JPS61221133A - Method of side chain alkylation of alkyl-substituted aromatic hydrocarbon - Google Patents
Method of side chain alkylation of alkyl-substituted aromatic hydrocarbonInfo
- Publication number
- JPS61221133A JPS61221133A JP60061881A JP6188185A JPS61221133A JP S61221133 A JPS61221133 A JP S61221133A JP 60061881 A JP60061881 A JP 60061881A JP 6188185 A JP6188185 A JP 6188185A JP S61221133 A JPS61221133 A JP S61221133A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- substituted aromatic
- catalyst
- aromatic hydrocarbon
- potassium carbonate
- 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 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005804 alkylation reaction Methods 0.000 title claims description 12
- 230000029936 alkylation Effects 0.000 title claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 35
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 29
- -1 aliphatic monoolefin Chemical class 0.000 claims abstract description 18
- 239000002612 dispersion medium Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 230000002152 alkylating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000011734 sodium Substances 0.000 description 11
- 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 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- FIPKSKMDTAQBDJ-UHFFFAOYSA-N 1-methyl-2,3-dihydro-1h-indene Chemical compound C1=CC=C2C(C)CCC2=C1 FIPKSKMDTAQBDJ-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
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 2
- XNXIYYFOYIUJIW-UHFFFAOYSA-N 3-methylbutylbenzene Chemical compound CC(C)CCC1=CC=CC=C1 XNXIYYFOYIUJIW-UHFFFAOYSA-N 0.000 description 2
- PVXCNEZDIJHZQB-UHFFFAOYSA-N 3-methylpentylbenzene Chemical compound CCC(C)CCC1=CC=CC=C1 PVXCNEZDIJHZQB-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000008118 PEG 6000 Substances 0.000 description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- NBJZEUQTGLSUOB-UHFFFAOYSA-N 1-chloro-4-isocyanato-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(N=C=O)=CC=C1Cl NBJZEUQTGLSUOB-UHFFFAOYSA-N 0.000 description 1
- SECAQUZEXAHWBA-UHFFFAOYSA-N 1-ethyl-2,3-dihydro-1h-indene Chemical compound C1=CC=C2C(CC)CCC2=C1 SECAQUZEXAHWBA-UHFFFAOYSA-N 0.000 description 1
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 1
- HMAMGXMFMCAOPV-UHFFFAOYSA-N 1-propylnaphthalene Chemical compound C1=CC=C2C(CCC)=CC=CC2=C1 HMAMGXMFMCAOPV-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
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-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
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002468 indanes Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SIXNTGDWLSRMIC-UHFFFAOYSA-N sodium;toluene Chemical compound [Na].CC1=CC=CC=C1 SIXNTGDWLSRMIC-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
【発明の詳細な説明】
〔技術分野〕
本発明は、特定の方法によって調製した、炭酸カリウム
粉体にアルカリ金属を担持せしめた触媒の存在下に、ア
ルキル置換芳香族炭化水素（ａ）を脂肪族モノオレフィ
ンを用いて側鎖アルキル化し、医薬、農薬等を製造する
際の中間体として有用な炭素数を増したアルキル置換芳
香族炭化水素（ｂ）を製造する方法に関する。Detailed Description of the Invention [Technical Field] The present invention provides a method for converting alkyl-substituted aromatic hydrocarbons (a) into fatty acids in the presence of a catalyst prepared by a specific method and having an alkali metal supported on potassium carbonate powder. The present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon (b) with an increased number of carbon atoms, which is useful as an intermediate in producing medicines, agricultural chemicals, etc., by alkylating the side chain using a group monoolefin.
アルキル置換芳香族炭化水素と脂肪族モノオレフィンを
反応させ側鎖アルキル化反応によって炭素数を増したア
ルキル置換芳香族炭化水素を製造する従来の方法に関し
ては、例えば英国特許明細書第１２６９２８０号には炭
酸カリウムに金属ナトリウムを担持した触媒を用いて該
反応を行う方法が開示されている。該公報には炭酸カリ
ウムにナトリウムを蒸着担持する方法、液体アンモニア
に溶解したナトリウムを沈着担持する方法、あるいは不
活性ガス雰囲気下に、１５０〜４００℃で熔融させたナ
トリウムを混合して担持する方法によって調製された触
媒を使用できる旨が記載されている。該公報の実施例の
触媒はいずれも高温でナトリウムを溶融担持する方法に
よって調製した触媒である。Regarding the conventional method of producing an alkyl-substituted aromatic hydrocarbon having an increased number of carbon atoms through a side chain alkylation reaction by reacting an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin, for example, British Patent Specification No. 1269280 describes A method is disclosed in which the reaction is carried out using a catalyst in which sodium metal is supported on potassium carbonate. The publication describes a method in which sodium is deposited and supported on potassium carbonate, a method in which sodium dissolved in liquid ammonia is deposited and supported, or a method in which sodium melted at 150 to 400°C is mixed and supported in an inert gas atmosphere. It is stated that a catalyst prepared by can be used. All of the catalysts in the Examples of this publication were prepared by a method of melting and supporting sodium at high temperatures.
一般に高温下にアルカリ金属を熔融担持するためには、
キルンなど特別な調製装置を必要とし操作が繁雑であり
、調製した触媒は容易に発火の危険性があることからそ
の取扱い上の安全性に課題をかかえている。又得られる
触媒においてはナトリウムの担体への分散が不均一であ
りＮａ−に間の交換率が低い。そのため該公報の実施例
の結果も含めて従来の触媒の活性は未だ充分とは言えな
い。Generally, in order to melt and support alkali metals at high temperatures,
It requires special preparation equipment such as a kiln and is complicated to operate, and the prepared catalyst can easily catch fire, posing safety issues when handling it. In addition, in the resulting catalyst, the dispersion of sodium in the carrier is non-uniform, and the exchange rate between Na- and Na- is low. Therefore, the activity of conventional catalysts, including the results of the examples in the publication, cannot be said to be sufficient.
本発明者等は側鎖アルキル化反応によって炭素数を増し
たアルキル置換芳香族炭化水素を製造する際に使用され
ている従来の触媒には前記した問題点のあることを認め
た。そこで、これを改良すべ〈従来に比べて簡単かつ安
全な方法によってしかも活性の高い触媒を調整し、これ
を用いてアルキル置換芳香族炭化水素（ａ）を脂肪族モ
ノオレフィンによって側鎖アルキル化して炭素数を増し
たアルキル置換芳香族炭化水素（ｂ）を従来の触媒に比
して高い収量で得る方法について検討した。The present inventors have recognized that the conventional catalysts used in the production of alkyl-substituted aromatic hydrocarbons with increased carbon numbers through side chain alkylation reactions have the above-mentioned problems. Therefore, it is necessary to improve this by preparing a highly active catalyst using a simpler and safer method than before, and using this to alkylate the side chain of an alkyl-substituted aromatic hydrocarbon (a) with an aliphatic monoolefin. We investigated a method for obtaining an alkyl-substituted aromatic hydrocarbon (b) with an increased number of carbon atoms in a higher yield than with conventional catalysts.
その結果、下記方法を採用すれば前記目的を達成できる
ことを見出し本発明を完成するに到った。As a result, the inventors discovered that the above object could be achieved by employing the following method and completed the present invention.
すなわち本発明の方法によれば、アルカリ置換芳香族炭
化水素を脂肪族モノオレフィンにより側鎖アルキル化す
るに際し、アルカリ金属と炭酸カリウム粉体をアルカリ
金属に対して不活性な液状の炭化水素からなる分散媒中
でアルカリ金属の融点以上の温度で混合することにより
炭酸カリウム粉体にアルカリ金属を担持せしめた触媒を
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
側鎖アルキル化方法、が提示される。That is, according to the method of the present invention, when side chain alkylating an alkali-substituted aromatic hydrocarbon with an aliphatic monoolefin, an alkali metal and potassium carbonate powder are replaced with a liquid hydrocarbon inert to alkali metals. A method for side chain alkylation of alkyl-substituted aromatic hydrocarbons is presented, which is characterized by using a catalyst in which an alkali metal is supported on potassium carbonate powder by mixing in a dispersion medium at a temperature equal to or higher than the melting point of the alkali metal. be done.
放−娠
本発明で使用される触媒は特定の方法によって炭酸カリ
ウム粉体にアルカリ金属を担持せしめた触媒である。す
なわち、本発明では、アルカリ金属と炭酸カリウム粉体
をアルカリ金属に対して不活性な液状の炭化水素からな
る分散媒中でアルカリ金属の融点以上の温度で混合する
ことにより炭酸カリウム粉体にアルカリ金属を担持せし
めた触媒を用いて、アルキル置換芳香族炭化水素の側鎖
アルキル化反応が行われる。Release The catalyst used in the present invention is a catalyst in which an alkali metal is supported on potassium carbonate powder by a specific method. That is, in the present invention, an alkali is added to the potassium carbonate powder by mixing the alkali metal and the potassium carbonate powder in a dispersion medium consisting of a liquid hydrocarbon that is inert to the alkali metal at a temperature higher than the melting point of the alkali metal. A side chain alkylation reaction of an alkyl-substituted aromatic hydrocarbon is carried out using a metal-supported catalyst.
本発明で使用されるアルカリ金属としてはりチウム、ナ
トリウム、カリウムなどであって、この中ではナトリウ
ムが好ましい。Alkali metals used in the present invention include lithium, sodium, potassium, etc. Among these, sodium is preferred.
本発明で用いられる炭酸カリウム粉体については、従来
から知られている方法によって得られる炭酸カリウム粉
体を使用することができる。本発明では特にどういった
物性の炭酸カリウムを用いなければならないということ
はないが、後述する反応の活性の点から本発明では以下
に示す物性を有する炭酸カリウム粉体を使用することが
特に好ましい。すなわち、嵩密度が通常０．８５ｇ／ｄ
以下、平均粒径が通常１００ないし８００μでかっ粒径
１００ないし８００μの範囲にある粉体重量が全粉体重
量の通常６０％以上を占める炭酸カリウム粉体を用いて
得られる触媒を使用した場合には、本発明の側鎖アルキ
ル化反応によって生成するアルキル置換芳香族炭化水素
の生成量が増大するので特に好ましい。なお前記平均粒
径はＪＩＳ規格標準ふるいを用いてふるい分は法によっ
て粒度分布を求めＲＲ３線図からメジアン径として求め
られる。Regarding the potassium carbonate powder used in the present invention, potassium carbonate powder obtained by a conventionally known method can be used. In the present invention, it is not particularly necessary to use potassium carbonate having physical properties, but from the viewpoint of the activity of the reaction described below, it is particularly preferable to use potassium carbonate powder having the physical properties shown below in the present invention. . That is, the bulk density is usually 0.85 g/d.
Below, when using a catalyst obtained using potassium carbonate powder, the average particle size is usually 100 to 800μ, and the powder weight in the range of 100 to 800μ usually accounts for 60% or more of the total powder weight. It is particularly preferable to increase the amount of alkyl-substituted aromatic hydrocarbons produced by the side chain alkylation reaction of the present invention. The average particle diameter is determined by using a JIS standard sieve, determining the particle size distribution by the sieve method, and determining the median diameter from the RR3 diagram.
本発明で使用されるアルカリ金属に対して不活性な液状
の炭化水素からなる分散媒として具体的には、ベンゼン
、トルエン、エチルベンゼン、イソプロピルベンゼン、
キシレン、メシチレン等のアルキル基で置換された芳香
族炭化水素およびヘキサン、ヘプタン、オクタン、デカ
ン、ドデカン、トリデカン等の脂肪族飽和炭化水素およ
びテトラリン、デカリン、シクロヘキサン等の脂環式炭
化水素などを例示できるが、本発明ではこの中でもトル
エン、キシレン、ヘキサン、ｎ−オクタン、ｎ−デカン
を用いることが好ましい。特に後述する本発明の反応に
おいて原料として用いられるアルキル置換芳香族炭化水
素（８１を前記分散媒として用いると、触媒調製に引き
続いて反応を開始できるので操作が簡単となり経済的か
つ安全上有利であるので特に好ましい。本発明では前記
分散媒は単独使用しても良いし、又必要に応じて混合使
用することもできる。Specifically, the dispersion medium made of liquid hydrocarbon inert to alkali metals used in the present invention includes benzene, toluene, ethylbenzene, isopropylbenzene,
Examples include aromatic hydrocarbons substituted with alkyl groups such as xylene and mesitylene, aliphatic saturated hydrocarbons such as hexane, heptane, octane, decane, dodecane, and tridecane, and alicyclic hydrocarbons such as tetralin, decalin, and cyclohexane. However, in the present invention, among these, toluene, xylene, hexane, n-octane, and n-decane are preferably used. In particular, when an alkyl-substituted aromatic hydrocarbon (81) used as a raw material in the reaction of the present invention, which will be described later, is used as the dispersion medium, the reaction can be started following catalyst preparation, which is advantageous in terms of ease of operation and economic and safety. Therefore, it is particularly preferable.In the present invention, the above-mentioned dispersion medium may be used alone, or may be used in combination as necessary.
本発明では、触媒を調製するに当たって使用される炭酸
カリウム粉体とアルカリ金属の割合については、該粉体
の１００重量部に対してアルカリ金属が通常０．５ない
し１０重量部、好ましくは１ないし７重量部である。ア
ルカリ金属の量が０．５重量部以下の場合には後述する
本発明の側鎖アルキル化反応の活性が低く、又１０重量
部以上の場合には均一な担持が困難であるばかりか、反
応中に高重合物を副生じ、触媒を被毒する。また極端な
場合にはピッチ様の固形物を発生し、反応器を閉塞する
等のトラブルを生ずるので好ましくない。また本発明で
前記分散媒を使用する場合の割合については、炭酸カリ
ウム粉体の１００重量部に対して通常１００ないし１０
００重量部、好ましくは１５０ないし５００重量部であ
る。In the present invention, the ratio of potassium carbonate powder and alkali metal used in preparing the catalyst is usually 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the powder. 7 parts by weight. If the amount of alkali metal is less than 0.5 parts by weight, the activity of the side chain alkylation reaction of the present invention, which will be described later, will be low, and if it is more than 10 parts by weight, not only will it be difficult to support the alkali metal uniformly, but the reaction will be delayed. Highly polymerized substances are produced as by-products, poisoning the catalyst. Furthermore, in extreme cases, pitch-like solids may be generated, which may cause troubles such as clogging of the reactor, which is not preferable. In addition, in the present invention, the proportion of the dispersion medium used is usually 100 to 10 parts by weight per 100 parts by weight of the potassium carbonate powder.
00 parts by weight, preferably 150 to 500 parts by weight.
本発明では、アルカリ金属と炭酸カリウム粉体を前記分
散媒中にアルカリ金属の融点以上の温度で混合すること
によってアルカリ金属を炭酸カリウム粉体に担持せしめ
て本発明の触媒が得られるわけであるが、この場合の該
温度としては通常１２０ないし２５０℃、好ましくは１
５０ないし２３０℃である。該温度が１２０℃以下の場
合には炭酸カリウムのカリウムイオンとアルカリ金属と
の相互作用ならびに炭酸カリウム粉体に由来するカリウ
ムと担持しようとするアルカリ金属例えばナトリウムと
の交換反応が起こりにくいため高活性な触媒が得られな
いので好ましくない。また温度が２５０℃以上の場合に
は、トルエン、エチルベンゼン、キシレン等を前記分散
媒として用いた場合にはこの分散媒自身のカップリング
反応等が触媒調製時に発生し、これによって触媒は被毒
されて活性を失ってしまい、又分散媒として前記脂肪族
飽和炭化水素を用いた場合も金属状のカリウムが多く副
生し、反応中にピッチ状の固形物を生成するので好まし
くない。In the present invention, the catalyst of the present invention is obtained by mixing an alkali metal and potassium carbonate powder in the dispersion medium at a temperature higher than the melting point of the alkali metal, thereby supporting the alkali metal on the potassium carbonate powder. However, the temperature in this case is usually 120 to 250°C, preferably 1
The temperature is 50 to 230°C. When the temperature is below 120°C, interaction between potassium ions in potassium carbonate and alkali metals and exchange reactions between potassium derived from potassium carbonate powder and alkali metals to be supported, such as sodium, are difficult to occur, resulting in high activity. This is not preferred because a suitable catalyst cannot be obtained. Furthermore, when the temperature is 250°C or higher, when toluene, ethylbenzene, xylene, etc. are used as the dispersion medium, a coupling reaction of the dispersion medium itself occurs during catalyst preparation, and the catalyst is poisoned by this. Furthermore, when the aliphatic saturated hydrocarbon is used as a dispersion medium, a large amount of metallic potassium is produced as a by-product, and a pitch-like solid is produced during the reaction, which is not preferable.
本発明では、前記方法によって炭酸カリウム粉体にアル
カリ金属を担持して得られる触媒は、この後分散媒を除
去して水分を含まない不活性ガス雰囲気中にて反応に供
する迄保存しても良いし、あるいはそのまま水分を含ま
ない前記分散媒中にて保存しても良い。この場合、分散
媒として後述する本発明の側鎖アルキル化反応の原料と
して用いるアルキル置換芳香族炭化水素（ａ）を用いた
場合には、調製した触媒をそのまま次の反応に供するこ
とができるので特に好ましいことは前述したとおりであ
る。In the present invention, the catalyst obtained by supporting an alkali metal on potassium carbonate powder by the above method may be stored after removing the dispersion medium in an inert gas atmosphere containing no moisture until it is subjected to the reaction. Alternatively, it may be stored as is in the dispersion medium that does not contain water. In this case, if the alkyl-substituted aromatic hydrocarbon (a) used as a raw material for the side chain alkylation reaction of the present invention, which will be described later, is used as a dispersion medium, the prepared catalyst can be directly used in the next reaction. What is particularly preferable is as described above.
前記した本発明の方法によって得られる触媒は、担体の
炭酸カリウム粉体に該炭酸カリウムに由来しないアルカ
リ金属が担体基準で通常０．５ないし１０重量％、好ま
しくは１ないし７重量％担持された触媒である。In the catalyst obtained by the method of the present invention described above, an alkali metal not derived from the potassium carbonate is supported on the potassium carbonate powder as a carrier, usually 0.5 to 10% by weight, preferably 1 to 7% by weight, based on the carrier. It is a catalyst.
本発明の方法によれば従来法に比べて比較的低温でしか
も簡単な方法によって後述する反応に対して高活性な触
媒が得られる。According to the method of the present invention, a highly active catalyst for the reactions described below can be obtained at a relatively low temperature and in a simple manner compared to conventional methods.
反−息
本発明では前記方法によって調製された触媒の存在下に
アルキル置換芳香族炭化水素（ａ）と脂肪族モノオレフ
ィンを反応させて側鎖アルキル化反応によって炭素数を
増したアルキル置換芳香族炭化水素（ｂ）が製造される
。In the present invention, an alkyl-substituted aromatic hydrocarbon (a) and an aliphatic monoolefin are reacted in the presence of a catalyst prepared by the above method to increase the number of carbon atoms through a side chain alkylation reaction. Hydrocarbon (b) is produced.
本発明で使用されるアルキル置換芳香族炭化水素（ａ）
として具体的にはトルエン、エチルベンゼン、ｎ−プロ
ピルベンゼン、イソプロピルベンゼン、ｎ−ブチルベン
ゼン、５ｅｃ−ブチルベンゼン、イソブチルベンゼン、
ｎ−デシルベンゼン、キシレン、メシチレン、テトラベ
ンゼン等のアルキル置換ベンゼン、メチルナフタレン、
ジメチルナフタレン、イソプロピルナフタレン等のアル
キル置換ナフタレンおよびメチルインダン、エチルイン
ダン等のアルキル置換インダンなどを例示でき、本発明
では側鎖アルキル基においてα位の炭素に水素原子が結
合したアルキル基を少なくとも１つ以上有するアルキル
置換芳香族炭化水素が使用される。本発明では前記した
アルキル置換芳香族炭化水素（ａ）の中でも特にトルエ
ンを使用することが好ましい。Alkyl-substituted aromatic hydrocarbon (a) used in the present invention
Specifically, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, 5ec-butylbenzene, isobutylbenzene,
Alkyl-substituted benzenes such as n-decylbenzene, xylene, mesitylene, and tetrabenzene, methylnaphthalene,
Examples include alkyl-substituted naphthalenes such as dimethylnaphthalene and isopropylnaphthalene, and alkyl-substituted indanes such as methylindane and ethylindane. An alkyl-substituted aromatic hydrocarbon having the above is used. In the present invention, it is particularly preferable to use toluene among the alkyl-substituted aromatic hydrocarbons (a) described above.
本発明で使用される脂肪族モノオレフィンとして具体的
にはエチレン、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、１−ヘプテン、２
−ヘプテン、２−オクテン、２−デセン、３−メチル−
１−ブテン、２−メチル−２−ブテン、４−メチル−１
−ペンテン等を例示できるが、この中ではエチレン、プ
ロピレン１，１−ブテン、２−ブテン、イソブチンを使
用することが好ましい。Specifically, the aliphatic monoolefins used in the present invention include ethylene, propylene, 1-butene, 2-butene,
Isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2
-Heptene, 2-octene, 2-decene, 3-methyl-
1-butene, 2-methyl-2-butene, 4-methyl-1
Examples include -pentene, among which ethylene, propylene 1,1-butene, 2-butene, and isobutyne are preferably used.
本発明の方法では、前記したアルキル置換芳香族炭化水
素（ａｌと脂肪族モノオレフィンを反応させる場合の条
件として、これら原料の仕込み割合については、アルキ
ル置換芳香族炭化水素（ａ）の１００モル部に対して脂
肪族モノオレフィンは通常１０ないし２０００モル部、
好ましくは１０口ないし７００モル部である。触媒の使
用量については、アルキル置換芳香族炭化水素（ａｌの
１００重量部当たり通常０．１ないし５０重量部、好ま
しくは１ないし２０重量部の触媒が用いられる。本発明
では触媒調製後、反応を行うに当たって必要に応じて例
えばベンゼン、エチルアミン、トリエチルアミン、ブチ
ルアミン、シクロヘキシルアミン、トルイジン、ｎ−デ
カリン、ヘキサン、シクロヘキサン等の反応溶媒を適宜
の量用いても差し支えない。In the method of the present invention, as the conditions for reacting the alkyl-substituted aromatic hydrocarbon (al) with the aliphatic monoolefin, the charging ratio of these raw materials is 100 molar parts of the alkyl-substituted aromatic hydrocarbon (a). The aliphatic monoolefin is usually 10 to 2000 mole parts,
Preferably it is 10 to 700 mole parts. Regarding the amount of catalyst used, the amount of catalyst used is usually 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight per 100 parts by weight of the alkyl-substituted aromatic hydrocarbon (al).In the present invention, after preparing the catalyst, the reaction In carrying out this process, an appropriate amount of a reaction solvent such as benzene, ethylamine, triethylamine, butylamine, cyclohexylamine, toluidine, n-decalin, hexane, cyclohexane, etc. may be used as necessary.
本発明の方法では、反応を例えば回分式の場合は以下の
方法によって実施することができる。オートクレーブ等
の反応器にアルキル置換芳香族炭化水素＋８）、触媒お
よび必要に応じて反応溶媒を所定量仕込み、所定の温度
に昇温してから脂肪族モノオレフィンを所定量注入する
方法を示すことができるが、本発明では必ずしもこの方
法に限定されるものではなく、反応の他の方式として固
定床加圧流通式を用いることができる。反応は攪拌下に
実施され、反応温度としては通常１４０ないし２５０℃
、好ましくは１５０ないし２００℃であり、反応圧力は
通常１０ないし２００気圧の範囲にある。反応時間は通
常１ないし２０時間である。In the method of the present invention, the reaction can be carried out by the following method, for example, in the case of a batch method. To show a method of charging a predetermined amount of an alkyl-substituted aromatic hydrocarbon + 8), a catalyst, and a reaction solvent if necessary into a reactor such as an autoclave, raising the temperature to a predetermined temperature, and then injecting a predetermined amount of aliphatic monoolefin. However, the present invention is not necessarily limited to this method, and a fixed bed pressurized flow method can be used as another reaction method. The reaction is carried out under stirring, and the reaction temperature is usually 140 to 250°C.
, preferably 150 to 200°C, and the reaction pressure is usually in the range of 10 to 200 atm. The reaction time is usually 1 to 20 hours.
反応終了後、反応混合物を濾過して触媒を除き、蒸留、
晶析等の通常の分離手段によって本発明の目的とする側
鎖アルキル化反応によって炭素数を増したアルキル置換
芳香族炭化水素（ｂ）を分離することができる。本発明
では該アルキル置換芳香族炭化水素（ｂ）として具体的
には、ｎ−プロピルベンゼン、ｎ−プロピルトルエン、
５ｅｃ−７’チルベンゼン、５ｅＣ−ブチルトルエン、
ｔｅｒｔ−アミルベンゼン、イソブチルベンゼン、イソ
ブチルトルエン、２−メチルベンゼン、２−メチルブチ
ルトルエン、ｎ−プロビルナフタレン、等を例示できる
が、この中ではｎ−プロピルベンゼン、ｎ−プロピルト
ルエン、イソブチルベンゼン、イソブチルトルエン、ｔ
ｅｒ ｔ−アミルベンゼン、２−メチルブチルベンゼン
、２−メチルブチルトルエンなどが好ましい。After the reaction is complete, the reaction mixture is filtered to remove the catalyst, distilled,
The alkyl-substituted aromatic hydrocarbon (b) having an increased number of carbon atoms due to the side chain alkylation reaction, which is the object of the present invention, can be separated by ordinary separation means such as crystallization. In the present invention, the alkyl-substituted aromatic hydrocarbon (b) specifically includes n-propylbenzene, n-propyltoluene,
5ec-7' thylbenzene, 5eC-butyltoluene,
Examples include tert-amylbenzene, isobutylbenzene, isobutyltoluene, 2-methylbenzene, 2-methylbutyltoluene, n-propylnaphthalene, among which n-propylbenzene, n-propyltoluene, isobutylbenzene, isobutyltoluene, t
Preferred are er t-amylbenzene, 2-methylbutylbenzene, 2-methylbutyltoluene, and the like.
本発明の方法によれば、従来法に比べて簡単な方法によ
って分散媒中で調製される、アルカリ金属を炭酸カリウ
ム粉体に担持した触媒を用いることにより、側鎖アルキ
ル化反応により炭素数を増したアルキル置換芳香族炭化
水素（ｂ）を従来法に比べて高い収量で得ることができ
る。According to the method of the present invention, by using a catalyst in which an alkali metal is supported on potassium carbonate powder, which is prepared in a dispersion medium by a simpler method than in the conventional method, the number of carbon atoms can be increased by a side chain alkylation reaction. The alkyl-substituted aromatic hydrocarbon (b) can be obtained in a higher yield than in the conventional method.
以下、本発明の方法を実施例によって具体的に説明する
。Hereinafter, the method of the present invention will be specifically explained using examples.
実施例１
炭酸カリウム１．５水和塩のスラリーを１５０℃で粉霧
乾燥して得られた顆粒状粉末を４００℃で２時間焼成し
た後、乾燥窒素雰囲気下に嵩密度および粒度分布をロー
タツブ法にて測定した。この炭酸カリウムの嵩密度は０
．６７ｇ／＊１であり、平均粒子径（メジアン径Ｄｍｅ
ｄ ）は４２０μであり、さらに１００〜８００μの粒
径の粒子が全体の９２％を占めた。Example 1 A granular powder obtained by spray-drying a slurry of potassium carbonate hemihydrate at 150°C was calcined at 400°C for 2 hours, and then the bulk density and particle size distribution were determined by rotary bubbling under a dry nitrogen atmosphere. Measured using the method. The bulk density of this potassium carbonate is 0
．． 67g/*1, and the average particle diameter (median diameter Dme
d) was 420μ, and particles with a particle size of 100 to 800μ accounted for 92% of the total.
この炭酸カリウム粉末５８ｇおよび金属ナトリウム２ｇ
をトルエン２００１！とともにオートクレーブ゛（１β
）に入れ、１９０℃で２時間、６００ｒｐｍの回転数で
攪拌することによって触媒を調製した。この触媒のアル
カリ金属を原子吸光法で分析したところ、金属に対金属
Ｎａの原子比は１０７対１であった。58g of this potassium carbonate powder and 2g of metallic sodium
Toluene 2001! Autoclave (1β
) and stirring at 600 rpm for 2 hours at 190°C. When the alkali metal of this catalyst was analyzed by atomic absorption spectroscopy, the atomic ratio of Na to metal was 107:1.
温度を １５０℃に低下した後、トルエンをさらに４０
０ｍ！加え、これにプロピレンを圧入し、初期反応圧力
を６０ｋｇ／ｃｆｆｌに設定した。プロピレン導入と同
時に反応が始まり、圧力低下が認められた。After reducing the temperature to 150°C, add toluene to an additional 40°C.
0m! In addition, propylene was pressurized into this, and the initial reaction pressure was set at 60 kg/cffl. The reaction started at the same time as propylene was introduced, and a pressure drop was observed.
容器内の圧力が３０ｋｇ／−になった時点で、再びプロ
ピレンを圧入して５０ｋｇ／ｃＪに戻し、反応を再開し
た。この操作を３回繰返した後反応を終了し、内容物を
ガスクロマトグラフィー（カラムＰＥＧ６０００、 ４
ｍ）で分析した。全反応時間は４時間であった。結果を
表１に示す。When the pressure inside the container reached 30 kg/-, propylene was again pressurized to return the pressure to 50 kg/cJ, and the reaction was restarted. After repeating this operation three times, the reaction was terminated and the contents were subjected to gas chromatography (column PEG6000, 4
m). Total reaction time was 4 hours. The results are shown in Table 1.
表 １
比較例１
実施例１で使用したものと同じ４００℃で焼成した炭酸
カリウムを攪拌装置のついた円筒形のセパラブルフラス
コに入れ、マントルヒーターを用いて実施例１と同じ１
９０℃に昇温した。窒素雰囲気下に攪拌しながら、金属
ナトリウム２ｇを少量づつ落下し、添加後も約１時間同
じ状態で攪拌を継続した。室温迄降温し、窒素雰囲気下
にオートクレーブに移し、トルエン、６００ｍｆを加え
て１５０℃に昇温した。この触媒の一部を原子吸光で分
析したところ金属に対金属Ｎａの原子比率は０．５３：
１であった。実施例１に準じプロピレンを導入し、６０
ｋｇ／ｃＩａまで昇温し、反応を繰返した。この時の全
反応時間は１３時間であった。結果を表１に示す。Table 1 Comparative Example 1 Potassium carbonate calcined at 400°C, the same as that used in Example 1, was placed in a cylindrical separable flask equipped with a stirring device, and the mixture was heated using a mantle heater.
The temperature was raised to 90°C. While stirring under a nitrogen atmosphere, 2 g of metallic sodium was dropped little by little, and stirring was continued in the same state for about 1 hour after the addition. The temperature was lowered to room temperature, transferred to an autoclave under a nitrogen atmosphere, toluene and 600 mf were added, and the temperature was raised to 150°C. When a part of this catalyst was analyzed by atomic absorption, the atomic ratio of Na to metal was 0.53:
It was 1. Propylene was introduced according to Example 1, and 60
The temperature was raised to kg/cIa and the reaction was repeated. The total reaction time at this time was 13 hours. The results are shown in Table 1.
実施例２
実施例１においてトルエンの替りにｐ−キシレンを用い
る以外はすべて同じ方法で触媒を調製した後、引継きｐ
−キシレンと１−ブテンの反応を行った。バラキシレン
４００ｍｆおよび触媒を入れた後、１７０℃に昇温し、
■−ブテンを導入して８０ｋｇ／ｒｕａにした。８時間
後生成物をガスクロマトグラフィー（ＰＥＧ ６０００
． ４ｍ）を用いて分析した。Example 2 A catalyst was prepared in the same manner as in Example 1 except that p-xylene was used instead of toluene, and then p-xylene was used instead of toluene.
- A reaction between xylene and 1-butene was carried out. After adding 400mf of baraxylene and a catalyst, the temperature was raised to 170°C,
①-Butene was introduced to make it 80 kg/rua. After 8 hours, the product was subjected to gas chromatography (PEG 6000
．． 4m).
表 ２
実施例３
炭酸カリウム水溶液をエバポレーターで濃縮して得られ
た結晶を遠心分離器で脱水した後粉砕し、４００℃で２
時間焼成することによって炭酸カリウム粉末を得た。こ
の顆粒状粉末は嵩密度が０．７８ｇ／ｍｌであり、平均
粒径（Ｄｍｅｄ ）は３２０ ｐ、かつ粒度分布は１０
０〜８００μの粒径の粒子が全体の８５％を占めた。Table 2 Example 3 The crystals obtained by concentrating an aqueous potassium carbonate solution using an evaporator were dehydrated using a centrifuge, and then ground, and the crystals were heated at 400°C for 2 hours.
Potassium carbonate powder was obtained by firing for a period of time. This granular powder has a bulk density of 0.78 g/ml, a mean particle size (Dmed) of 320 p, and a particle size distribution of 10
Particles with a particle size of 0 to 800 μ accounted for 85% of the total.
この炭酸カリウム５７ｇおよび金属ナトリウム３ｇなら
びにｎ−デカン２００ｍｊとともにオートクレーブに入
れ、２３０度で３時間６００ｒｐｍの回転数で攪拌する
ことによって触媒を開裂した。反応器の温度を１６０℃
に下げ、β−メチルナフタレン２００ｇを加えた後、エ
チレンを容器内の圧力が５０ｋｇ／−に達するまで圧入
した。２時間後容器内の圧力は２８ｋｇ／−を示した。The catalyst was placed in an autoclave together with 57 g of potassium carbonate, 3 g of sodium metal, and 200 mj of n-decane, and stirred at 600 rpm for 3 hours at 230 degrees to cleave the catalyst. The temperature of the reactor is 160℃
After adding 200 g of β-methylnaphthalene, ethylene was pressurized until the pressure inside the container reached 50 kg/-. After 2 hours, the pressure inside the container was 28 kg/-.
結果を第３表に示す。The results are shown in Table 3.
比較例２
比較例１と同じ方法で調製した触媒６０ｇをｎ−デカン
２００ｍ！ならびにβ−メチルナフタレン２００ｇとと
もにオートクレーブに入れ、１６０℃でエチレンを５０
ｋｇ／ｃ＋＆まで圧入して反応させた結果を表３に示し
た。Comparative Example 2 60 g of catalyst prepared in the same manner as Comparative Example 1 was added to 200 m of n-decane! and 200 g of β-methylnaphthalene in an autoclave, and 50 g of ethylene was added at 160°C.
Table 3 shows the results of the reaction at a pressure of up to kg/c+&.
なお５時間で容器内の圧力は３２ｋｇ／ｃ１ａを示した
。Note that the pressure inside the container was 32 kg/c1a after 5 hours.
Claims (1)
ィンにより側鎖アルキル化するに際し、アルカリ金属と
炭酸カリウム粉体をアルカリ金属に対して不活性な炭化
水素からなる分散媒中でアルカリ金属の融点以上の温度
で混合することにより炭酸カリウム粉体にアルカリ金属
を担持せしめた触媒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側鎖アルキル化方法。(1) When side-chain alkylating an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin, the alkali metal and potassium carbonate powder are mixed in a dispersion medium consisting of a hydrocarbon that is inert to the alkali metal at the melting point of the alkali metal. A method for side chain alkylation of alkyl-substituted aromatic hydrocarbons, characterized by using a catalyst in which an alkali metal is supported on potassium carbonate powder by mixing at a temperature above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60061881A JPH0699329B2 (en) | 1985-03-28 | 1985-03-28 | Method for side-chain alkylation of alkyl-substituted aromatic hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60061881A JPH0699329B2 (en) | 1985-03-28 | 1985-03-28 | Method for side-chain alkylation of alkyl-substituted aromatic hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61221133A true JPS61221133A (en) | 1986-10-01 |
| JPH0699329B2 JPH0699329B2 (en) | 1994-12-07 |
Family
ID=13183923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60061881A Expired - Fee Related JPH0699329B2 (en) | 1985-03-28 | 1985-03-28 | Method for side-chain alkylation of alkyl-substituted aromatic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699329B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4916100A (en) * | 1986-12-31 | 1990-04-10 | Neste Oy | Process for preparing a catalyst system for selective alkylation of toluene with propylene |
| US5157186A (en) * | 1990-11-13 | 1992-10-20 | Ethyl Corporation | Process for catalytic coupling of an alkene with an aromatic hydrocarbon |
| FR2703678A1 (en) * | 1993-04-08 | 1994-10-14 | Inst Francais Du Petrole | Process for the preparation of isobutylbenzene in the presence of a supported catalyst |
| US5625102A (en) * | 1993-12-27 | 1997-04-29 | Mitsubishi Oil Co., Ltd. | Method of alkylating the side chain of alkyl-substituted aromatic hydrocarbons |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153229A (en) * | 1984-08-22 | 1986-03-17 | Nippon Petrochem Co Ltd | Alkylation process |
| JPS6157526A (en) * | 1984-08-29 | 1986-03-24 | Nippon Petrochem Co Ltd | Production of aromatic hydrocarbon |
-
1985
- 1985-03-28 JP JP60061881A patent/JPH0699329B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6153229A (en) * | 1984-08-22 | 1986-03-17 | Nippon Petrochem Co Ltd | Alkylation process |
| JPS6157526A (en) * | 1984-08-29 | 1986-03-24 | Nippon Petrochem Co Ltd | Production of aromatic hydrocarbon |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4916100A (en) * | 1986-12-31 | 1990-04-10 | Neste Oy | Process for preparing a catalyst system for selective alkylation of toluene with propylene |
| US5157186A (en) * | 1990-11-13 | 1992-10-20 | Ethyl Corporation | Process for catalytic coupling of an alkene with an aromatic hydrocarbon |
| FR2703678A1 (en) * | 1993-04-08 | 1994-10-14 | Inst Francais Du Petrole | Process for the preparation of isobutylbenzene in the presence of a supported catalyst |
| US5625102A (en) * | 1993-12-27 | 1997-04-29 | Mitsubishi Oil Co., Ltd. | Method of alkylating the side chain of alkyl-substituted aromatic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699329B2 (en) | 1994-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01207137A (en) | Carrier for catalyst and manufacture of catalyst and dimerization method of olefin | |
| JP2748631B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| JPS61221133A (en) | Method of side chain alkylation of alkyl-substituted aromatic hydrocarbon | |
| JPH03165837A (en) | Manufacture of catalytic support and olefin dimer process | |
| EP0328940B1 (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| EP0357031B1 (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| JPH05310613A (en) | Production of monoalkenylbenzene | |
| JP2748646B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| US5104843A (en) | Catalyst composition for coupling process | |
| EP0406867A1 (en) | Catalysts and catalyst supports, with inorganic nitrates, for olefin dimerization | |
| JPH10259147A (en) | Production of monoalkenylbenzenes | |
| JP2625985B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| JPH0639396B2 (en) | Method for side-chain alkylation of alkyl-substituted aromatic hydrocarbons | |
| US5227559A (en) | Process for preparing alkyl-subtituted aromatic hydrocarbons | |
| JP2830129B2 (en) | Preparation of alkyl-substituted aromatic hydrocarbons | |
| JP3028020B2 (en) | Method for producing monoalkenylbenzenes | |
| JP2596108B2 (en) | Preparation of alkyl-substituted aromatic hydrocarbons | |
| GB2254802A (en) | Catalyst composition for coupling process | |
| US5347062A (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| US5157186A (en) | Process for catalytic coupling of an alkene with an aromatic hydrocarbon | |
| JPS61263643A (en) | Preparation of catalyst deposited with alkali metal | |
| JP2748577B2 (en) | Process for producing alkyl-substituted aromatic hydrocarbons | |
| JP2792132B2 (en) | Process for producing alkyl-substituted aromatic hydrocarbons | |
| JP2745706B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| JPH06256233A (en) | Side chain alkalation of alkyl-substituted aromatic hydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |