JPH02138230A - Production of alkyl-substituted aromatic hydrocarbon - Google Patents
Production of alkyl-substituted aromatic hydrocarbonInfo
- Publication number
- JPH02138230A JPH02138230A JP1201033A JP20103389A JPH02138230A JP H02138230 A JPH02138230 A JP H02138230A JP 1201033 A JP1201033 A JP 1201033A JP 20103389 A JP20103389 A JP 20103389A JP H02138230 A JPH02138230 A JP H02138230A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- solid base
- aromatic hydrocarbon
- reaction
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000007787 solid Substances 0.000 claims abstract description 51
- 239000002585 base Substances 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims abstract description 13
- 150000008046 alkali metal hydrides Chemical class 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 230000002152 alkylating effect Effects 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 21
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 11
- 229910000105 potassium hydride Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- SUDBRAWXUGTELR-HPFNVAMJSA-N 5-[[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxymethyl]-1h-pyrimidine-2,4-dione Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OCC1=CNC(=O)NC1=O SUDBRAWXUGTELR-HPFNVAMJSA-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- BEQGRRJLJLVQAQ-UHFFFAOYSA-N 3-methylpent-2-ene Chemical compound CCC(C)=CC BEQGRRJLJLVQAQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 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
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
〈産業上の利用分野〉
本発明はアルキル置換芳香族炭化水素の製造法に関し、
詳しくは特定の温度下でアルミナ、アルカリ金属水酸化
物およびアルカリ金属水素化物から調製した固体塩基の
存在下に、側鎖のα位に水素原子を有する芳香族炭化水
素とオレフィンとを反応させてα位をアルキル化せしめ
ることによるアルキル置換芳香族炭化水素の製造法に関
するものである。
〈従来の技術〉
アルキル置換芳香族炭化水素は農・医薬品、化成品等フ
ァインケミカルズの中間原料とし７で有用であり、塩基
触媒の存在下に側鎖のα位に水素を有する芳香族炭化水
素とオレフィンとを反応させることにより得られる。
例えば、触媒として金属ナトリウムとクロルトルエンか
らなる触媒を用いる方法、金属ナトリウムを炭酸カリウ
ムに担持した触媒を用いる方法等が知られている（Ｊ、
Ａｍ、ＣｈｅＩＩｌ、Ｓｏｃ、、７８．４３１６（１９
５６）、英国、特許第１２６９２８０号、特開昭６１−
５３２２９号公報）。
〈発明が解決しようとする課題〉
しかしながら、上記のような触媒を用いた場合、触媒活
性が充分ではなく、生成するアルキル置換芳香族炭化水
素の触媒光たりの収量が低いという問題、触媒と生成物
の分ぬ１が煩雑であるという問題、更には触媒が大気中
の空気、水分と接した場合に失活し易くまた発火の危険
を伴うという問題等があった。
く課題を解決するための手段〉
本発明者らは芳香族炭化水素のα位のアルキル化による
アルキル置換芳香族炭化水素の優れた製造法を開発すべ
く、アルキル化触媒について鋭意検討を重ねた結果、ア
ルミナ、アルカリ金属水酸化物およびアルカリ金属水素
化物を加熱処理して得られる特定の固体塩基が、著しく
高いアルキル化活性を示し、少ない触媒量で効率良く目
的とするアルキル置換芳香族炭化水素を生成せしめ、し
かも反応生成物との分離も容易であり、そのうえ該固体
塩基は大気中の空気、水分と接触しても発火の危険が少
なく、取扱いが極めて容易であることを見出すとともに
、更に種々の検討を加えて本発明を完成した。
すなわち本発明は、側鎖のα位に水素原子を有する芳香
族炭化水素をオレフィンでアルキル化して、アルキル置
換芳香族炭化水素を製造するに当たり、触媒としてアル
ミナ、アルカリ金属水酸化物およびアルカリ金属水素化
物を不活性ガス雰囲気中、２００乃至８００℃の温度下
で加熱処理してなる固体塩基を用いることを特徴とする
工業的にイ】れたアルキル置換芳香族炭化水素の製造方
法を提供するものである。
本発明はアルミナ、アルカリ金属水酸化物、アルカリ金
属水素化物を特定温度下で加熱処理してなる固体塩基を
用いることを特徴とするものであるが、アルミナとして
はα−アルミナ以外の種々の形ｊＢのものが使用し得、
中でもｒ−２χ−１ρ−型のような表面積の大きなアル
ミナが好ましく用いられる。
またアルカリ金属水素化物としては周期律表第！族のリ
チウム、ナトリウム、カリウム、ルビジウム等のアルカ
リ金属の水素化物が用いられ、好ましくはナトリウム水
素化物、カリウム水素化物もしくはこれ等ｑ）混合物、
更に好ましくはカリウム水素化物が用いられる。アルカ
リ金属水素化物の使用量はアルミナに対し通常２乃至１
５ｗｔχである。
アルカリ金属水酸化物としては、例えば水酸化リチウム
、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウ
ム、水酸化セシウム等が挙げられるが、好ましくは水酸
化ナトリウム、水酸化カリウム、水酸化セシウムが用い
られる。アルカリ金属水酸化物は２種以上用いることも
できる。１吏用量はアルミナに対し、通常５乃至４０ｗ
ｔχである。
固体塩基を調製するに当たっては不活性ガス雰囲気下で
、先ずアルミナにアルカリ金属水酸化物を、次いでアル
カリ金属水素化物を作用させるのが好ましい。
例えば、アルミナにアルカリ金属水酸化物を加えて加熱
作用せしめ、次いでこれにアルカリ金属水素化物を加え
て加熱作用せしめる方法、アルミナをアルカリ金属水酸
化物の溶液に含浸、乾燥した後、加熱作用せしめ、次い
でこれにアルカリ金属水素化物を加えて加熱作用せしめ
る方法等が挙げられる。
不活性ガスとしては窒素、ヘリウム、アルゴン等が挙げ
られる。
触媒調製温度は重要であり、通常２００乃至８００’Ｃ
１好ましくはアルミナとアルカリ金属水酸化物とを作用
せしめる温度は２５０乃至７００℃１より好ましくは２
６０乃至４８０℃である。アルカリ金属水素化ワフを作
用せしめる温度は、好ましくは２００乃至４５０’Ｃで
ある。 加熱時間は選定する温度条件等にもよるが、ア
ルカリ金属水酸化物を作用せしめる工程は通常０．５乃
至１０時間で充分であり、アルカリ金属水素化物を作用
せしめる工程は通常１０乃至３゜０分である。
かくして、高活性なうえに流動性、操作性が良好でしか
も空気にふれても発火の危険性のない固体塩基が得られ
る。
本発明はかかる固体塩基を用いて、側鎖のα位に水素を
有する芳香族炭化水素とオレフィンとを反応させるもの
であるが、咳芳香族炭化水素としては通常重環芳香族炭
化水素の他、縮合多環芳香族炭化水素が用いられる。こ
れらは側鎖が結合して環を形成していても良い。
例エバ）ルエン、エチルベンゼン、イソプロピルベンゼ
ン、ｎ−プロビルヘンゼン、ｎ−プチルベンセン、５ｅ
ｅ−ブチルベンゼン、イソブチレンゼン、キシレン、シ
メン、ジイソプロピルベンゼン、メチルナフタレン、テ
トラヒドロナフタレン、インダン等が例示できる。トル
エン、エチルベンゼン、イソプロビルヘンゼンが好まし
く使用される。
またオレフィンとしては炭素数が２〜２０のオレフィン
が通常用いられ、直鎖のもの、分岐のものいずれでも良
い。また二重結合が末端、内部いずれにあっても使用で
きる。末端オレフィンが好ましく用いられる。
これらの具体化合物としては、例えばエチレン、プロピ
レン、１−ブテン、２−ブテン、イソブチレン、１−ペ
ンテン、２−ペンテン、１−ヘキセン、２−ヘキセン、
３−ヘキセン、シクロヘキセン、ｌ−ヘプテン、２−ヘ
プテン、３−ヘプテン、オクテン、ノネン、３−メチル
−１−ブテン、２−メチル−２−ブテン、３−メチル−
１−ペンテン、３−メチル−２−ペンテン等が挙げられ
る。
エチレン、プロピレン、１−ブテン、２−ブテンが好ま
しく使用される。
アルキル化反応を実施するに当たっては、バ・ノチ方式
、流動床、固定床を用いた流通方式いずれも採用できる
。
反応温度は通常Ｏ乃至３００℃１好ましくは２０乃至２
００℃であり１反応圧力は通常大気圧乃至２００Ｋｇ／
ｃｍ”、好ましくは２乃至１００にｇ／ｃｅｂ”である
。
また芳香族炭化水素に対するオレフィンのモル比は通常
０．１乃至ｌＯ１好ましくは０．２乃至５である。
バッチ方式における触媒の使用量は通常、使用する芳香
族炭化水素の０．０１乃至２０−<Industrial Application Field> The present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon,
Specifically, an aromatic hydrocarbon having a hydrogen atom at the α-position of the side chain is reacted with an olefin in the presence of a solid base prepared from alumina, an alkali metal hydroxide, and an alkali metal hydride at a specific temperature. This invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon by alkylating the α-position. <Prior art> Alkyl-substituted aromatic hydrocarbons are useful as intermediate raw materials for fine chemicals such as agricultural products, pharmaceuticals, and chemical products. Obtained by reacting with olefin. For example, a method using a catalyst consisting of metallic sodium and chlorotoluene as a catalyst, a method using a catalyst in which metallic sodium is supported on potassium carbonate, etc. are known (J,
Am, CheIII, Soc, 78.4316 (19
56), UK, Patent No. 1269280, JP-A-61-
53229). <Problems to be Solved by the Invention> However, when the above-mentioned catalyst is used, there are problems such as insufficient catalytic activity and a low yield of alkyl-substituted aromatic hydrocarbons per catalytic light; There is a problem that the catalyst is complicated, and furthermore, the catalyst is easily deactivated when it comes into contact with air or moisture in the atmosphere, and there is a risk of ignition. Means for Solving the Problems> In order to develop an excellent method for producing alkyl-substituted aromatic hydrocarbons by alkylating the α-position of aromatic hydrocarbons, the present inventors conducted intensive studies on alkylation catalysts. As a result, specific solid bases obtained by heat treating alumina, alkali metal hydroxides, and alkali metal hydrides exhibit significantly high alkylation activity, and can efficiently convert target alkyl-substituted aromatic hydrocarbons with a small amount of catalyst. It has been found that the solid base can be easily separated from the reaction products, and that the solid base has little risk of ignition even when it comes into contact with air or moisture in the atmosphere, and is extremely easy to handle. The present invention was completed after various studies. That is, the present invention involves alkylating an aromatic hydrocarbon having a hydrogen atom at the α-position of the side chain with an olefin to produce an alkyl-substituted aromatic hydrocarbon, using alumina, an alkali metal hydroxide, and an alkali metal hydrogen as a catalyst. Provided is an industrial method for producing alkyl-substituted aromatic hydrocarbons, characterized in that a solid base obtained by heat-treating a compound at a temperature of 200 to 800°C in an inert gas atmosphere is used. It is. The present invention is characterized by using a solid base obtained by heat-treating alumina, alkali metal hydroxide, or alkali metal hydride at a specific temperature. jB's can be used,
Among them, alumina having a large surface area such as r-2χ-1ρ-type is preferably used. Also, it is the number one alkali metal hydride in the periodic table! q) mixtures thereof, preferably sodium hydride, potassium hydride or mixtures thereof;
More preferably, potassium hydride is used. The amount of alkali metal hydride used is usually 2 to 1 per alumina.
5wtχ. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc., but sodium hydroxide, potassium hydroxide, and cesium hydroxide are preferably used. . Two or more types of alkali metal hydroxides can also be used. The dosage is usually 5 to 40 w for alumina.
It is tχ. In preparing the solid base, it is preferable to first treat alumina with an alkali metal hydroxide and then with an alkali metal hydride under an inert gas atmosphere. For example, a method of adding an alkali metal hydroxide to alumina and applying a heating effect to the alumina, then adding an alkali metal hydride to the alumina and applying a heating effect, or a method of impregnating alumina with a solution of an alkali metal hydroxide, drying it, and then applying a heating effect to the alumina. Then, a method of adding an alkali metal hydride to the mixture and applying a heating effect to the mixture can be mentioned. Examples of the inert gas include nitrogen, helium, and argon. The catalyst preparation temperature is important and is usually between 200 and 800'C.
1 Preferably, the temperature at which the alumina and alkali metal hydroxide are allowed to interact is 250 to 700°C1, more preferably 2
The temperature is 60 to 480°C. The temperature at which the alkali metal hydrogenation waff is applied is preferably 200 to 450'C. The heating time depends on the selected temperature conditions, etc., but normally 0.5 to 10 hours is sufficient for the step of applying an alkali metal hydroxide, and usually 10 to 3 hours for the step of applying an alkali metal hydride. It's a minute. In this way, a solid base is obtained which is highly active, has good fluidity and operability, and has no risk of ignition even when exposed to air. The present invention uses such a solid base to react an aromatic hydrocarbon having hydrogen at the α-position of the side chain with an olefin. , a fused polycyclic aromatic hydrocarbon is used. These may have side chains bonded to form a ring. Example Eva) Luene, ethylbenzene, isopropylbenzene, n-propylbenzene, n-butylbenzene, 5e
Examples include e-butylbenzene, isobutylene, xylene, cymene, diisopropylbenzene, methylnaphthalene, tetrahydronaphthalene, and indane. Toluene, ethylbenzene and isopropyrhenzene are preferably used. Further, as the olefin, an olefin having 2 to 20 carbon atoms is usually used, and either a linear or branched olefin may be used. Further, it can be used regardless of whether the double bond is located at the terminal or internally. Terminal olefins are preferably used. Specific examples of these compounds include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene,
3-hexene, cyclohexene, l-heptene, 2-heptene, 3-heptene, octene, nonene, 3-methyl-1-butene, 2-methyl-2-butene, 3-methyl-
Examples include 1-pentene and 3-methyl-2-pentene. Ethylene, propylene, 1-butene, 2-butene are preferably used. In carrying out the alkylation reaction, any of the Ba-Noti method, fluidized bed, and flow method using a fixed bed can be adopted. The reaction temperature is usually 0 to 300°C, preferably 20 to 20°C.
00℃, and the reaction pressure is usually atmospheric pressure to 200Kg/
cm", preferably 2 to 100 g/ceb". The molar ratio of olefin to aromatic hydrocarbon is usually 0.1 to 101, preferably 0.2 to 5. The amount of catalyst used in the batch process is usually 0.01 to 20-20% of the aromatic hydrocarbon used.
【χ、好ましくは０．
０５乃至５ ｗＬＸ ”ｉｌ’ Ｔｏ ”）、反応は通
常０．５７［５０時間、好ましくはｌ乃至２５時間であ
る。また流通反応における芳香族炭化水素と脂肪族オレ
フィンの合計の供給速度はＬＨ３Ｖで通常０．１乃至６
００ｈｒ川、好ましくは０．５乃至４００ｈｒ−’が採
用される。
〈発明の効果〉
かくして、アルキル置換芳香族炭化水素が生成するが、
本発明によれば少ない触媒量で、しかも緩和な条件下で
も、極めて効率良く目的とするアルキル置換芳香族炭化
水素を製造し得る。
加えて、触媒の取扱いのみならず反応後の後処理も極め
て容易であるので、本発明方法はこの点でも有利である
。
〈実施例〉
以下、実施例により本発明をさらに詳細に説明するが、
本発明はこれら実施例のみに限定されるものではない。
触媒調製例
（固体塩基Ａ）
４２〜２００メツシユに揃えた活性アルミナ２６．５ｇ
を窒素雰囲気下５１０’Ｃで１時間撹拌し、次いで３８
０℃に冷却した後、水酸化カリウム２．５ｇを加えて、
同温度で３時間撹拌した。
次いで３１０”Ｃに冷却した後、水素化カリウム２．３
３ｇを加えて、同温度で０．２時間撹拌した。 これを
室温まで放冷して２４．２ ｇの固体塩基Ａを得た。
（固体塩基Ｂ）
固体塩基Ａにおいて、水素化カリウム１．７８ｇを用い
る以外は固体塩基Ａの調製例に準りして実施して固体塩
基Ｂを得た。
（固体塩基Ｃ）
固体塩基Ａにおいて、水酸化カリウムを加える時の温度
およびその後の撹拌温度を３８０℃から５５０℃に代え
、水素化カリウム１．８１ ｇを用いる以外は固体塩基
Ａの調製例に準拠して実施し、固体塩基Ｃを得た。
（固体塩基Ｄ）
固体塩基Ａで用いたと同じ活性アルミナ２６．５ ｇを
水酸化カリウム２．５ ｇと水５０ｇからなる溶液に加
え、これを７０℃減圧下にロータリーエバポレーターを
用いて乾燥した。
次いで、このものを窒素雰囲気、２５０℃下で３時間撹
拌した後、３１０℃に昇温しで水素化カリウム３．１８
ｇを加え、同温度で０．２時間撹拌した。これを室温ま
で冷却して固体塩基りを得た。
（固体塩基Ｅ）
固体塩基りにおいて、水酸化カリウムを加える前の温度
を２５０″Ｃから３８０℃に代え、水素化カワウム３．
１５ｇを用いる以外は固体塩基りの調製例に準拠して実
施し、固体塩基Ｅを得た。
（固体塩基Ｆ）
固体塩基りにおいて、水酸化カリウムを加える前の温度
を２５０℃から５５０’Ｃに代え、水素化カリウム３．
２５ｇを用いる以外は固体塩基りの調製例に準拠して実
施し、固体塩基Ｆを得た。
（固体塩基Ｇ）
固体塩基りにおいて、水酸化カリウムを加える前の温度
を２５０℃から７００’Ｃに代え、水素化カリウム３．
１５ｇを用いる以外は固体塩基りのｍ製例に準拠して実
施し、固体塩基Ｇを得た。
（固体塩基Ｈ）
固体塩基Ａにおいて、水酸化カリウムの代わりに水酸化
ナトリウム２．５ｇを用い、２．０ｇの水素化カリウム
を用いる以外は固体塩基Ａの調製例に準拠して実施し、
固体塩基Ｈを得た。
（固体塩基り
固体塩基Ａにおいて、水素化カリウムの代わりに水素化
ナトリウム２．５ｇを用いる以外は固体塩基Ａの調製例
に準拠して実施し、固体塩基１を得たた。
（固体塩基Ｊ）
固体塩５Ａで用いたと同じ活性アルミナ２６．５ｇと、
水酸化カリウム２．５ ｇとを混合粉砕した後、これを
坩堝に入れてマツフル炉で１０００℃下、３時間撹拌し
た０次いで２００℃まで冷却した後、窒素雰囲気下、デ
シケータ−中で室温迄冷却して微細な粉体を得た。
これを窒素雰囲気下、３１０℃に加熱した後、撹拌しな
がらこれに水素化ナトリウム２．６ｇを加えて同温度で
０．２時間撹拌した。これを室温まで冷却して固体塩基
Ｊを得た。
実施例１
電磁撹拌器付６００−オートクレーブに窒素雰囲気下、
固体塩基Ｄ ０．３２ｇ、７ メ７２４０ｇを入ａ、１
０００ｒ、ｐ、ｍ、撹拌下に１００℃に昇ａ後、同温度
でエチレンガスを１０にｇ／ｃｗｈ”・Ｇで供給しなが
ら３時間反応を行った。
反応後オートクレーブを冷却し、触媒を濾別した後、反
応液をガスクロマトグラフィーで分析した。 反応結果
を表１に示した。
実施例２〜１０、比較例１
実施例１において、固体塩ｉＡの代わりに固体塩基へ〜
Ｊをそれぞれ用い、表１に示す条件以外は実施例１に準
じて実施した０反応結果を表１に示した。 尚、実施例
１−１０においては、反応終了後の触媒はなお活性であ
り、更に反応を行なったところ該反応が進行した。
比較例２
窒素雰囲気下で電磁撹拌器付２００ａｌオートクレーブ
に、あらかじめ４００℃５窒素雰囲気下で２時間焼成し
た無水炭酸カリウム８．１９ｇ、ナトリウム０．３０
ｇ、クメン２６．７ｇを加えた後、１９０℃に昇温し、
同温度で２時間１０００ｒ、ｐ、ｍ、で撹拌を続けた。
次いでオートクレーブを冷却し、クメン５３．３ｇ、を
追加した後、１０００ｒ、ｐ、ｍ、撹拌下１６０℃に昇
温し、同温度でエチレンガスを１０Ｋｇ／ｃｍ”・Ｇで
供給しながら３時間反応を行った。 反応後、実施例１
と同様にしてガスクロマトグラフィーで分析した。
反応結果を表１に示した。
表１
実施例１以外は反応温度１６０’ｃで実施した。
ＴＡＢ・ｔｅｒし アミルベンゼン
実施例１１
電弧ｄ撹拌器付３００ＩｎＲオートクレーブに窒素雰囲
気下、固体塩５Ａ ０．９９ｇ、クメン８０ｇを入れ、
液化プロピレン１００ｍｆｆ１を圧入した後、１６０℃
で２４時間撹拌を続けた。
反応終了後、オートクレーブを冷却した後、反応液を実
施例１と同様にしてガスクロマトグラフィーで分析した
。 反応結果はクメン転化率７１．１％、１，１．２−
） ＋Ｊ ／ チルプロピルベンゼン（ＴＭＰＩＩ）
’Ｍ Ｗ率８５．７％であった。
尚、反応終了後の触媒はなお活性であり、更に反応を行
なったところ該反応が進行した。
比較例３
窒素雰囲気下で電磁撹拌器付２００ｄオートクレーブに
、あらかじめ４００℃、窒素雰囲気下で２時間焼成した
無水炭酸カリウム８．８６ｇ、ナトリウム０．３０ｇ、
クメン８１．２ ｇを加えた後、１９０℃に昇温し、同
温度で２時間撹拌を続けた。
次いでオートクレーブを冷却し、液化プロピレン７０ｍ
１を圧入した後、１６０℃で２４時間撹拌した。
反応後、実ｈｔｉｉ例】と同様にしてガスクロマトグラ
フィーで分析したところクメン転化率８．０％、丁ＭＰ
Ｂ選択率８１．５％であった。
実施例１２
電磁撹拌器付３００ ｄオートクレーブに窒素雰囲気下
、固体塩基Ａ ２．８１ｇ、トルエン８０ｇを入れ、液
化プロピレン７０ｍ１を圧入した後、１６０℃で６時間
撹拌を続けた。
反応終了後、オートクレーブを冷却した後、反応液を実
施例１と同様にしてガスクロマトグラフィーで分析した
０反応結果はトルエン転化率２２．９％、イソブチルベ
ンゼン（ＩＢＢ） Ｍ沢率９１．０％であった。
尚、反応終了後の触媒はなお活性であり、更に反応を行
なったところ該反応が進行した。
比較例４
窒素雰囲気下で電磁撹拌器付２００ｄオートクレーブに
、あらかじめ４００℃１窒素雰囲気下で２時間焼成した
無水炭酸カリウム８．４５ｇ、ナトリウム０．３０ ｇ
、トルエン２６．６ｇを加えた後、１９０℃に昇温し、
同温度で２時間撹拌を続けた。
次いでオートクレーブを冷却してトルエン５３．２ｇ、
？＆化プロピレン７０ｄを圧入した後、１６０℃で２４
時間撹拌した。 反応後、実施例１と同様にしてガスク
ロマトグラフィーで分析したところトルエン転化率３，
５％、ＩＩＩＢ選択率８９．２％であった。[χ, preferably 0.
05 to 5 wLX "il'To"), the reaction time is usually 0.57 [50 hours, preferably 1 to 25 hours. In addition, the total feed rate of aromatic hydrocarbons and aliphatic olefins in the flow reaction is usually 0.1 to 6 at LH3V.
00 hr river, preferably 0.5 to 400 hr-' is employed. <Effect of the invention> In this way, alkyl-substituted aromatic hydrocarbons are produced,
According to the present invention, target alkyl-substituted aromatic hydrocarbons can be produced extremely efficiently with a small amount of catalyst and even under mild conditions. In addition, the method of the present invention is advantageous in this respect as not only the handling of the catalyst but also the post-treatment after the reaction is extremely easy. <Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited only to these examples. Catalyst preparation example (solid base A) 26.5 g of activated alumina arranged in a mesh of 42 to 200
was stirred at 510'C for 1 hour under nitrogen atmosphere, then 38
After cooling to 0°C, add 2.5g of potassium hydroxide,
The mixture was stirred at the same temperature for 3 hours. Then, after cooling to 310"C, 2.3% potassium hydride
3 g was added and stirred at the same temperature for 0.2 hours. This was allowed to cool to room temperature to obtain 24.2 g of solid base A. (Solid Base B) Solid base B was obtained in the same manner as in the preparation example of solid base A except that 1.78 g of potassium hydride was used. (Solid base C) Same as the preparation example of solid base A except that in solid base A, the temperature when adding potassium hydroxide and the subsequent stirring temperature were changed from 380°C to 550°C, and 1.81 g of potassium hydride was used. A solid base C was obtained. (Solid base D) 26.5 g of the same activated alumina used in solid base A was added to a solution consisting of 2.5 g of potassium hydroxide and 50 g of water, and this was dried at 70° C. under reduced pressure using a rotary evaporator. Next, this material was stirred for 3 hours at 250°C in a nitrogen atmosphere, and then heated to 310°C, and 3.18% of potassium hydride was added.
g was added thereto, and the mixture was stirred at the same temperature for 0.2 hours. This was cooled to room temperature to obtain a solid base. (Solid base E) In the solid base preparation, the temperature before adding potassium hydroxide was changed from 250"C to 380"C, and potassium hydride 3.
Solid base E was obtained in accordance with the preparation example of solid base except that 15 g was used. (Solid base F) In solid base formation, the temperature before adding potassium hydroxide was changed from 250°C to 550'C, and potassium hydride 3.
Solid base F was obtained in accordance with the preparation example of solid base except that 25 g was used. (Solid base G) In solid base formation, the temperature before adding potassium hydroxide was changed from 250°C to 700'C, and potassium hydride 3.
Solid base G was obtained by carrying out the procedure according to Example M for solid base preparation except that 15 g was used. (Solid base H) In solid base A, the procedure was carried out according to the preparation example of solid base A, except that 2.5 g of sodium hydroxide was used instead of potassium hydroxide and 2.0 g of potassium hydride was used.
A solid base H was obtained. (Solid base A) Solid base 1 was obtained by following the preparation example of solid base A except that 2.5 g of sodium hydride was used instead of potassium hydride. (Solid base J ) 26.5 g of the same activated alumina used in solid salt 5A,
After mixing and pulverizing 2.5 g of potassium hydroxide, the mixture was placed in a crucible and stirred for 3 hours at 1000°C in a Matsufuru furnace. After cooling to 200°C, the mixture was heated to room temperature in a desiccator under a nitrogen atmosphere. After cooling, a fine powder was obtained. After heating this to 310° C. under a nitrogen atmosphere, 2.6 g of sodium hydride was added thereto while stirring, and the mixture was stirred at the same temperature for 0.2 hours. This was cooled to room temperature to obtain solid base J. Example 1 In a 600-autoclave with a magnetic stirrer under a nitrogen atmosphere,
Add 7240 g of solid base D, 0.32 g, 7 a, 1
After raising the temperature to 100°C with stirring at 000r, p, m, the reaction was carried out at the same temperature for 3 hours while supplying ethylene gas at 10g/cwh''.G.After the reaction, the autoclave was cooled and the catalyst was removed. After filtering, the reaction solution was analyzed by gas chromatography. The reaction results are shown in Table 1. Examples 2 to 10, Comparative Example 1 In Example 1, solid base was used instead of solid salt iA.
Table 1 shows the results of the 0 reaction, which was carried out according to Example 1 except for the conditions shown in Table 1, using J. In Examples 1-10, the catalyst was still active after the reaction was completed, and when the reaction was further carried out, the reaction proceeded. Comparative Example 2 8.19 g of anhydrous potassium carbonate and 0.30 g of sodium were calcined in advance at 400° C. for 2 hours under a nitrogen atmosphere in a 200 al autoclave equipped with a magnetic stirrer under a nitrogen atmosphere.
After adding 26.7 g of cumene, the temperature was raised to 190°C,
Stirring was continued at 1000 r, p, m for 2 hours at the same temperature. Next, the autoclave was cooled, and after adding 53.3 g of cumene, the temperature was raised to 160° C. with stirring at 1000 r, p, m, and reacted for 3 hours at the same temperature while supplying ethylene gas at 10 kg/cm”・G. After the reaction, Example 1
Analyzed by gas chromatography in the same manner as above. The reaction results are shown in Table 1. Table 1 Except for Example 1, the reaction temperature was 160'C. TAB・ter. Amylbenzene Example 11 In a 300 InR autoclave equipped with an electric arc stirrer, 0.99 g of solid salt 5A and 80 g of cumene were placed in a nitrogen atmosphere.
After pressurizing 100 mff1 of liquefied propylene, the temperature was increased to 160°C.
Stirring was continued for 24 hours. After the reaction was completed, the autoclave was cooled, and the reaction solution was analyzed by gas chromatography in the same manner as in Example 1. The reaction results were cumene conversion rate of 71.1%, 1,1.2-
) +J/Tylpropylbenzene (TMPII)
'MW rate was 85.7%. It should be noted that the catalyst was still active after the reaction was completed, and when the reaction was further carried out, the reaction proceeded. Comparative Example 3 8.86 g of anhydrous potassium carbonate, 0.30 g of sodium, which had been previously calcined at 400° C. for 2 hours in a 200 d autoclave with a magnetic stirrer under a nitrogen atmosphere, and 0.30 g of sodium.
After adding 81.2 g of cumene, the temperature was raised to 190°C, and stirring was continued at the same temperature for 2 hours. The autoclave was then cooled and 70 m of liquefied propylene was added.
After pressurizing 1, the mixture was stirred at 160°C for 24 hours. After the reaction, analysis by gas chromatography in the same manner as in Actual Example] revealed that the cumene conversion rate was 8.0%.
The B selectivity was 81.5%. Example 12 2.81 g of solid base A and 80 g of toluene were placed in a 300 d autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, and after 70 ml of liquefied propylene was pressurized, stirring was continued at 160° C. for 6 hours. After the reaction was completed, the autoclave was cooled, and the reaction solution was analyzed by gas chromatography in the same manner as in Example 1.The reaction results were as follows: toluene conversion rate 22.9%, isobutylbenzene (IBB) M content rate 91.0%. Met. It should be noted that the catalyst was still active after the reaction was completed, and when the reaction was further carried out, the reaction proceeded. Comparative Example 4 8.45 g of anhydrous potassium carbonate and 0.30 g of sodium were calcined in advance at 400° C. for 2 hours under a nitrogen atmosphere in a 200 d autoclave equipped with a magnetic stirrer under a nitrogen atmosphere.
, after adding 26.6g of toluene, the temperature was raised to 190°C,
Stirring was continued for 2 hours at the same temperature. Then, the autoclave was cooled and 53.2 g of toluene was added.
? After press-fitting 70d of propylene, it was heated at 160°C for 24
Stir for hours. After the reaction, analysis by gas chromatography in the same manner as in Example 1 revealed that the toluene conversion rate was 3,
5%, and the IIIB selectivity was 89.2%.
Claims (1)
ィンでアルキル化して、アルキル置換芳香族炭化水素を
製造するに当たり、触媒としてアルミナ、アルカリ金属
水酸化物およびアルカリ金属水素化物を不活性ガス雰囲
気中、２００乃至８００℃の温度下で加熱処理してなる
固体塩基を用いることを特徴とするアルキル置換芳香族
炭化水素の製造法。When producing an alkyl-substituted aromatic hydrocarbon by alkylating an aromatic hydrocarbon having a hydrogen atom at the α-position of the side chain with an olefin, alumina, alkali metal hydroxide, and alkali metal hydride are used as a catalyst in an inert gas. A method for producing an alkyl-substituted aromatic hydrocarbon, characterized by using a solid base obtained by heat treatment at a temperature of 200 to 800° C. in an atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1201033A JP2748577B2 (en) | 1988-08-12 | 1989-08-01 | Process for producing alkyl-substituted aromatic hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-202468 | 1988-08-12 | ||
| JP20246888 | 1988-08-12 | ||
| JP1201033A JP2748577B2 (en) | 1988-08-12 | 1989-08-01 | Process for producing alkyl-substituted aromatic hydrocarbons |
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| Publication Number | Publication Date |
|---|---|
| JPH02138230A true JPH02138230A (en) | 1990-05-28 |
| JP2748577B2 JP2748577B2 (en) | 1998-05-06 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57170863A (en) * | 1981-04-13 | 1982-10-21 | Toyo Pairu Hiyuumukan Seisakus | Inorganic heat-insulating board manufacture and heat-insulating board |
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1989
- 1989-08-01 JP JP1201033A patent/JP2748577B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57170863A (en) * | 1981-04-13 | 1982-10-21 | Toyo Pairu Hiyuumukan Seisakus | Inorganic heat-insulating board manufacture and heat-insulating board |
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|---|---|
| JP2748577B2 (en) | 1998-05-06 |
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