JP2020143017A - Method of producing terminal double bond-containing compound - Google Patents
Method of producing terminal double bond-containing compound Download PDFInfo
- Publication number
- JP2020143017A JP2020143017A JP2019041394A JP2019041394A JP2020143017A JP 2020143017 A JP2020143017 A JP 2020143017A JP 2019041394 A JP2019041394 A JP 2019041394A JP 2019041394 A JP2019041394 A JP 2019041394A JP 2020143017 A JP2020143017 A JP 2020143017A
- Authority
- JP
- Japan
- Prior art keywords
- group
- double bond
- terminal double
- containing compound
- methyl
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 32
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 30
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- -1 n-octyl group Chemical group 0.000 description 67
- 239000002994 raw material Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- LGAQJENWWYGFSN-PLNGDYQASA-N (z)-4-methylpent-2-ene Chemical compound C\C=C/C(C)C LGAQJENWWYGFSN-PLNGDYQASA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000010813 internal standard method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 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 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 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
- 125000000579 2,2-diphenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C1=C([H])C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 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
- 238000009835 boiling Methods 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本発明は、末端二重結合含有化合物を高い選択率で得ることが出来る製造方法に関するものである。 The present invention relates to a production method capable of obtaining a terminal double bond-containing compound with a high selectivity.
４−メチル−１−ペンテンなどの分子末端に二重結合を有する化合物は、オレフィン重合体の原料として有用である。二重結合を有する化合物を製造する方法としては、例えば、特許文献１には、酸化ジルコニウムを触媒に用いる、２級アルコールから二重結合を有する化合物を製造する方法が記載されている。 Compounds having a double bond at the molecular end, such as 4-methyl-1-pentene, are useful as raw materials for olefin polymers. As a method for producing a compound having a double bond, for example, Patent Document 1 describes a method for producing a compound having a double bond from a secondary alcohol using zirconium oxide as a catalyst.
特許文献２には、１重量％の水酸化ナトリウム水溶液に２０時間含浸し、乾燥した酸化ジルコニウム触媒を用いる、２級アルコールから二重結合を有する化合物を製造する方法が記載されており、この方法では、末端二重結合を有する化合物の選択率が向上している。 Patent Document 2 describes a method for producing a compound having a double bond from a secondary alcohol using a dried zirconium oxide catalyst impregnated with a 1 wt% sodium hydroxide aqueous solution for 20 hours. In, the selectivity of the compound having a terminal double bond is improved.
しかしながら、特許文献１に記載された方法では、末端二重結合含有化合物の異性体の生成割合が高いことが開示されている。即ち、特許文献１に記載された方法に対しては、末端二重結合含有化合物の更なる選択率の向上が求められていた。 However, the method described in Patent Document 1 discloses that the production ratio of isomers of the terminal double bond-containing compound is high. That is, the method described in Patent Document 1 has been required to further improve the selectivity of the terminal double bond-containing compound.
特許文献２に記載された方法でも、実用化の観点からは、末端二重結合を有する化合物の選択率が未だ満足するものとは言えない。特に、目的物が４−メチル−１−ペンテンである場合、４−メチル−１−ペンテンは、副生物である４−メチル−２−ペンテンとの沸点の差が極めて小さいこともあり、４−メチル−１−ペンテンの選択率の向上は大変重要なポイントである。 Even with the method described in Patent Document 2, from the viewpoint of practical use, it cannot be said that the selectivity of the compound having a terminal double bond is still satisfactory. In particular, when the target product is 4-methyl-1-pentene, the difference in boiling point between 4-methyl-1-pentene and 4-methyl-2-pentene, which is a by-product, may be extremely small, and 4-methyl-1-pentene is 4-methyl-1-pentene. Improving the selectivity of methyl-1-pentene is a very important point.
さらに特許文献２に記載された方法では、劇物であり、強塩基性化合物である水酸化ナトリウムの調製、触媒への含浸、含浸液の廃液処理等が必要である等、設備上の種々の制約が発生する可能性があるという問題がある。 Further, the method described in Patent Document 2 is a deleterious substance and requires preparation of sodium hydroxide, which is a strongly basic compound, impregnation into a catalyst, waste liquid treatment of an impregnating solution, and the like. There is a problem that constraints can occur.
これらの観点から、更なる選択率の向上と、より安全かつ簡単に末端二重結合を有する化合物を製造する方法の開発が要求される。
本発明の課題は、末端二重結合を有する化合物を高い選択率で、安全かつ簡単に製造する方法を提供することである。
From these viewpoints, further improvement of selectivity and development of a safer and easier method for producing a compound having a terminal double bond are required.
An object of the present invention is to provide a safe and easy method for producing a compound having a terminal double bond with a high selectivity.
本発明者らは、前記課題を解決するために鋭意検討を重ねた結果、例えば、触媒を充填した固定床流通反応器に２級アルコールを特定の圧力で流通させることにより、末端二重結合含有化合物を高選択的に合成できることを見出し、本発明を完成した。 As a result of diligent studies to solve the above problems, the present inventors, for example, by circulating a secondary alcohol at a specific pressure in a fixed bed flow reactor filled with a catalyst, contain a terminal double bond. We have found that compounds can be synthesized with high selectivity, and completed the present invention.
すなわち本発明は、金属酸化物触媒の存在下で、下記一般式（Ｉ）で表される化合物を０ＭＰａ−Ｇ未満の圧力で反応させて、下記一般式（ＩＩ）で表される末端二重結合含有化合物を製造する、末端二重結合含有化合物の製造方法である。 That is, in the present invention, the compound represented by the following general formula (I) is reacted at a pressure of less than 0 MPa-G in the presence of a metal oxide catalyst, and the terminal double represented by the following general formula (II) is reacted. This is a method for producing a terminal double bond-containing compound, which produces a bond-containing compound.
前記製造方法において、前記の反応が、２８０〜３５０℃の範囲の温度で実施されることが好ましい。
前記製造方法において、前記一般式(Ｉ) で表される化合物は４−メチル−２−ペンタノールであり、前記一般式(ＩＩ) で表される化合物は４−メチル−１−ペンテンであることが好ましい。
In the production method, it is preferable that the reaction is carried out at a temperature in the range of 280 to 350 ° C.
In the production method, the compound represented by the general formula (I) is 4-methyl-2-pentanol, and the compound represented by the general formula (II) is 4-methyl-1-pentene. Is preferable.
前記製造方法において、前記金属酸化物触媒は酸化ジルコニウムであることが好ましい。
前記製造方法の好適な態様として、固定床流通反応器に前記金属酸化物触媒を充填し、前記固定床流通反応器に前記一般式（Ｉ）で表される化合物を、０ＭＰａ−Ｇ未満の圧力で、連続的に供給する。
ここで、圧力の単位「ＭＰａ−Ｇ」とは、いわゆるメガパスカル単位の「ゲージ圧」の単位を指す。（例えば、ゼロＭＰａ−Ｇとは、常圧と実質的に同意である。）
In the production method, the metal oxide catalyst is preferably zirconium oxide.
As a preferred embodiment of the production method, the fixed bed flow reactor is filled with the metal oxide catalyst, and the fixed bed flow reactor is filled with the compound represented by the general formula (I) at a pressure of less than 0 MPa-G. And supply continuously.
Here, the unit of pressure "MPa-G" refers to the unit of "gauge pressure" in the so-called megapascal unit. (For example, zero MPa-G is substantially the same as normal pressure.)
本発明によれば、末端の二重結合を有する化合物を高い選択率で、安全かつ簡単に製造することが出来る。 According to the present invention, a compound having a double bond at the terminal can be safely and easily produced with a high selectivity.
以下、本発明に実態の形態について、詳細に説明する。
本発明は、金属酸化物触媒の存在下で、下記一般式（Ｉ）で表される化合物（以下、化合物（Ｉ）ともいう）を０ＭＰａ−Ｇ未満の圧力で反応させて、下記一般式（ＩＩ）で表される末端二重結合含有化合物（以下、化合物（ＩＩ）ともいう）を製造する、末端二重結合含有化合物の製造方法である。すなわち、本発明の末端二重結合含有化合物の製造方法は、一般式（Ｉ）で表される化合物を金属酸化物触媒の存在下で、０ＭＰａ−Ｇ未満の圧力で処理し、一般式（Ｉ）で表される化合物の水酸基と、１位の炭素原子に結合する水素原子とを脱水反応により除去して、一般式（ＩＩ）で表される末端二重結合含有化合物を製造する方法である。
Hereinafter, the actual form of the present invention will be described in detail.
In the present invention, a compound represented by the following general formula (I) (hereinafter, also referred to as compound (I)) is reacted at a pressure of less than 0 MPa-G in the presence of a metal oxide catalyst, and the following general formula (hereinafter, also referred to as compound (I)) This is a method for producing a terminal double bond-containing compound, which comprises producing the terminal double bond-containing compound represented by II) (hereinafter, also referred to as compound (II)). That is, in the method for producing a terminal double bond-containing compound of the present invention, the compound represented by the general formula (I) is treated with a pressure of less than 0 MPa-G in the presence of a metal oxide catalyst, and the general formula (I) is used. This is a method for producing a terminal double bond-containing compound represented by the general formula (II) by removing the hydroxyl group of the compound represented by) and the hydrogen atom bonded to the carbon atom at the 1-position by a dehydration reaction. ..
本発明の末端二重結合含有化合物の製造方法によれば、末端二重結合含有化合物を高い選択率で得ることができる。本発明において、末端二重結合含有化合物の選択率とは、原料として用いられた化合物（Ｉ）の反応による減少量に対する、生成した化合物（ＩＩ）の量の比率（モル比）を意味する。また、原料として用いられた化合物（Ｉ）の量に対する、前記化合物（Ｉ）の反応による減少量の比率（モル比）を転化率という。 According to the method for producing a terminal double bond-containing compound of the present invention, a terminal double bond-containing compound can be obtained with a high selectivity. In the present invention, the selectivity of the terminal double bond-containing compound means the ratio (molar ratio) of the amount of the produced compound (II) to the amount of decrease due to the reaction of the compound (I) used as a raw material. Further, the ratio (molar ratio) of the amount of decrease due to the reaction of the compound (I) to the amount of the compound (I) used as a raw material is referred to as a conversion rate.
本発明の末端二重結合含有化合物の製造方法によれば、反応の転化率を好ましくは２３％以上にすることができる。より好ましい下限は２５％、さらに好ましい下限は２７％、特に好ましい下限は３０％である。 According to the method for producing a terminal double bond-containing compound of the present invention, the conversion rate of the reaction can be preferably 23% or more. A more preferred lower limit is 25%, a more preferred lower limit is 27%, and a particularly preferred lower limit is 30%.
本発明の末端二重結合含有化合物の製造方法によれば、末端二重結合含有化合物の選択率を好ましくは８７．０％以上にすることができる。より好ましい下限は８８．０％、さらに好ましい下限は９０．０％である。したがって、本発明の工業的な価値は高いと考えられる。 According to the method for producing a terminal double bond-containing compound of the present invention, the selectivity of the terminal double bond-containing compound can be preferably 87.0% or more. A more preferable lower limit is 88.0%, and a more preferable lower limit is 90.0%. Therefore, the industrial value of the present invention is considered to be high.
上記一般式（Ｉ）および一般式（ＩＩ）におけるＲ1およびＲ2は、炭化水素基であれば、特に限定はなく、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、イソペンチル基、ｎ−ヘキシル基、ｎ−へプチル基、ｎ−オクチル基、ｎ−デシル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−エイコシル基、シクロヘキシル基、アダマンチル基等が挙げられる。 R 1 and R 2 in the general formula (I) and the general formula (II) are not particularly limited as long as they are hydrocarbon groups, and are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-. Butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, n-eicosyl group Examples thereof include a cyclohexyl group and an adamantyl group.
前記炭化水素基として、例えば炭素原子数６〜２０のアリール基を挙げることができ、炭素原子数６〜２０のアリール基としては、例えば、フェニル基、２−トリル基、３−トリル基、４−トリル基、２，３−キシリル基、２，４−キシリル基、２，５−キシリル基、２，６−キシリル基、３，４−キシリル基、３，５−キシリル基、２，３，４−トリメチルフェニル基、２，３，５−トリメチルフェニル基、２，３，６−トリメチルフェニル基、２，４，６−トリメチルフェニル基、３，４，５−トリメチルフェニル基、２，３，４，５−テトラメチルフェニル基、２，３，４，６−テトラメチルフェニル基、２，３，５，６−テトラメチルフェニル基、ペンタメチルフェニル基、２−エチルフェニル基、２，３−ジエチルフェニル基、２，３，４−トリエチルフェニル基、２−ｎ−プロピルフェニル基、２−イソプロピルフェニル基、２−ｎ−ブチルフェニル基、２−ｓｅｃ−ブチルフェニル基、２−ｔｅｒｔ−ブチルフェニル基、２−ｎ−ペンチルフェニル基、２−ネオペンチルフェニル基、２−ｎ−ヘキシルフェニル基、２−ｎ−オクチルフェニル基、２−ｎ−デシルフェニル基、２−ｎ−ドデシルフェニル基、２−ｎ−テトラデシルフェニル基、ナフチル基、アントラセニル基等が挙げられる。 Examples of the hydrocarbon group include an aryl group having 6 to 20 carbon atoms, and examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 2-tolyl group, a 3-tolyl group, and 4 -Trill group, 2,3-kisilyl group, 2,4-kisilyl group, 2,5-kisilyl group, 2,6-xsilyl group, 3,4-kisilyl group, 3,5-kisilyl group, 2,3 4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3 4,5-Tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, 2-ethylphenyl group, 2,3- Diethylphenyl group, 2,3,4-triethylphenyl group, 2-n-propylphenyl group, 2-isopropylphenyl group, 2-n-butylphenyl group, 2-sec-butylphenyl group, 2-tert-butylphenyl Group, 2-n-pentylphenyl group, 2-neopentylphenyl group, 2-n-hexylphenyl group, 2-n-octylphenyl group, 2-n-decylphenyl group, 2-n-dodecylphenyl group, 2 Examples thereof include -n-tetradecylphenyl group, naphthyl group and anthracenyl group.
前記炭化水素基として、例えば炭素原子数７〜２０のアラルキル基を挙げることができ、炭素原子数７〜２０のアラルキル基としては、例えば、ベンジル基、（２−メチルフェニル）メチル基、（３−メチルフェニル）メチル基、（４−メチルフェニル）メチル基、（２，３−ジメチルフェニル）メチル基、（２，４−ジメチルフェニル）メチル基、（２，５−ジメチルフェニル）メチル基、（２，６−ジメチルフェニル）メチル基、（３，４−ジメチルフェニル）メチル基、（４，６−ジメチルフェニル）メチル基、（２，３，４−トリメチルフェニル）メチル基、（２，３，５−トリメチルフェニル）メチル基、（２，３，６−トリメチルフェニル）メチル基、（３，４，５−トリメチルフェニル）メチル基、（２，４，６−トリメチルフェニル）メチル基、（２，３，４，５−テトラメチルフェニル）メチル基、（２，３，４，６−テトラメチルフェニル）メチル基、（２，３，５，６−テトラメチルフェニル）メチル基、（ペンタメチルフェニル）メチル基、（２−エチルフェニル）メチル基、（２−ｎ−プロピルフェニル）メチル基、（２−イソプロピルフェニル）メチル基、（２−ｎ−ブチルフェニル）メチル基、（２−ｓｅｃ−ブチルフェニル）メチル基、（２−ｔｅｒｔ−ブチルフェニル）メチル基、（２−ｎ−ペンチルフェニル）メチル基、（２−ネオペンチルフェニル）メチル基、（２−ｎ−ヘキシルフェニル）メチル基、（２−ｎ−オクチルフェニル）メチル基、（２−ｎ−デシルフェニル）メチル基、（２−ｎ−デシルフェニル）メチル基、（２−ｎ−テトラデシルフェニル）メチル基、ナフチルメチル基、アントラセニルメチル基、２−フェニルエチル基、３−フェニルプロピル基、４−フェニルブチル基、ジフェニルメチル基、２，２−ジフェニルエチル基、３，３−ジフェニルプロピル基、４，４−ジフェニルブチル基等が挙げられる。 Examples of the hydrocarbon group include an aralkyl group having 7 to 20 carbon atoms, and examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a (2-methylphenyl) methyl group, and (3). -Methylphenyl) Methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, ( 2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3) 5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,6) 3,4,5-Tetramethylphenyl) Methyl Group, (2,3,4,5-Tetramethylphenyl) Methyl Group, (2,3,5,6-Tetramethylphenyl) Methyl Group, (Pentamethylphenyl) Methyl group, (2-ethylphenyl) methyl group, (2-n-propylphenyl) methyl group, (2-isopropylphenyl) methyl group, (2-n-butylphenyl) methyl group, (2-sec-butylphenyl) ) Methyl group, (2-tert-butylphenyl) methyl group, (2-n-pentylphenyl) methyl group, (2-neopentylphenyl) methyl group, (2-n-hexylphenyl) methyl group, (2-n-hexylphenyl) methyl group n-octylphenyl) methyl group, (2-n-decylphenyl) methyl group, (2-n-decylphenyl) methyl group, (2-n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl Group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, diphenylmethyl group, 2,2-diphenylethyl group, 3,3-diphenylpropyl group, 4,4-diphenylbutyl group and the like. Be done.
これらの中でもより好ましくは、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等のアルキル基、ビニル基、アリル基等のアルケニル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、フェニル基、トリル基、キシリル基等の芳香族基等が挙げられる。さらに好ましくは、直鎖状の炭化水素基であり、具体的にはメチル基、エチル基、ｎ−プロピル基であり、特に好ましくはメチル基である。 Of these, more preferably, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, a vinyl group, an allyl group and the like. Examples thereof include cycloalkyl groups such as alkenyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group, and aromatic groups such as phenyl group, tolyl group and xsilyl group. More preferably, it is a linear hydrocarbon group, specifically, a methyl group, an ethyl group, an n-propyl group, and particularly preferably a methyl group.
上記一般式（Ｉ）および一般式（ＩＩ）におけるＲ1およびＲ2が結合し、Ｒ1およびＲ2が結合している炭素原子とともに形成される環としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等が挙げられる。 The rings formed by the carbon atoms in which R 1 and R 2 in the general formula (I) and the general formula (II) are bonded and R 1 and R 2 are bonded include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The basis etc. can be mentioned.
上記化合物（Ｉ）として特に好ましいのは４−メチル−２−ペンタノールであり、上記化合物（ＩＩ）として特に好ましいのは４−メチル−１−ペンテンである。
また化合物（Ｉ）は、必要に応じて、溶媒と併用することも可能である。溶媒としては、公知の化合物を制限なく用いることが出来るが、好ましくは炭化水素溶媒、更には脂肪族炭化水素溶媒が好ましい。具体的にはヘキサン、シクロヘキサン、ヘプタン、オクタン、デカン、メチルシクロヘキサン、エチルシクロヘキサン等を挙げることが出来る。
4-Methyl-2-pentanol is particularly preferable as the compound (I), and 4-methyl-1-pentene is particularly preferable as the compound (II).
Compound (I) can also be used in combination with a solvent, if necessary. As the solvent, known compounds can be used without limitation, but a hydrocarbon solvent is preferable, and an aliphatic hydrocarbon solvent is preferable. Specific examples thereof include hexane, cyclohexane, heptane, octane, decane, methylcyclohexane, ethylcyclohexane and the like.
前記金属酸化物触媒としては、化合物（Ｉ）の脱水反応を触媒することができれば特に制限されない。例えば周期表の１〜４族、１１〜１４族の金属元素の酸化物を例示することが出来る。具体例としては、酸化ジルコニウム、酸化カルシウム、酸化イットリウム、酸化アルミニウム、シリカアルミナ、ゼオライト、チタニア等が挙げられる。これらの中で、前記金属酸化物触媒としては、化合物（ＩＩ）の高い選択率が得られる観点から、酸化ジルコニウムが特に好ましい。 The metal oxide catalyst is not particularly limited as long as it can catalyze the dehydration reaction of compound (I). For example, oxides of metal elements of groups 1 to 4 and 11 to 14 of the periodic table can be exemplified. Specific examples include zirconium oxide, calcium oxide, yttrium oxide, aluminum oxide, silica-alumina, zeolite, titania and the like. Among these, zirconium oxide is particularly preferable as the metal oxide catalyst from the viewpoint of obtaining a high selectivity of the compound (II).
前記の金属酸化物は、そのまま用いてもよいが、例えば、触媒を固定床に配置する態様で用いる場合、嵩密度を高めて触媒効率を高めたり、原料の固定床内での流動性を考慮すると、例えば、打錠成形を行い、形状のそろった粒子や錠剤として用いることが好ましい。この際の粒子径は、好ましくは１〜２０ｍｍである。また、好ましいアスペクト比は１〜３である。 The metal oxide may be used as it is, but for example, when the catalyst is used in a fixed bed arrangement, the bulk density is increased to increase the catalyst efficiency, and the fluidity of the raw material in the fixed bed is taken into consideration. Then, for example, it is preferable to perform tableting molding and use it as particles or tablets having a uniform shape. The particle size at this time is preferably 1 to 20 mm. The preferred aspect ratio is 1-3.
本発明の末端二重結合含有化合物の製造方法において、化合物（Ｉ）と金属酸化物との質量比（化合物（Ｉ）／触媒）は、０．１〜１０であることが好ましく、０．３〜５であることがより好ましく、０．５〜２．０であることがさらに好ましい。い。前記質量比が前記範囲内であると、高い反応速度が得られ、効率的な化合物（ＩＩ）の製造が容易になる。 In the method for producing a terminal double bond-containing compound of the present invention, the mass ratio of compound (I) to a metal oxide (compound (I) / catalyst) is preferably 0.1 to 10, preferably 0.3. It is more preferably ~ 5, and even more preferably 0.5 to 2.0. No. When the mass ratio is within the above range, a high reaction rate can be obtained, and efficient production of the compound (II) becomes easy.
本発明の末端二重結合含有化合物の製造方法において、反応圧力は、０ＭＰａ−Ｇ未満であり、好ましくは、−０．０５ＭＰａＭＰａ−Ｇ以下、さらに好ましくは−０．０８ＭＰａ−Ｇ以下である。反応圧力は低いほど、化合物（Ｉ）の転化率や４−メチルー１−ペンテン等の化合物（ＩＩ）の選択率が高くなる点で、好ましい。 In the method for producing a terminal double bond-containing compound of the present invention, the reaction pressure is less than 0 MPa-G, preferably -0.05 MPaMPa-G or less, and more preferably -0.08 MPa-G or less. The lower the reaction pressure, the higher the conversion rate of compound (I) and the selectivity of compound (II) such as 4-methyl-1-pentene, which is preferable.
反応圧力の下限値は特に制約はない。ただし、原料化合物である化合物（Ｉ）の蒸気圧以下の条件では、反応効率が低下する可能性がある。この為、用いる原料の種類にもよるが、反応圧力の好ましい下限値は−０．９５ＭＰａ−Ｇ、より好ましくは−０．８ＭＰａ−Ｇ、更には−０．５ＭＰａ−Ｇ、特には−０．３ＭＰａ−Ｇである。 The lower limit of the reaction pressure is not particularly limited. However, the reaction efficiency may decrease under the condition of the vapor pressure or less of the raw material compound (I). Therefore, although it depends on the type of raw material used, the preferable lower limit of the reaction pressure is -0.95 MPa-G, more preferably -0.8 MPa-G, further -0.5 MPa-G, and particularly -0. It is 3 MPa-G.
反応圧力が所定の圧力を超えると、反応速度および末端二重結合含有化合物である化合物（ＩＩ）の選択率が低下する傾向がある。
本発明の末端二重結合含有化合物の製造方法において、反応温度は、通常２００〜４００℃であり、好ましくは２８０〜３５０℃である。反応温度が２００未満では脱水反応速度が著しく低下する場合があり、反応温度が４００℃を超えると末端二重結合含有化合物である化合物（ＩＩ）の選択率が著しく低下する場合がある。
When the reaction pressure exceeds a predetermined pressure, the reaction rate and the selectivity of compound (II), which is a terminal double bond-containing compound, tend to decrease.
In the method for producing a terminal double bond-containing compound of the present invention, the reaction temperature is usually 200 to 400 ° C, preferably 280 to 350 ° C. If the reaction temperature is less than 200, the dehydration reaction rate may be significantly reduced, and if the reaction temperature exceeds 400 ° C., the selectivity of compound (II), which is a terminal double bond-containing compound, may be significantly reduced.
本発明の末端二重結合含有化合物の製造方法において、その反応時間や滞留時間は、通常０．１〜１０時間である。好ましい上限値は７時間、より好ましくは５時間である。上記の範囲であれば、効率よく反応を進めることが出来る。 In the method for producing a terminal double bond-containing compound of the present invention, the reaction time and residence time are usually 0.1 to 10 hours. The preferred upper limit is 7 hours, more preferably 5 hours. Within the above range, the reaction can proceed efficiently.
本発明の末端二重結合含有化合物の製造方法においては、０ＭＰａ−Ｇ未満という特定の圧力範囲で反応を行うことにより、末端二重結合含有化合物である化合物（ＩＩ）が高い選択率で製造される。末端二重結合含有化合物の選択率が高まる原因は、現時点で解明されていない。ただ、本発明者らは、以下のような推察を行っている。 In the method for producing a terminal double bond-containing compound of the present invention, compound (II), which is a terminal double bond-containing compound, is produced with a high selectivity by carrying out the reaction in a specific pressure range of less than 0 MPa-G. To. The cause of the increased selectivity of end double bond-containing compounds has not been elucidated at this time. However, the present inventors make the following inferences.
本発明の製造方法において、目的物である末端二重結合含有化合物は、対応するアルコール化合物である化合物（Ｉ）の脱水反応によって得られると考えられる。
通常、酸触媒による脱水反応は、内部オレフィン構造を有する化合物生成の選択的が高いことが知られている。一方、塩基触媒を用いると、酸化が優先する。例えば、酸性サイトと塩基性サイトとが適切な割合で近傍に存在する触媒では、酸性サイトがアルコールの酸素原子と相互作用を持ち、特に本発明に用いる化合物（Ｉ）の様な構造のアルコールの場合、その立体構造の影響で塩基性のサイトはα位の水素（末端の炭素に結合する水素）と相互作用を持ち易い傾向にあるであろう。そうであれば、結果的に上記の脱水反応によってＯＨ基とα位の水素とがアルコール化合物から脱離して、末端二重結合含有化合物が得られることが推測される。
In the production method of the present invention, the target end double bond-containing compound is considered to be obtained by the dehydration reaction of the corresponding alcohol compound (I).
Generally, it is known that the acid-catalyzed dehydration reaction is highly selective for producing compounds having an internal olefin structure. On the other hand, when a base catalyst is used, oxidation has priority. For example, in a catalyst in which acidic sites and basic sites are present in an appropriate ratio in the vicinity, the acidic sites interact with the oxygen atom of the alcohol, and in particular, the alcohol having a structure like compound (I) used in the present invention. In this case, the basic site will tend to interact with the hydrogen at the α-position (hydrogen bonded to the terminal carbon) due to its three-dimensional structure. If so, it is presumed that as a result, the OH group and the hydrogen at the α-position are desorbed from the alcohol compound by the above dehydration reaction to obtain a terminal double bond-containing compound.
ここで、例えば、本発明に用いられる金属酸化物触媒に、酸性のサイトと塩基性サイトとが存在していると仮定した場合、通常の条件では、脱水反応によって発生する水分子が塩基性のサイトの働きを弱める傾向があること、あるいは、原料のアルコールと水とが相互作用を持ちながら塩基性のサイトの働きを弱めることで、内部オレフィン構造を有する化合物の選択率が高まる傾向があることが考えられる。 Here, for example, assuming that the metal oxide catalyst used in the present invention has acidic sites and basic sites, under normal conditions, the water molecules generated by the dehydration reaction are basic. There is a tendency to weaken the function of the site, or by weakening the function of the basic site while having an interaction between the raw material alcohol and water, the selectivity of the compound having an internal olefin structure tends to increase. Can be considered.
上記の仮説に従えば、本発明では、減圧環境にすることにより、水と触媒との相互作用を弱める、あるいは水を効率的に除去することで、塩基性サイトの機能を高め、その結果、末端二重結合含有化合物の選択率を高めることが出来たのではないかと推測される。 According to the above hypothesis, in the present invention, the reduced pressure environment weakens the interaction between water and the catalyst, or efficiently removes water to enhance the function of the basic site, and as a result, It is speculated that the selectivity of the terminal double bond-containing compound could be increased.
本発明の末端二重結合含有化合物の製造方法において、化合物（Ｉ）の上記反応の反応形式としては、液相反応又は気相反応のどちらでも良く、例えば、槽型反応器を用いる回分式、半連続式もしくは連続式のスラリー法、又は管型反応器を用いる連続式の固定床法等が挙げられる。槽型反応器としては、通常、一段又は多段の混合槽が使用される。管型反応器としては、単管又は多数の管を並列に配列した多管式熱交換型の構造を持つものを単一又は複数を直列にさせた固定床反応器が挙げられる。大規模な工業的操作の場合には、操作性、経済性の観点から、管型反応器を用いる連続式の固定床法等による気相反応が好ましい。 In the method for producing a terminal double bond-containing compound of the present invention, the reaction form of the above reaction of compound (I) may be either a liquid phase reaction or a gas phase reaction, for example, a batch type using a tank reactor. Examples thereof include a semi-continuous type or a continuous type slurry method, a continuous type fixed bed method using a tubular reactor, and the like. As the tank reactor, a one-stage or multi-stage mixing tank is usually used. Examples of the tubular reactor include a fixed bed reactor in which one or a plurality of reactors having a multi-tube heat exchange type structure in which a single tube or a large number of tubes are arranged in parallel are connected in series. In the case of a large-scale industrial operation, a gas phase reaction by a continuous fixed bed method using a tubular reactor or the like is preferable from the viewpoint of operability and economy.
本発明の末端二重結合含有化合物の製造方法を、管型反応器を用いる連続式の固定床法による気相反応により実施する場合、管型反応器に前記金属酸化物触媒を充填し、管型反応器に前記化合物（Ｉ）を連続的に供給すればよい。このとき、管型反応器内の圧力が０ＭＰａ−Ｇ未満になるように調整する。前記化合物（Ｉ）の供給速度は、ＷＨＳＶ（重量空間速度）が０．０１〜１０．０ｈｒ-1であることが好ましく、より好ましい上限値は３．０ｈｒ-1であり、さらに好ましくは１．０ｒ-1である。一方より好ましい下限値は０．０５ｈｒ-1であり、さらに好ましくは０．１ｈｒ-1である。 When the method for producing a terminal double bond-containing compound of the present invention is carried out by a gas phase reaction by a continuous fixed bed method using a tubular reactor, the tubular reactor is filled with the metal oxide catalyst and a tube is used. The compound (I) may be continuously supplied to the type reactor. At this time, the pressure in the tubular reactor is adjusted to be less than 0 MPa-G. The supply rate of the compound (I) is preferably WHSV (weight space velocity) of 0.01 to 10.0 hr -1 , and a more preferable upper limit is 3.0 hr -1 , and more preferably 1. It is 0r -1 . On the other hand, a more preferable lower limit value is 0.05 hr -1 , and even more preferably 0.1 hr -1 .
以下に実施例に基づいて本発明をより詳細に説明する。
４−メチル−２−ペンタノール（ＭＩＢＣ）の転化率、４−メチル−１−ペンテン（４ＭＰ１）の選択率、ならびに副生物である４−メチル−２−ぺンテン（４ＭＰ２）およびメチルイソブチルケトン（ＭＩＢＫ）の選択率は、ガスクロマトグラフィー組成分析値から求めた。
The present invention will be described in more detail below based on examples.
Conversion rate of 4-methyl-2-pentanol (MIBC), selectivity of 4-methyl-1-pentene (4MP1), and by-products 4-methyl-2-pentene (4MP2) and methyl isobutyl ketone ( The selectivity of MIBK) was determined from the gas chromatography composition analysis value.
詳細な分析条件を下に示す。
使用機器： ＧＣ-２０１０plus
使用カラム：ＤＢ-５ （df ＝1.0 μm, ID =0.25 mm, L =60m）
INJ： 200℃ DET(FID)： 200℃
オーブンプログラム：40℃, 7 min保持 →5℃/minで170℃まで昇温→ 170℃, 5min 保持
キャリアガス： N2
制御モード： 圧力
圧力 ： 100.0 kPa
全流量 ： 35.4 mL/min SPL : 49
主要成分のR.T（ピーク位置の時間（min））：
アセトン 10.5
IPA 10.7
4MP-1 13.4
cis-4MP-2 13.9
trans-4MP-2 14.1
MIBK 23.5
MIBC 24.6
トルエン(内標) 25.5
Detailed analysis conditions are shown below.
Equipment used: GC-2010plus
Column used: DB-5 (df = 1.0 μm, ID = 0.25 mm, L = 60 m)
INJ: 200 ℃ DET (FID): 200 ℃
Oven program: 40 ° C, 7 min retention → Heat up to 170 ° C at 5 ° C / min → 170 ° C, 5 min retention Carrier gas: N2
Control mode: Pressure Pressure: 100.0 kPa
Total flow rate: 35.4 mL / min SPL: 49
Main component RT (peak position time (min)):
Acetone 10.5
IPA 10.7
4MP-1 13.4
cis-4MP-2 13.9
trans-4MP-2 14.1
MIBK 23.5
MIBC 24.6
Toluene (internal standard) 25.5
具体的には、４−メチル−２−ペンタノールの転化率は、使用した原料の４−メチルー２−ペンタノールのモル量から、内標法によって求めた反応後の４−メチル−２−ペンタノールのモル量を引き算し、前記原料４−メチルー２−ペンタノールのモル量で割った値とした。４−メチル−１−ペンテンの選択率は、内標法によって求めた反応後の４−メチル−１−ペンテンのモル量を、使用した原料の４−メチル−２−ペンタノールのモル量から内標法によって求めた反応後の４−メチル−２−ペンタノールのモル量を引き算した値で割った値とした。４−メチル−２−ぺンテンおよびメチルイソブチルケトンの選択率は、上記４−メチル−１−ペンテンと同様に、内標法によって求めた反応後の４−メチル−２−ペンテンもしくはメチルイソブチルケトンのモル量を、使用した原料の４−メチル−２−ペンタノールのモル量から内標法によって求めた反応後の４−メチル−２−ペンタノールのモル量を引き算した値で割った値とした。 Specifically, the conversion rate of 4-methyl-2-pentanol was determined from the molar amount of 4-methyl-2-pentanol used as the raw material after the reaction by the internal standard method. The molar amount of tanol was subtracted and divided by the molar amount of the raw material 4-methyl-2-pentanol. The selectivity of 4-methyl-1-pentene is such that the molar amount of 4-methyl-1-pentene after the reaction determined by the internal standard method is included in the molar amount of 4-methyl-2-pentanol used as the raw material. The value was obtained by dividing the molar amount of 4-methyl-2-pentanol after the reaction determined by the standard method by the subtracted value. The selectivity of 4-methyl-2-pentene and methyl isobutyl ketone is the same as that of 4-methyl-1-pentene described above, that of 4-methyl-2-pentene or methyl isobutyl ketone after the reaction determined by the internal standard method. The molar amount was calculated by dividing the molar amount of 4-methyl-2-pentanol of the raw material used by subtracting the molar amount of 4-methyl-2-pentanol after the reaction obtained by the internal standard method. ..
［実施例１］
金属製管型反応器（内径１５ｍｍ、長さ５０ｃｍ）に第一稀元素化学工業社製の酸化ジルコニウム（商品名：Ｚ−２９７８）を１３．４２ｇ充填し（充填長６．８ｃｍ）、金属製管型反応器内の圧力を−０．０８ＭＰａ−Ｇ、温度を３２０℃とした条件下で、金属製管型反応器に４−メチル−２−ペンタノールを０．１５ｍＬ／ｍｉｎの速度で供給した。金属製管型反応器から排出されたガスをガスクロマトグラフィーにより分析し、４−メチル−２−ペンタノールの転化率、ならびに４−メチル−１−ペンテン、４−メチル−２−ぺンテンおよびメチルイソブチルケトンの選択率を求めた。結果を表１に示す。
[Example 1]
A metal tube reactor (inner diameter 15 mm, length 50 cm) is filled with 13.42 g of zirconium oxide (trade name: Z-2978) manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. (filling length 6.8 cm) and made of metal. 4-Methyl-2-pentanol is supplied to the metal tubular reactor at a rate of 0.15 mL / min under the conditions that the pressure in the tubular reactor is -0.08 MPa-G and the temperature is 320 ° C. did. The gas discharged from the metal tube reactor was analyzed by gas chromatography, and the conversion rate of 4-methyl-2-pentanol, as well as 4-methyl-1-pentene, 4-methyl-2-pentene and methyl were analyzed. The selectivity of isobutyl ketone was determined. The results are shown in Table 1.
［比較例１］
金属製管型反応器内の圧力を０．０５ＭＰａ−Ｇとしたこと以外は実施例１と同様の操作を行った。結果を表１に示す。
[Comparative Example 1]
The same operation as in Example 1 was performed except that the pressure in the metal tube reactor was set to 0.05 MPa-G. The results are shown in Table 1.
［比較例２］
金属製管型反応器内の圧力を０．５０ＭＰａ−Ｇとしたこと以外は実施例１と同様の操作を行った。結果を表１に示す。
[Comparative Example 2]
The same operation as in Example 1 was carried out except that the pressure in the metal tube reactor was 0.50 MPa-G. The results are shown in Table 1.
［比較例３］
金属製管型反応器内の圧力を０．９０ＭＰａ−Ｇとしたこと以外は実施例１と同様の操作を行った。結果を表１に示す。
[Comparative Example 3]
The same operation as in Example 1 was carried out except that the pressure in the metal tube reactor was 0.90 MPa-G. The results are shown in Table 1.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019041394A JP2020143017A (en) | 2019-03-07 | 2019-03-07 | Method of producing terminal double bond-containing compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019041394A JP2020143017A (en) | 2019-03-07 | 2019-03-07 | Method of producing terminal double bond-containing compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2020143017A true JP2020143017A (en) | 2020-09-10 |
Family
ID=72353180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019041394A Pending JP2020143017A (en) | 2019-03-07 | 2019-03-07 | Method of producing terminal double bond-containing compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2020143017A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3961676A1 (en) | 2020-08-26 | 2022-03-02 | Tokyo Ohka Kogyo Co., Ltd. | Etching method and photosensitive resin composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153230A (en) * | 1984-08-24 | 1986-03-17 | Sumitomo Chem Co Ltd | Production of compound having bouble bond at terminal |
| JPS61130240A (en) * | 1984-11-28 | 1986-06-18 | Sumitomo Chem Co Ltd | Production of compound containing double bond at end |
| JPS62114649A (en) * | 1985-11-11 | 1987-05-26 | Sumitomo Chem Co Ltd | Preparation of compound having double bond at terminal |
| JPH01213237A (en) * | 1988-02-19 | 1989-08-28 | Sumitomo Chem Co Ltd | Production of vinylcyclohexane |
| JP2004284993A (en) * | 2003-03-24 | 2004-10-14 | Nippon Oxirane Kk | Method for producing both propylene oxide and styrene monomer |
| JP2011184385A (en) * | 2010-03-10 | 2011-09-22 | Sumitomo Chemical Co Ltd | Method for producing double-bond-bearing compound |
-
2019
- 2019-03-07 JP JP2019041394A patent/JP2020143017A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153230A (en) * | 1984-08-24 | 1986-03-17 | Sumitomo Chem Co Ltd | Production of compound having bouble bond at terminal |
| JPS61130240A (en) * | 1984-11-28 | 1986-06-18 | Sumitomo Chem Co Ltd | Production of compound containing double bond at end |
| JPS62114649A (en) * | 1985-11-11 | 1987-05-26 | Sumitomo Chem Co Ltd | Preparation of compound having double bond at terminal |
| JPH01213237A (en) * | 1988-02-19 | 1989-08-28 | Sumitomo Chem Co Ltd | Production of vinylcyclohexane |
| JP2004284993A (en) * | 2003-03-24 | 2004-10-14 | Nippon Oxirane Kk | Method for producing both propylene oxide and styrene monomer |
| JP2011184385A (en) * | 2010-03-10 | 2011-09-22 | Sumitomo Chemical Co Ltd | Method for producing double-bond-bearing compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3961676A1 (en) | 2020-08-26 | 2022-03-02 | Tokyo Ohka Kogyo Co., Ltd. | Etching method and photosensitive resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2006514085A (en) | Method for producing dimethyl ether from methanol | |
| JP5919198B2 (en) | Catalyst for producing olefin from alcohol, method for producing olefin, polyolefin and olefin oxide | |
| JP6386909B2 (en) | Method for producing copper-based catalyst precursor for isomerization | |
| JP2011148720A (en) | Method for producing butadiene | |
| CN107107042A (en) | Prepare catalyst of glycol ether and its preparation method and application | |
| JPH01203035A (en) | Method for performing exothermic reaction between two or more kinds of reactants under substantially isothermal condition in fixed bed catalytic reactor | |
| JPWO2009013964A1 (en) | Method for reactivating metathesis catalyst and method for producing olefins including reactivation step thereof | |
| JPH0288529A (en) | Oligomerization of olefin | |
| JP2020143017A (en) | Method of producing terminal double bond-containing compound | |
| JP6091310B2 (en) | Method for producing butadiene | |
| JP2014513049A (en) | Method for producing high-purity isobutene using glycol ether | |
| JP2016098149A (en) | Manufacturing method of aei type zeolite | |
| CN108097324A (en) | A kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof | |
| EP0589557A2 (en) | Preparation of silica-alumine supported catalysts and of tertiary olefins by means of these catalysts | |
| JP2020143018A (en) | Method of producing terminal double bond-containing compound | |
| US4357479A (en) | Production of alcohols | |
| JP6426711B2 (en) | Method for producing unsaturated hydrocarbon | |
| CN102791375A (en) | Catalyst composition for direct conversion of ethanol to propylene | |
| JP2694180B2 (en) | Cumene recipe | |
| WO2012157578A1 (en) | Catalyst for producing alcohol compound or olefin compound, and method for producing alcohol compound or olefin compound | |
| EP3315194B1 (en) | Catalyst for glycerin dehydration reaction, preparation method therefor, and method for preparing acrolein by using catalyst | |
| CN110577459A (en) | Method for preparing low-carbon olefin and coproducing aromatic hydrocarbon by using methanol and/or dimethyl ether | |
| US4405499A (en) | Zeolite-ruthenium-borane catalyst composition | |
| WO2014196517A1 (en) | Production method for olefin, and dehydration catalyst employed in same | |
| JPH0231695B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220117 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230110 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230704 |