JPH085825B2 - Method for producing alkylphenols - Google Patents
Method for producing alkylphenolsInfo
- Publication number
- JPH085825B2 JPH085825B2 JP63145893A JP14589388A JPH085825B2 JP H085825 B2 JPH085825 B2 JP H085825B2 JP 63145893 A JP63145893 A JP 63145893A JP 14589388 A JP14589388 A JP 14589388A JP H085825 B2 JPH085825 B2 JP H085825B2
- Authority
- JP
- Japan
- Prior art keywords
- alkylphenols
- catalyst
- reaction
- group
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- QFVBCWBVMGRFQN-UHFFFAOYSA-N [Ba].[Cr].[Cu] Chemical compound [Ba].[Cr].[Cu] QFVBCWBVMGRFQN-UHFFFAOYSA-N 0.000 claims description 4
- AQZDDTMGEKEQLL-UHFFFAOYSA-N [Mn].[Ba].[Cr].[Cu] Chemical compound [Mn].[Ba].[Cr].[Cu] AQZDDTMGEKEQLL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 2,6-diethyl-4-methoxymethylphenol 2,6-diethyl-4-methoxymethylphenol Chemical compound 0.000 description 3
- SCXYLTWTWUGEAA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(methoxymethyl)phenol Chemical compound COCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SCXYLTWTWUGEAA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- AHXXIALEMINDAW-UHFFFAOYSA-N 4-(methoxymethyl)phenol Chemical compound COCC1=CC=C(O)C=C1 AHXXIALEMINDAW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- DTSIGNYUHXFIGO-UHFFFAOYSA-N 2,6-di(butan-2-yl)-4-(methoxymethyl)phenol Chemical compound CCC(C)C1=CC(COC)=CC(C(C)CC)=C1O DTSIGNYUHXFIGO-UHFFFAOYSA-N 0.000 description 1
- WGVZSBFOBJXWND-UHFFFAOYSA-N 2,6-dicyclohexyl-4-(methoxymethyl)phenol Chemical compound OC=1C(C2CCCCC2)=CC(COC)=CC=1C1CCCCC1 WGVZSBFOBJXWND-UHFFFAOYSA-N 0.000 description 1
- UHZLTTPUIQXNPO-UHFFFAOYSA-N 2,6-ditert-butyl-3-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1C(C)(C)C UHZLTTPUIQXNPO-UHFFFAOYSA-N 0.000 description 1
- UCKUPWJWVMQSKH-UHFFFAOYSA-N 2,6-ditert-butyl-4-(ethoxymethyl)phenol Chemical compound CCOCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 UCKUPWJWVMQSKH-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IEWCKTWDZYPKSZ-UHFFFAOYSA-N 2-tert-butyl-4-(methoxymethyl)-6-methylphenol Chemical compound COCC1=CC(C)=C(O)C(C(C)(C)C)=C1 IEWCKTWDZYPKSZ-UHFFFAOYSA-N 0.000 description 1
- XCSJNCBKRFGJKY-UHFFFAOYSA-N 4-(ethoxymethyl)-2,6-di(propan-2-yl)phenol Chemical compound CCOCC1=CC(C(C)C)=C(O)C(C(C)C)=C1 XCSJNCBKRFGJKY-UHFFFAOYSA-N 0.000 description 1
- MFCLYZSYMMDQRI-UHFFFAOYSA-N 4-(methoxymethyl)-2,6-di(propan-2-yl)phenol Chemical compound COCC1=CC(C(C)C)=C(O)C(C(C)C)=C1 MFCLYZSYMMDQRI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000002309 gasification Methods 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
- 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 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
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、アルキルフェノール類の製造方法に関
し、詳しくは、アルコキシアルキル基を有するフェノー
ル類を水素ガスの存在下に触媒により接触分解してアル
キルフェノール類を製造する方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing alkylphenols, and more particularly, to an alkylphenol which is obtained by catalytically decomposing a phenol having an alkoxyalkyl group with a catalyst in the presence of hydrogen gas. The present invention relates to a method of manufacturing.
［従来の技術］ 2,6−ジ−ｔ−ブチル−メチルフェノールのようなア
ルキルフェノール類は、酸化防止剤やその他の化成品原
料として有用な化合物である。[Prior Art] Alkylphenols such as 2,6-di-t-butyl-methylphenol are useful compounds as antioxidants and other raw materials for chemical products.
このような多くの用途が期待されているアルキルフェ
ノール類の製造方法は数多く提案されている。Many methods for producing alkylphenols, which are expected to have such many uses, have been proposed.
たとえば、特公昭36−9074号公報には、2,6−ジ−ｔ
−ブチル−４−メトキシメチルフェノールを出発原料と
してナトリウムメトキシドおよびメタノールを耐圧容器
に採り、温度200℃の条件下に４時間かけて反応させた
のち、内容物を水洗してからジエチルエーテルで抽出し
て2,6−ジ−ｔ−ブチル−ｐ−クレゾールを製造した
り、2,6−ジ−イソプロピル−４−エトキシメチルフェ
ノールを用いて同様の手法により2,6−ジ−イソプロピ
ル−４−メチルフェノールを得ることなどを記載してい
る。For example, Japanese Patent Publication No. 36-9074 discloses 2,6-ge-t.
-Butyl-4-methoxymethylphenol was used as a starting material, and sodium methoxide and methanol were placed in a pressure vessel and reacted at a temperature of 200 ° C for 4 hours, then the contents were washed with water and extracted with diethyl ether. To produce 2,6-di-t-butyl-p-cresol, or 2,6-di-isopropyl-4-ethoxymethylphenol is used in a similar manner to produce 2,6-di-isopropyl-4- It describes how to obtain methylphenol.
また、米国特許第3006969号公報には、前記のような
アルコキシアルキル基を有するフェノール類を水素ガス
および銅−クロム系触媒の存在下に接触分解してアルキ
ルフェノール類を製造することも記載されている。Also, US Pat. No. 3,0069,693 discloses that an alkylphenol is produced by catalytically decomposing a phenol having an alkoxyalkyl group as described above in the presence of hydrogen gas and a copper-chromium catalyst. .
［発明が解決しようとする課題］ しかしながら、前者に記載されているアルコキシアル
キル基含有アルキルフェノール類を原料とするアルキル
フェノール類の製造方法は、反応温度がおよそ200〜300
℃という比較的高い温度を使用しなければならず、しか
もこの手法によって得られるアルキルフェノール類の生
成量は、例えば出発原料である2,6−ジ−ｔ−ブチル−
４−メトキシメチルフェノールから2,6−ジ−ｔ−ブチ
ル−ｐ−クレゾールを製造する場合、およそ85％に止ま
り、充分に満足できるものには至っていないというもの
であった。[Problems to be Solved by the Invention] However, in the method for producing alkylphenols starting from the alkoxyalkyl group-containing alkylphenols described in the former, the reaction temperature is about 200 to 300.
The relatively high temperature of ° C must be used, and the amount of alkylphenols obtained by this method is, for example, 2,6-di-t-butyl-, which is the starting material.
When 2,6-di-t-butyl-p-cresol was produced from 4-methoxymethylphenol, it was only about 85%, which was not completely satisfactory.
また、この方法の工程についてみると、反応終了後の
処理において水洗、中和、抽出および蒸留という工程の
組み合わせを必要とする複雑さがあり、不都合なもので
あった。Further, the steps of this method are inconvenient because they require a combination of steps of washing with water, neutralization, extraction and distillation in the treatment after the completion of the reaction.
一方、後者に記載されているアルキルフェノール類の
製造方法は、その成績においてほぼ満足すべき水準であ
るものの、触媒寿命が短く、比較的短時間で触媒の活性
低下をきたし、実用上重大な解決すべき課題を有してい
た。On the other hand, the method for producing alkylphenols described in the latter is almost satisfactory in terms of the results, but the catalyst life is short and the activity of the catalyst decreases in a relatively short time, which is a serious problem in practical use. Had an issue to be addressed.
この発明は、このような従来の製造方法における欠点
を解消し、寿命の長い触媒を用いて成績よくアルキルフ
ェノール類を製造する方法を提供することを目的とす
る。It is an object of the present invention to solve the drawbacks of the conventional production method and to provide a method for producing alkylphenols with good performance by using a catalyst having a long life.
［課題を解決するための手段］ 発明者は前記目的を達成するために、従来知られてい
る銅−クロム系二元触媒を基にして、この触媒の改良に
ついて種々検討した結果、第三または第四の特定の金属
と組み合わせ、三元または四元の触媒とすることによっ
て、前記目的を達成しうることを見い出し、この知見に
基づいてこの発明を完成するに至った。[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventor has conducted various studies on the improvement of this catalyst based on a conventionally known copper-chromium binary catalyst, It was found that the above object can be achieved by combining with a fourth specific metal to form a three-way or four-way catalyst, and the present invention has been completed based on this finding.
すなわち、この発明によれば、次式［１］； （ただし、式［１］中、R1、R2およよびR3は水素原子ま
たは炭素数１〜10であるアルキル基を表し、R4は低級ア
ルキル基を表す。） で示されるアルコキシアルキル基含有アルキルフェノー
ル類を水素ガスおよび銅−クロム−バリウム系触媒また
は銅−クロム−バリウム−マンガン系触媒の存在下に接
触分解することを特徴とする次式［２］； （ただし、式［２］中、R1、R2、およびR3は前記と同じ
意味を表す。） で示されるアルキルフェノール類の製造方法が提供され
る。That is, according to the present invention, the following formula [1]; (However, in the formula [1], R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 4 represents a lower alkyl group.) Group-containing alkylphenols are catalytically decomposed in the presence of hydrogen gas and a copper-chromium-barium-based catalyst or a copper-chromium-barium-manganese-based catalyst, the following formula [2]; (However, in the formula [2], R 1 , R 2 , and R 3 have the same meanings as described above.) A method for producing the alkylphenols is provided.
この発明の反応工程は、概略次式のように示すことが
できる。The reaction process of the present invention can be roughly represented by the following formula.
この発明で使用する出発原料であるアルコキシアルキ
ル基含有アルキルフェノール類としては、2,6−ジ−ｔ
−ブチル−４−メトキシメチルフェノール、 2,6−ジ−sec−ブチル−４−メトキシメチルフェノー
ル、 2,6−ジ−イソプロピル−４−メトキシメチルフェノー
ル、 2,6−ジエチル−４−メトキシメチルフェノール、 2,6−ジエチル−４−メトキシメチルフェノール、 2,6−ジシクロヘキシル−４−メトキシメチルフェノー
ル、 ２−メチル−４−メトキシメチル−６−ｔ−ブチルフェ
ノール、 2,6−ジ−ｔ−ブチル−４−エトキシメチルフェノール などが挙げられる。これらの外に、前記R1、R2およびR3
が水素原子、メチル基、エチル基、プロピル基、ブチル
基、ペンチル基、ヘキシル基、ヘプチル基、オクチル
基、ノニル基、デシル基などであり、またR4がメチル
基、エチル基、ブチル基、プロピル基などである各種の
アルコキシアルキル基含有アルキルフェノール類をこの
発明の範囲に含めることができる。 The alkoxyphenol-containing alkylphenols used as the starting material in the present invention include 2,6-di-t
-Butyl-4-methoxymethylphenol, 2,6-di-sec-butyl-4-methoxymethylphenol, 2,6-di-isopropyl-4-methoxymethylphenol, 2,6-diethyl-4-methoxymethylphenol 2,6-diethyl-4-methoxymethylphenol, 2,6-dicyclohexyl-4-methoxymethylphenol, 2-methyl-4-methoxymethyl-6-t-butylphenol, 2,6-di-t-butyl- 4-ethoxymethylphenol and the like can be mentioned. In addition to these, R 1 , R 2 and R 3
Is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc., and R 4 is a methyl group, an ethyl group, a butyl group, Various alkoxyalkyl group-containing alkylphenols such as propyl group can be included in the scope of the present invention.
これらの中でも、好ましいのは2,6−ジ−ｔ−ブチル
−４−メトキシメチルフェノールである。Among these, 2,6-di-t-butyl-4-methoxymethylphenol is preferable.
上述の式によって進行する反応は、触媒の存在下に行
われ、ここで用いる触媒は、銅−クロム−バリウム系ま
たは銅−クロム−バリウム−マンガン系触媒である。The reaction proceeding according to the above formula is carried out in the presence of a catalyst, and the catalyst used here is a copper-chromium-barium catalyst or a copper-chromium-barium-manganese catalyst.
これら三元または四元金属系触媒は、使用に際し、そ
れぞれの金属が酸化物となっているものが好ましい。It is preferable that each of these ternary or quaternary metal-based catalysts is an oxide when used.
担体は特に必要ではないが、所望によりシリカ、アル
ミナ、マグネシア、ジルコニア、酸化ニオブ、トリア、
ボリア、シリカ−アルミナ、シリカ−マグネシア、クロ
ミア−アルミナ、アルミナ−ボリア、モリブデナ−アル
ミナ、酸化タングステン−アルミナ、シリカ−チタニ
ア、ゼオライト、ハイシリカゼオライト、モルデナイ
ド、ガロシリケート、鉄シリケート、シリカライト、ホ
ージャサイト、結晶性リン酸アルミニウム、ペロブスカ
イト、クレー、活性炭、炭素繊維、ケイソウ土などの担
体に担持させたものを用いてもよい。A carrier is not particularly necessary, but if desired, silica, alumina, magnesia, zirconia, niobium oxide, thoria,
Boria, silica-alumina, silica-magnesia, chromia-alumina, alumina-boria, molybdena-alumina, tungsten oxide-alumina, silica-titania, zeolite, high silica zeolite, mordenide, gallosilicate, iron silicate, silicalite, faujasite. Alternatively, those supported on a carrier such as crystalline aluminum phosphate, perovskite, clay, activated carbon, carbon fiber, or diatomaceous earth may be used.
これら三元または四元金属触媒における金属の割合に
特に制限はないが、銅−クロム−バリウム系触媒におい
ては通常、銅20〜42重量％、クロム17〜33重量％、バリ
ウム２〜20重量％であり、銅−クロム−バリウム−マン
ガン系触媒においては通常、銅15〜45重量％、クロム12
〜40重量％、バリウム0.5〜15重量％、マンガン0.5〜15
重量％である。There is no particular limitation on the proportion of the metal in these three-way or four-way metal catalyst, but in the copper-chromium-barium catalyst, usually 20-42 wt% copper, 17-33 wt% chromium, 2-20 wt% barium. In a copper-chromium-barium-manganese-based catalyst, copper is usually 15 to 45% by weight and chromium 12
~ 40 wt%, barium 0.5-15 wt%, manganese 0.5-15
% By weight.
この触媒の使用量についても特に制限はないが通常
は、前記アルコキシアルキル基含有アルキルフェノール
類１モルに対して0.001〜30g、好ましくは0.01〜15gの
範囲である。The amount of the catalyst used is not particularly limited, but is usually in the range of 0.001 to 30 g, preferably 0.01 to 15 g, relative to 1 mol of the alkoxyalkyl group-containing alkylphenol.
触媒の使用量が、アルコキシアルキル基含有アルキル
フェノール類１モルに対して0.001gより少ないと、充分
な触媒作用が現れず目的物であるアルキルフェノール類
の収率が低下することがある。一方、30gを超えて使用
しても、その使用量に見合った収率向上が現れなくなる
ことがある。When the amount of the catalyst used is less than 0.001 g per 1 mol of the alkoxyalkyl group-containing alkylphenols, sufficient catalytic action does not appear and the yield of the target alkylphenols may decrease. On the other hand, even if the amount used exceeds 30 g, the yield improvement commensurate with the amount used may not appear.
この発明における反応は、メタノール、エタノール、
イソプロパノールなどのアルコール、ペンタン、ヘキサ
ン、ヘプタン、オクタン、ノナン、デカン、などの脂肪
族炭化水素を溶媒として進行させることができる。The reaction in this invention is methanol, ethanol,
An alcohol such as isopropanol, an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, nonane, and decane can be used as a solvent.
これら溶媒を用いるときは、アルコキシアルキル基含
有アルキルフェノール類１モルに対し、10〜5000g、好
ましくは50〜1000gの範囲である。When these solvents are used, the amount is in the range of 10 to 5000 g, preferably 50 to 1000 g, relative to 1 mol of the alkoxyalkyl group-containing alkylphenol.
この発明においては、以下の条件下に反応が進行す
る。In this invention, the reaction proceeds under the following conditions.
すなわち、反応温度は80〜250℃、好ましくは100〜20
0℃であり、この反応温度が、80℃より低い温度である
ときには、反応が充分に早まらない現象が起り、また、
250℃を超えるときには収率が上らないことが起り得
る。That is, the reaction temperature is 80 to 250 ° C, preferably 100 to 20
When the reaction temperature is 0 ° C and the temperature is lower than 80 ° C, a phenomenon occurs in which the reaction does not proceed sufficiently, and
When the temperature exceeds 250 ° C, the yield may not increase.
この発明における反応を行う際には、水素ガスの存在
を必要とし、この発明の場合にはそのガス圧の範囲を０
〜100kg/cm2・Ｇ、好ましくは０〜30kg/cm2・Ｇとする
ことによって目的を達成させることができる。When carrying out the reaction in the present invention, the presence of hydrogen gas is required, and in the case of the present invention, the range of the gas pressure is 0.
The purpose can be achieved by setting the amount to 100 kg / cm 2 · G, preferably 0 to 30 kg / cm 2 · G.
前述の水素ガス圧が0kg/cm2・Ｇより少ないときに
は、反応は充分に進行せず、また30kg/cm2・Ｇを超えた
圧力としても収率向上に反映しない結果となることがあ
る。When the hydrogen gas pressure is less than 0 kg / cm 2 · G, the reaction does not proceed sufficiently, and even if the pressure exceeds 30 kg / cm 2 · G, the result may not be reflected in the yield improvement.
ここで使用する水素は十分に精製されたものを用いる
のが好ましく、たとえば、水の電解、水性ガスの変性、
石油類のガス化、天然ガスの変性など種々の方法により
得られたものを使用することができる。また、場合によ
り、水素がスと不活性ガスたとえば窒素、ヘリウム、ア
ルゴンなどとの混合ガスを使用しても良い。混合ガスを
使用する場合、水素分圧が前記水素ガス圧となるように
調製するのが好ましい。It is preferable to use sufficiently purified hydrogen used here, for example, electrolysis of water, modification of water gas,
Those obtained by various methods such as gasification of petroleum and modification of natural gas can be used. In some cases, a mixed gas of hydrogen gas and an inert gas such as nitrogen, helium, or argon may be used. When a mixed gas is used, it is preferable to adjust the hydrogen partial pressure to the hydrogen gas pressure.
反応を行う時間は、通常0.5〜10時間、好ましくは１
〜８時間である。The reaction time is usually 0.5 to 10 hours, preferably 1
~ 8 hours.
この反応時間が0.5時間より短い場合には、アルキル
フェノール類が充分に生成せず、また、10時間より長く
してもアルキルフェノール類の収率向上にそれ程寄与し
なくなる傾向となる。If the reaction time is shorter than 0.5 hours, the alkylphenols are not sufficiently produced, and if the reaction time is longer than 10 hours, it tends not to contribute much to the yield improvement of the alkylphenols.
以上のような各種要因を満足させた上で実施する反応
は、回分式、半回分式あるいは連続式などの各種の反応
操作によって行うことができる。The reaction carried out after satisfying the above various factors can be carried out by various reaction operations such as a batch system, a semi-batch system or a continuous system.
この発明では、反応終了後、得られる反応生成液をろ
過するだけの簡単な操作で、アルキルフェノール類が単
離される。In the present invention, after completion of the reaction, the alkylphenols are isolated by a simple operation of filtering the obtained reaction product liquid.
［実施例］ 以下、実施例および比較例を挙げて、この発明をさら
に詳しく説明する。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１〜８および比較例１〜３ 容量300mlのオートクレーブに、2,6−ジ−ｔ−ブチル
−４−メトキシメチルフェノールを表示の量、表示の溶
媒および触媒を表示の量仕込み、水素ガスを充填して、
表示の条件で反応を行った。Examples 1 to 8 and Comparative Examples 1 to 3 An autoclave having a volume of 300 ml was charged with the indicated amount of 2,6-di-t-butyl-4-methoxymethylphenol, the indicated solvent and the indicated amount, and hydrogen gas. Fill the
The reaction was performed under the indicated conditions.
反応終了後、内容物を25℃に冷却し、ろ過することに
より触媒を分離除去して、生成物からサンプリングして
ガスクロマトグラフィーにより2,6−ジ−ｔ−ブチル−
４−メチルフェノールの収率を求めた。After the completion of the reaction, the content was cooled to 25 ° C., the catalyst was separated and removed by filtration, the product was sampled, and 2,6-di-t-butyl-
The yield of 4-methylphenol was determined.
結果を表に示す。 The results are shown in the table.
［発明の効果］ この発明によれば、反応に用いる触媒の寿命が長く、
このため反応終了後、触媒を回収して再使用しても活性
の低下がなく、きわめて効率的なアルキルフェノール類
の製造方法が提供される。しかもアルキルフェノール類
はほぼ100％に近い高収率で得うることができる。 According to the present invention, the life of the catalyst used in the reaction is long,
Therefore, after the reaction is completed, the activity is not lowered even if the catalyst is recovered and reused, and a very efficient method for producing alkylphenols is provided. Moreover, alkylphenols can be obtained in a high yield of almost 100%.
このため、酸化防止剤やその他各種の化成品原料とし
て有用なアルキルフェノール類の製造工業の分野につと
めて多大の貢献をなす製造方法が提供される。Therefore, a production method is provided which makes a great contribution to the field of the production industry of alkylphenols useful as antioxidants and other raw materials for various chemical products.
Claims (1)
は炭素数１〜10であるアルキル基を表し、R4は低級アル
キル基を表す。） で示されるアルコキシアルキル基含有アルキルフェノー
ル類を水素ガスおよび銅−クロム−バリウム系触媒また
は銅−クロム−バリウム−マンガン系触媒の存在下に接
触分解することを特徴とする次式［２］； （ただし、式［２］中、R1、R2、およびR3は前記と同じ
意味を表す。） で示されるアルキルフェノール類の製造方法。1. The following formula [1]; (However, in the formula [1], R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 4 represents a lower alkyl group.) The following formula [2] characterized by catalytically decomposing an alkylphenol in the presence of hydrogen gas and a copper-chromium-barium-based catalyst or a copper-chromium-barium-manganese-based catalyst; (However, in the formula [2], R 1 , R 2 , and R 3 have the same meanings as described above.) A method for producing an alkylphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63145893A JPH085825B2 (en) | 1988-06-15 | 1988-06-15 | Method for producing alkylphenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63145893A JPH085825B2 (en) | 1988-06-15 | 1988-06-15 | Method for producing alkylphenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01316334A JPH01316334A (en) | 1989-12-21 |
| JPH085825B2 true JPH085825B2 (en) | 1996-01-24 |
Family
ID=15395488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63145893A Expired - Fee Related JPH085825B2 (en) | 1988-06-15 | 1988-06-15 | Method for producing alkylphenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085825B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1653019A (en) * | 2002-05-13 | 2005-08-10 | 新日本理化株式会社 | Process for the preparation of methyl-substituted aromatic compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3006969A (en) | 1956-11-13 | 1961-10-31 | Shell Oil Co | Alkylated phenols |
-
1988
- 1988-06-15 JP JP63145893A patent/JPH085825B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3006969A (en) | 1956-11-13 | 1961-10-31 | Shell Oil Co | Alkylated phenols |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01316334A (en) | 1989-12-21 |
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