropyr, t-butyl, pentyl,
The linear or branched alkyl groups R1 and R2 such as hexyl, heptyl and octyl groups may be different from each other.
【００１５】これらのアルキル基の中で、炭素数１〜４
のアルキル基、特にメチル基が好ましい。Among these alkyl groups, the number of carbon atoms is 1 to 4
Alkyl groups of, especially methyl groups are preferred.
【００１６】アリール基としては、フェニル、ナフチ
ル、アントリル基などが例示される。置換基としては、
例えば塩素、臭素、ヨウ素などのハロゲン原子メチル、
エチル、プロピル、イソプロピル、ブチル基などのアル
キル基、シクロヘキシル基などのシクロアルキル基、メ
トキシ、エトキシ、プロポキシ、ブトキシなどのアルコ
キシ基、シクロアルキルオキシ基、フェノキシ、ナフト
オキシ基などのアリールオキシ基、ベンジル、フェネチ
ル基などのアルキル基、ニトロ基、シアノ基などが挙げ
られる。これらの置換基は、アリール基の任意の位置に
１または２以上置換してよい。Examples of the aryl group include phenyl, naphthyl and anthryl groups. As a substituent,
For example, halogen atom methyl such as chlorine, bromine, iodine,
Alkyl groups such as ethyl, propyl, isopropyl and butyl groups, cycloalkyl groups such as cyclohexyl groups, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, cycloalkyloxy groups, phenoxy, aryloxy groups such as naphthoxy groups, benzyl, Examples thereof include an alkyl group such as a phenethyl group, a nitro group, and a cyano group. One or two or more of these substituents may be substituted at any position of the aryl group.
【００１７】前記式２で表わされる化合物としては、例
えば炭酸ジメチル、炭酸ジエチル、炭酸ジプロピル、炭
酸ジイソプロピル、炭酸ジブル、炭酸ジヘキシル、炭酸
ジオクチル、メチルーフェニル炭酸ジエステル、エチル
ーフェニル炭酸ジエステル、プロピルーフェニル炭酸ジ
エステル、イソプルピルーフェニル炭酸ジエステル、ブ
チルーフェニル炭酸ジエステルなどが挙げられる。これ
らの中で、特に好ましい化合物は、炭酸ジメチルであ
る。Examples of the compound represented by the above formula 2 are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibble carbonate, dihexyl carbonate, dioctyl carbonate, methyl-phenyl carbonate diester, ethyl-phenyl carbonate diester, propyl-phenyl. Examples thereof include carbonic acid diester, isopropyl phenyl carbonic acid diester, and butyl-phenyl carbonic acid diester. Of these, a particularly preferred compound is dimethyl carbonate.
【００１８】前記式３で表わされる化合物において、置
換基を有していてもよいアリール基としては、前記と同
様の基が挙げられる。また、アシル基としては前記アル
キル基に対応するアシル基が例示される。式３で表わさ
れる化合物の中で、好ましい化合物はフェノールであ
る。In the compound represented by the above formula 3, examples of the aryl group which may have a substituent include the same groups as described above. Examples of the acyl group include acyl groups corresponding to the above alkyl groups. Among the compounds of formula 3, the preferred compound is phenol.
【００１９】本発明の製造方法は、工業的に入手が容易
であり、かつ有利なアルキル炭酸ジエステルとフェノー
ル化合物とのエステル交換反応に好ましく適用される。The production method of the present invention is industrially easily available and is preferably applied to the transesterification reaction of an advantageous alkyl carbonic acid diester with a phenol compound.
【００２０】式２で表わされる化合物と式３で表わされ
る化合物との割合は、任意の比率で変えることが可能で
あるが、このましくはモル比１：２〜１：１０程度であ
る。The ratio of the compound represented by the formula 2 to the compound represented by the formula 3 can be changed at any ratio, but the molar ratio is preferably about 1: 2 to 1:10.
【００２１】エステル交換反応において、前記エステル
交換反応用触媒は、反応の進行を妨げない広い範囲で使
用できる。触媒量は通常、式３の化合物に対して、０．
００１〜１．０モル％、好ましくは０．０１〜０．１モ
ル％程度である。In the transesterification reaction, the transesterification catalyst can be used in a wide range without hindering the progress of the reaction. The amount of catalyst is usually 0.
It is about 001 to 1.0 mol%, preferably about 0.01 to 0.1 mol%.
【００２２】式２で表される化合物と式３で表される化
合物とのエステル交換反応は、通常平衡反応である。従
って、反応の進行を円滑に行うために、生成物の一部、
例えば、生成するアルコールを連続的または間欠的に除
去しながら反応するのが好ましい。反応温度は式２で表
される化合物と式３で表される化合物の種類およびその
組成、反応圧力などに応じて決定できるが、通常５０〜
２００℃、好ましくは７０〜１５０℃程度である。The transesterification reaction between the compound represented by the formula 2 and the compound represented by the formula 3 is usually an equilibrium reaction. Therefore, in order to smoothly proceed the reaction, a part of the product,
For example, it is preferable to react while continuously or intermittently removing the produced alcohol. The reaction temperature can be determined according to the type and composition of the compound represented by Formula 2 and the compound represented by Formula 3, the reaction pressure, etc.
The temperature is 200 ° C, preferably about 70 to 150 ° C.
【００２３】エステル交換反応により得られた芳香族炭
酸ジエステルは、慣用の分離精製方法により単離でき
る。The aromatic carbonic acid diester obtained by the transesterification reaction can be isolated by a conventional separation and purification method.
【００２４】[0024]
【実施例】以下に、実施例に基づいて本発明をより詳細
に説明する。EXAMPLES The present invention will be described in more detail based on the following examples.
【００２５】[0025]
【実施例１】フェノール２４４．７ｍｍｏｌ、炭酸ジメ
チル５５．５ｍｍｏｌ、ジブチル２、３ブトキシスズ
５．５７ｍｍｏｌとベンゼン３０ｇを２００ｍｌの三ツ
口反応フラスコに入れフラスコの上部にモレキュラーシ
ーブス４Ａ４０ｇが充填された５０ｍｌのソックスレー
抽出器を連結した。さらに、抽出器の上部にコンデンサ
ーを設け反応液の温度を８５〜９０℃で８時間、加熱還
流した。Example 1 Phenol 244.7 mmol, dimethyl carbonate 55.5 mmol, dibutyl 2,3 butoxytin 5.57 mmol and 30 g of benzene were placed in a 200 ml three-necked reaction flask and 50 ml of Soxhlet extraction with 40 g of molecular sieves 4A filled in the upper part of the flask. The vessels were connected. Furthermore, a condenser was provided above the extractor, and the temperature of the reaction solution was heated to reflux at 85 to 90 ° C. for 8 hours.
【００２６】反応液をガスクロマトグラフィーで分析し
た結果メチルフェニルカーボネートが４２重量％、ジフ
ェニルカーボネートが４５重量％の収率で生成した。ま
た、アニソールは０．１重量％以下の生成量であった。As a result of analyzing the reaction liquid by gas chromatography, 42% by weight of methylphenyl carbonate and 45% by weight of diphenyl carbonate were produced. Further, the amount of anisole produced was 0.1% by weight or less.
【００２７】[0027]
【実施例２】実施例１と同様にして、フェノール２４
４．４ｍｍｏｌ、ＤＭＣ５５．６ｍｍｏｌ、ベンゼン３
０ｇと触媒としてジブチル１、２ープロポキシスズプロ
ポキシドを５．５０ｍｍｏｌを用いて反応を行った。反
応液をガスクロマトグラフィーで分析した結果メチルフ
ェニルカーボネートが４２重量％、ジフェニルカーボネ
ートが４２重量％の収率で生成した。また、アニソール
は０．１重量％以下の生成量であった。Example 2 Phenol 24 was prepared in the same manner as in Example 1.
4.4 mmol, DMC55.6 mmol, benzene 3
The reaction was carried out using 0 g and 5.50 mmol of dibutyl 1,2-propoxytin propoxide as a catalyst. As a result of analyzing the reaction liquid by gas chromatography, 42% by weight of methylphenyl carbonate and 42% by weight of diphenyl carbonate were produced. Further, the amount of anisole produced was 0.1% by weight or less.
【００２８】[0028]
【実施例３】実施例１と同様にして、フェノール２４
４．０ｍｍｏｌ、ＤＭＣ５５．８ｍｍｏｌ、ベンゼン３
０ｇと触媒としてジブチルスズカテコキシド５．００ｍ
ｍｏｌを用いて反応を行った。Example 3 Phenol 24 was prepared in the same manner as in Example 1.
4.0 mmol, DMC55.8 mmol, benzene 3
0g and 5.00m of dibutyltin catecholoxide as a catalyst
The reaction was performed using mol.
【００２９】反応液をガスクロマトグラフィーで分析し
た結果メチルフェニルカーボネートが３９重量％、ジフ
ェニルカーボネートが４０重量％の収率で生成した。ま
た、アニソールは０．１重量％以下の生成量であった。As a result of analyzing the reaction liquid by gas chromatography, 39% by weight of methylphenyl carbonate and 40% by weight of diphenyl carbonate were produced. Further, the amount of anisole produced was 0.1% by weight or less.
【００３０】[0030]
【実施例４】ジブチルスズオキサイド１００ｍｍｏｌ、
２，３ーブタンジオール１００ｍｍｏｌおよびベンゼン
１００ｇを３００ｍｌの三ツ口フラスコに入れデーン
アンド スターク セパレーターを用いながら２時間加
熱還流させた後、ベンゼンで再結晶を行った。確認は
119 ＳｎＮＭＲを用いた。（δ＝１５５）ジブチル２，
３ブトキシスズを収率６３％で得た。Example 4 100 mmol of dibutyltin oxide,
100 mmol of 2,3-butanediol and 100 g of benzene were placed in a 300 ml three-necked flask and Dane.
After heating and refluxing for 2 hours using an And Stark separator, recrystallization was performed with benzene. Confirmation
119 SnNMR was used. (Δ = 155) dibutyl 2,
3 Butoxytin was obtained with a yield of 63%.
【００３１】[0031]
【比較例１】触媒としてジｎ−ブチルスズオキサイド
５．５ｍｍｏｌを使用する以外は、実施例１と同様に反
応を行った。反応液をガスクロマトグラフィーで分析し
た結果、メチルフェニルカーボネートが３８．１重量
％、ジフェニルカーボネートが１０．５重量％の収率で
生成した。またアニソールは０．５重量％以上生成して
いた。この生成量は実施例１と比較して、約５倍以上で
ある。Comparative Example 1 The reaction was performed in the same manner as in Example 1 except that 5.5 mmol of di-n-butyltin oxide was used as the catalyst. As a result of analyzing the reaction liquid by gas chromatography, methyl phenyl carbonate was produced in a yield of 38.1 wt% and diphenyl carbonate was produced in a yield of 10.5 wt%. Moreover, 0.5% by weight or more of anisole was produced. This production amount is about 5 times or more as compared with Example 1.
【００３２】[0032]
【比較例２】触媒としてテトラブトキシチタネート５．
５ｍｍｏｌを使用する以外は、実施例１と同様に反応を
行った。反応液をガスクロマトグラフィーで分析した結
果、メチルフェニルカーボネートが５０．５重量％ジフ
ェニルカーボネートが７．６重量％の収率で生成した。
また、反応液は実施例１では見られなかった濃赤色に着
色していた。Comparative Example 2 Tetrabutoxy titanate as a catalyst 5.
The reaction was performed in the same manner as in Example 1 except that 5 mmol was used. As a result of analyzing the reaction solution by gas chromatography, 50.5% by weight of methylphenyl carbonate and 7.6% by weight of diphenyl carbonate were produced.
Further, the reaction liquid was colored in deep red which was not found in Example 1.
【００３３】[0033]
【発明の効果】本発明のエステル交換反応用触媒は、触
媒活性が高く、芳香族炭酸ジエステルを収率よく得るこ
とができる。EFFECT OF THE INVENTION The catalyst for transesterification reaction of the present invention has a high catalytic activity, and an aromatic carbonic acid diester can be obtained in good yield.
【００３４】また、本発明の芳香族炭酸ジエステルの製
造方法は、副反応を抑制して芳香族炭酸ジエステルを効
率よく製造できる。Further, the method for producing an aromatic carbonic acid diester of the present invention can efficiently produce an aromatic carbonic acid diester by suppressing side reactions.
Claims (2)
Ｓｎと５員環を形成するジオールでかつ５員環が硬い構
造であるもの）で示される中から選択されたエステル交
換反応用触媒。1. R2 Sn = Y ... Formula 1 (wherein R is an alkyl group, Y is a diol that forms a 5-membered ring with Sn such as catechol, and the 5-membered ring has a hard structure). A catalyst for transesterification reaction selected from those shown.
アルキル炭酸ジエステルと、フェノール化合物とのエス
テル交換反応を、請求項１記載のエステル交換反応用触
媒の存在下で行なう芳香族炭酸ジエステルの製造方法。2. A process for producing an aromatic carbonic acid diester, wherein the transesterification reaction between an alkyl carbonic acid diester or an aryl-alkyl carbonic acid diester and a phenol compound is carried out in the presence of the transesterification reaction catalyst according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3293035A JPH05123579A (en) | 1991-11-08 | 1991-11-08 | Catalyst for ester exchange reaction and manufacture of aromatic carbonic acid diester using catalyst the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3293035A JPH05123579A (en) | 1991-11-08 | 1991-11-08 | Catalyst for ester exchange reaction and manufacture of aromatic carbonic acid diester using catalyst the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05123579A true JPH05123579A (en) | 1993-05-21 |
Family
ID=17789652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3293035A Pending JPH05123579A (en) | 1991-11-08 | 1991-11-08 | Catalyst for ester exchange reaction and manufacture of aromatic carbonic acid diester using catalyst the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05123579A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727192A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | The preparation method of dipheryl carbonate esters compound |
| CN110950759A (en) * | 2019-12-04 | 2020-04-03 | 四川中蓝国塑新材料科技有限公司 | Method for controlling by-product anisole in diphenyl carbonate production |
-
1991
- 1991-11-08 JP JP3293035A patent/JPH05123579A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727192A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | The preparation method of dipheryl carbonate esters compound |
| CN110950759A (en) * | 2019-12-04 | 2020-04-03 | 四川中蓝国塑新材料科技有限公司 | Method for controlling by-product anisole in diphenyl carbonate production |
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