JP4413919B2 - スチレン系オレフィンの新しい製造方法 - Google Patents
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 119
- 238000004519 manufacturing process Methods 0.000 title claims description 49
- 150000001336 alkenes Chemical class 0.000 title claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 49
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000007858 starting material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 18
- -1 alkyl sulfone Chemical class 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000005264 aryl amine group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005104 aryl silyl group Chemical group 0.000 claims description 4
- 125000005110 aryl thio group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000003106 haloaryl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000005353 silylalkyl group Chemical group 0.000 claims description 4
- 238000001577 simple distillation Methods 0.000 claims description 4
- 125000004149 thio group Chemical group *S* 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims description 3
- 241001120493 Arene Species 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001502 aryl halides Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 238000004440 column chromatography Methods 0.000 claims 1
- 238000010898 silica gel chromatography Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006297 dehydration reaction Methods 0.000 description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 9
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006384 oligomerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- IMXTYZIZHGRRMC-UHFFFAOYSA-N 1-(4-butylphenyl)ethanol Chemical compound CCCCC1=CC=C(C(C)O)C=C1 IMXTYZIZHGRRMC-UHFFFAOYSA-N 0.000 description 1
- CYEIZTMWVNXOQH-UHFFFAOYSA-N 1-(4-cyclohexylphenyl)ethanol Chemical compound C1=CC(C(O)C)=CC=C1C1CCCCC1 CYEIZTMWVNXOQH-UHFFFAOYSA-N 0.000 description 1
- QOWWXERCAKCLCM-UHFFFAOYSA-N 1-(4-hexylphenyl)ethanol Chemical compound CCCCCCC1=CC=C(C(C)O)C=C1 QOWWXERCAKCLCM-UHFFFAOYSA-N 0.000 description 1
- SFVHIVPPUKKRCA-UHFFFAOYSA-N 1-[4-(3-bicyclo[2.2.1]heptanyl)phenyl]ethanol Chemical compound C1=CC(C(O)C)=CC=C1C1C(C2)CCC2C1 SFVHIVPPUKKRCA-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-SPBYTNOZSA-N 1-phenylethanol Chemical group [13CH3][13CH](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-SPBYTNOZSA-N 0.000 description 1
- PNEYDEFKLLISRB-UHFFFAOYSA-N 1-phenylethanol;toluene Chemical compound CC1=CC=CC=C1.CC(O)C1=CC=CC=C1 PNEYDEFKLLISRB-UHFFFAOYSA-N 0.000 description 1
- DJXNOUQKRHKGOS-UHFFFAOYSA-N 2-(1-phenylcyclohexa-2,4-dien-1-yl)ethanol Chemical compound C=1C=CC=CC=1C1(CCO)CC=CC=C1 DJXNOUQKRHKGOS-UHFFFAOYSA-N 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
- 0 CC(c1c(*)c(*)c(*)c(*)c1*)O Chemical compound CC(c1c(*)c(*)c(*)c(*)c1*)O 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/10—Chlorides
- C07C2527/11—Hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
- C07C2527/173—Phosphoric acid or other acids with the formula Hn+2PnO3n+1
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/025—Sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Description
トルエンが含有された2口フラスコに適正量のパラ−トルエンスルホン酸を溶かし、ディーン・スターク・トラップ(Dean‐Stark trap)と滴下漏斗(dropping funnel)をそれぞれ設けた。次に、設けられた滴下漏斗には1.0M濃度の1−フェニル−エタノールトルエン溶液を加えた。外部加熱によりトルエン溶液の温度を昇温させて還流状態を確認した後、滴下漏斗を使用して徐々に一定速度で所定時間アルコール溶液を滴加した。
1H NMR (CDCl3):δ5.22 (d, 1H), 5.72 (d, 1H), 6.70 (q, 1H), 7.31 (m, 3H), 7.39 (d, 2H)
1−(パラ−n−ブチルフェニル)−エタノールを使用して前記実施例1と同様に反応させ、但し、下記表2のような反応条件で実施して、下記化学式4のスチレンを製造した。
1H NMR (CDCl3):δ0.75 (t, 3H), 1.15 (sextet, 2H), 1.41 (quintet, 2H), 2.41 (t, 2H), 5.01 (d, 1H), 5.52 (d, 1H), 6.52 (q, 1H), 6.97 (d, 2H), 7.17 (d, 2H)
1−(パラ−n−ヘキシルフェニル)−エタノールを使用して前記実施例1と同様に反応させ、但し、下記表3のような反応条件で実施して、下記化学式5のスチレンを製造した。
1H NMR (CDCl3):δ0.88 (t, 3H), 1.28 (m, 6H), 1.60 (quintet, 2H), 2.58 (t, 2H), 5.18 (d, 1H), 5.68 (d, 1H), 6.69 (q, 1H), 7.13 (d, 2H), 7.30 (d, 2H)
1−(パラ−シクロヘキシルフェニル)−エタノールを使用して前記実施例1と同様に反応させ、但し、下記表4のような反応条件で実施して、下記化学式6のスチレンを製造した。
1H NMR (CDCl3):δ1.30 (m, 1H), 1.46 (m, 4H), 1.78 (m, 1H), 1.88 (m, 4H), 2.53 (s, 1H), 5.21 (d, 1H), 5.73 (d, 1H), 6.73 (q, 1H), 7.20 (d, 2H), 7.37 (d, 2H)
1−(パラ−(2−ノルボルニル)フェニル)−エタノールを使用して前記実施例1と同様に反応させ、但し、下記表5のような反応条件で実施して、下記化学式7のスチレンを製造した。
1H NMR (CDCl3):δ143-1.50 (m, 7H), 1.76 (m, 2H), 1.88 (s, 1H), 2.78 (s, 1H), 5.18 (d, 1H), 5.61 (d, 1H), 6.63 (q, 1H), 7.10 (d, 2H), 7.25 (d, 2H)
1−(ビフェニル)−エタノールを使用して前記実施例1と同様に反応させ、但し、下記表6のような反応条件で実施して、下記化学式8のスチレンを製造した。
1H NMR (CDCl3):δ5.20 (d, 1H), 5.63 (d, 1H), 6.70 (q, 1H), 7.22 (t, 1H), 7.30 (d, 2H), 7.36 (d, 2H), 7.41 (d, 2H), 7.47 (d, 2H)
前記実施例1〜実施例6で得たスチレン系誘導体の製造の結果、ベンゼン環に長いアルキル鎖(C6以上)又はsec−、tert−アルキルが導入された1−アルキルフェニル−エタノールを使用して多様な合成を試みて、下記表7のような反応条件と結果を得た。
ディーン・スターク・トラップが設けられた2口フラスコに1−フェニル−エタノールと適正量のパラ−トルエンスルホン酸をトルエンに共に溶かし、外部加熱により溶液の温度を昇温させて還流させた。
1H NMR (CDCl3):δ5.22 (d, 1H), 5.72 (d, 1H), 6.70 (q, 1H), 7.31 (m, 3H), 7.39 (d, 2H)
前記比較例1と同様に反応させ、但し、下記表9のような反応条件で実施して、下記化学式4、5、6のアルキルスチレンを製造した。
1H NMR (CDCl3):δ0.75 (t, 3H), 1.15 (sextet, 2H), 1.41 (quintet, 2H), 2.41 (t, 2H), 5.01 (d, 1H), 5.52 (d, 1H), 6.52 (q, 1H), 6.97 (d, 2H), 7.17 (d, 2H)
1H NMR (CDCl3):δ0.88 (t, 3H), 1.28 (m, 6H), 1.60 (quintet, 2H), 2.58 (t, 2H), 5.18 (d, 1H), 5.68 (d, 1H), 6.69 (q, 1H), 7.13 (d, 2H), 7.30 (d, 2H)
1H NMR (CDCl3):δ1.30 (m, 1H), 1.46 (m, 4H), 1.78 (m, 1H), 1.88 (m, 4H), 2.53 (s, 1H), 5.21 (d, 1H), 5.73 (d, 1H), 6.73 (q, 1H), 7.20 (d, 2H), 7.37 (d, 2H)
Claims (9)
- 反応器に触媒と溶媒を添加して昇温させて還流状態を形成する還流形成段階であって、前記触媒が、酢酸、ハロ酢酸、燐酸、塩酸、硫酸、炭素原子数1〜20のアルキルスルホン酸、アリールスルホン酸、アルキルアリールスルホン酸、ハロアリールスルホン酸、アルキルハロアリールスルホン酸、アルキルカルボン酸、アリールカルボン酸、ハロアルキルカルボン酸、ハロアリールカルボン酸、及びアルキルハロアリールカルボン酸からなる群から1以上選択され、前記溶媒が、炭素原子数1〜20のアルカン、シクロアルカン、アレーン、アルキルアレーン、ハロアルカン、ハロシクロアルカン、ハロアレーン、及びアルキルハロアレーンからなる群から1以上選択される、段階と、
前記反応器に前記溶媒中のアルコール出発物質を0.05〜5Mの濃度で0.1〜4時間滴加するアルコール出発物質滴加段階であって、前記アルコール出発物質が、下記の式1:
で表される物質である、段階と、
前記アルコール出発物質を最後に加えた後、直後に又は2時間以内に加熱を停止する段階と、
前記アルコール出発物質の滴加により形成される水を前記反応器から除去する水除去段階と、
前記の各段階を経て生成されたスチレン系オレフィンを精製する精製段階と、
を含んでなることを特徴とする、以下の式2:
で表されるスチレン系オレフィンの製造方法。 - 前記触媒が、前記アルコール出発物質に対して0.1〜20モル%であることを特徴とする請求項1に記載のスチレン系オレフィンの製造方法。
- 前記還流形成段階で、反応温度が50〜200℃であることを特徴とする請求項1に記載のスチレン系オレフィンの製造方法。
- 前記水除去段階が、蒸留方法で行われることを特徴とする請求項1に記載のスチレン系オレフィンの製造方法。
- 前記水除去段階が、無水硫酸マグネシウム(MgSO4)、無水硫酸カルシウム(CaSO4)、無水塩化マグネシウム(MgCl2)、無水塩化カルシウム(CaCl2)、アルミナ(Al2O3)、及びシリカゲル(SiO2)からなる群から1以上選択される乾燥剤を使用する方法で行われることを特徴とする請求項1に記載のスチレン系オレフィンの製造方法。
- 前記精製段階が、単純蒸留及び真空蒸留方法で行われることを特徴とする請求項1に記載のスチレン系オレフィンの製造方法。
- 前記精製方法が、アルミナカラムクロマトグラフィー又はシリカゲルカラムクロマトグラフィーによって行われることを特徴とする請求項1に記載のスチレン系オレフィンの製造方法。
- 前記蒸留方法で、蒸留器内部及び周囲の温度が25〜400℃であることを特徴とする請求項6に記載のスチレン系オレフィンの製造方法。
- 前記蒸留方法で、真空度が0.5〜10−6気圧であることを特徴とする請求項6に記載のスチレン系オレフィンの製造方法。
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KR1020030071139A KR100572473B1 (ko) | 2003-10-13 | 2003-10-13 | 스티렌계 올레핀의 새로운 제조 방법 |
PCT/KR2004/002613 WO2005035468A1 (en) | 2003-10-13 | 2004-10-13 | Novel method for preparing styrenic olefins |
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JP5362790B2 (ja) * | 2004-08-30 | 2013-12-11 | 株式会社クラレ | 耐熱性に優れる重合体の製造方法 |
JP5388044B2 (ja) * | 2006-03-01 | 2014-01-15 | 国立大学法人東京農工大学 | 重合体および重合体の製造方法 |
US7541417B2 (en) | 2006-03-30 | 2009-06-02 | Sabic Innovative Plastics Ip B.V. | Process for the purification of dihydric phenols |
US7528210B2 (en) | 2006-03-30 | 2009-05-05 | Sabic Innovative Plastics Ip B.V. | Method of purification of dihydric phenols |
WO2017087105A1 (en) | 2015-11-20 | 2017-05-26 | Exxonmobil Chemical Patents Inc. | Preparation and use of phenylstyrene |
JP7299795B2 (ja) | 2019-08-20 | 2023-06-28 | 住友化学株式会社 | アミノ芳香族化合物の製造方法 |
CN113372187B (zh) * | 2021-06-02 | 2022-12-30 | 西安瑞联新材料股份有限公司 | 一种bvpe的工业化合成方法 |
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JPS56140935A (en) | 1980-04-03 | 1981-11-04 | Sumitomo Chem Co Ltd | Preparation of styrene compound |
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US4521637A (en) * | 1983-12-16 | 1985-06-04 | Atlantic Richfield Company | Process for the production of bis(alpha-alkylbenzyl) ethers |
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US7485762B2 (en) | 2009-02-03 |
EP1673319A4 (en) | 2009-11-25 |
WO2005035468A1 (en) | 2005-04-21 |
CN100577615C (zh) | 2010-01-06 |
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