JPH0356427A - Production of cyclic dimer of 3-butadiene - Google Patents
Production of cyclic dimer of 3-butadieneInfo
- Publication number
- JPH0356427A JPH0356427A JP1190565A JP19056589A JPH0356427A JP H0356427 A JPH0356427 A JP H0356427A JP 1190565 A JP1190565 A JP 1190565A JP 19056589 A JP19056589 A JP 19056589A JP H0356427 A JPH0356427 A JP H0356427A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- catalyst
- butadiene
- alcohol
- organic phosphorus
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 26
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 16
- 230000000447 dimerizing effect Effects 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 22
- 239000004912 1,5-cyclooctadiene Substances 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 13
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 8
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 8
- -1 aluminum alkoxide Chemical class 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RMTMGXCQEXSWLI-UHFFFAOYSA-N (2-tert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)O RMTMGXCQEXSWLI-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 description 1
- XCPQQZKNXRQMIQ-UHFFFAOYSA-L nickel(2+);oct-2-enoate Chemical compound [Ni+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O XCPQQZKNXRQMIQ-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- MCWWHQMTJNSXPX-UHFFFAOYSA-N tribenzylalumane Chemical compound C=1C=CC=CC=1C[Al](CC=1C=CC=CC=1)CC1=CC=CC=C1 MCWWHQMTJNSXPX-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 1
- FQMMZTDQJFUYSA-UHFFFAOYSA-N triheptylalumane Chemical compound CCCCCCC[Al](CCCCCCC)CCCCCCC FQMMZTDQJFUYSA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZEAQEZGTGCQGBN-UHFFFAOYSA-N tris(2-methoxyphenyl) phosphite Chemical compound COC1=CC=CC=C1OP(OC=1C(=CC=CC=1)OC)OC1=CC=CC=C1OC ZEAQEZGTGCQGBN-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 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
- 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】
〔産業上の利用分野〕
本発明は、１．３−ブタジエンを環状二量化することに
よる１．５−シクロオクタジエン（以下ＣＯＤと略す）
の工業的製造法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention provides 1,5-cyclooctadiene (hereinafter abbreviated as COD) by cyclic dimerization of 1,3-butadiene.
Concerning industrial manufacturing methods.
１．３−プタジエンの環状二量体であるＣＯＤは主にス
ベリン酸の原料として用いられる。又、アルキッド樹脂
、ポリア果ド、可塑剤、難燃剤、触媒、その他工業化学
品の原料又は中間体としても重要である．
〔従来の技術〕
１．３−ブタジエンを二量化してＣＯＤを製造する方法
は、従来より種々提案されている。従来の製造方法にお
いては、一般的に、触媒として、０価のニッケル錯化合
物、又は２価のニッケル化合物を還元したものと、有機
燐化合物等の電子供与体からなるものが、用いられてき
た（特公昭３Ｂ−１６８８２、同３９−１４２２３、同
３９一１４６７３、同３９−１７２７５、同４０−７３
３２、同４０−２１６１８、同４１−７０７１、同４３
−２０９３、同４３−２２９７５、同４５−１０３３５
、同４６−２２４５２、同４７−２０８９、同６１−１
５８４７、同６１−３８１７５）。COD, which is a cyclic dimer of 1,3-ptadiene, is mainly used as a raw material for suberic acid. It is also important as a raw material or intermediate for alkyd resins, polyamides, plasticizers, flame retardants, catalysts, and other industrial chemicals. [Prior Art] Various methods have been proposed in the past for producing COD by dimerizing 1,3-butadiene. In conventional production methods, a catalyst consisting of a zero-valent nickel complex compound or a reduced divalent nickel compound and an electron donor such as an organic phosphorus compound has generally been used. (Tokuko Sho 3B-16882, Sho 39-14223, Sho 39-14673, Sho 39-17275, Sho 40-73
32, 40-21618, 41-7071, 43
-2093, 43-22975, 45-10335
, 46-22452, 47-2089, 61-1
5847, 61-38175).
０価のニッケル化合物と電子供与体からなる触媒を用い
る方法においては、取扱が極めて困難な０価のニッケル
化合物を用いなくてはならないという問題点がある．
一方、２価のニッケル化合物を還元したものと電子供与
体からなる触媒を用いる方法においては、このような欠
点はない。しかし、２価のニッケル化合物を還元するの
にトリアルキルアルミニウムを用いた場合、４−ビニル
シクロヘキセン（以下４−ＶＣＨと略す）及び１．５．
９−シクロドデ力トリエン（以下ＣＤＴと略す）の副生
量が多くなり、ＣＯＤの選択率が低くなる。The method using a catalyst consisting of a zero-valent nickel compound and an electron donor has the problem that a zero-valent nickel compound, which is extremely difficult to handle, must be used. On the other hand, the method using a catalyst consisting of a reduced divalent nickel compound and an electron donor does not have this drawback. However, when trialkylaluminum is used to reduce a divalent nickel compound, 4-vinylcyclohexene (hereinafter abbreviated as 4-VCH) and 1.5.
The amount of by-product of 9-cyclododetriene (hereinafter abbreviated as CDT) increases, and the selectivity of COD decreases.
２価のニッケル化合物の還元にジアルキルアルミニウム
アルコキシドを用いることにより、ブタジエン転化率及
びＣＯＤの選択率を改善できる（特公昭４７−２０８９
）。しかし、従来は別途合威したジアルキルアルミニウ
ムアルコキシドを使用していたので、選択率の改善は充
分ではなかった。By using a dialkylaluminum alkoxide to reduce a divalent nickel compound, the butadiene conversion rate and COD selectivity can be improved (Japanese Patent Publication No. 47-2089
). However, since a separately prepared dialkylaluminum alkoxide has been used in the past, the selectivity has not been improved sufficiently.
又、還元に用いるジアルキルアルミニウムアルコキシド
を別途合威することは高くつくという問題点もある。特
に、ＣＯＤを工業的連続製造法で製造する場合には不利
である。Another problem is that it is expensive to separately prepare the dialkyl aluminum alkoxide used for reduction. This is particularly disadvantageous when producing COD using an industrial continuous production method.
一方、電子供与体である有機燐化合物に、シリル基を有
するもの等特殊な燐化合物を用いることによってもＣＯ
Ｄを８６〜９６％の高い選択率で合成できることが知ら
れている（特公昭６ １−１５８４７、特公昭６１−３
８１７５）。しかし、これらの有機燐化合物は極めて高
価で人手が困難である。On the other hand, it is also possible to reduce CO
It is known that D can be synthesized with a high selectivity of 86 to 96% (Japanese Patent Publication No. 61-15847, Japanese Patent Publication No. 61-3
8175). However, these organic phosphorus compounds are extremely expensive and difficult to handle.
本発明は、１．３−ブタジエンの二量化によりＣＯＤを
製造する方法において、シリル基を有する燐化合物等の
特殊な燐化合物を用いることなく、高い選択率でＣＯＤ
を合成できる方法を提供することを目的とする。The present invention provides a method for producing COD by dimerization of 1,3-butadiene, which produces COD with high selectivity without using a special phosphorus compound such as a phosphorus compound having a silyl group.
The purpose is to provide a method that can synthesize .
本発明は、２価のニッケル化合物を還元したものを電子
供与体と共に用いて、１．３−ブタジエンを二量化して
ＣＯＤを合威する方法であって、■（ａ）２価のニッケ
ル化合物と、
イ）トリアルキルアルミニウム化合物を、アルコール類
の存在下で反応させたものと、■有機燐化合物、
を触媒として使用する方法である。The present invention is a method for dimerizing 1,3-butadiene to synthesize COD by using a reduced divalent nickel compound together with an electron donor, comprising: (a) a divalent nickel compound; This method uses as catalysts: (a) a trialkylaluminum compound reacted in the presence of an alcohol; and (i) an organic phosphorus compound.
本発明の製造法において、アルコール類及びトリアルキ
ルアルミニウムは２価のニッケル化合物を還元するため
のものである。In the production method of the present invention, alcohols and trialkyl aluminum are used to reduce the divalent nickel compound.
又、有機燐化合物は、電子供与体として作用する。The organophosphorus compound also acts as an electron donor.
本発明の製造法は、１．３〜ブタジェンを溶液系で二量
化しＣＯＤとする方法において、２価のニッケル化合物
を還元したものと電子供与体からなる触媒を用いる従来
の方法を改良した製造法である。The production method of the present invention is an improved production method using a catalyst consisting of a reduced divalent nickel compound and an electron donor in the method of dimerizing 1.3-butadiene to form COD in a solution system. It is the law.
即ち、反応器内で、アルコール類の存在下で、トルアル
キルアルミニウムにより２価のニッケル化合物を還元し
、これに電子供与体を組み合わせて触媒とするものであ
る。That is, a divalent nickel compound is reduced with tolualkylaluminum in the presence of an alcohol in a reactor, and an electron donor is combined with the divalent nickel compound to form a catalyst.
本発明の合成方法により、シリル基を有する有機燐化合
物のような特殊で高価な有機燐化合物を用いることなく
、８８〜９５％の高い選択率でＣＯＤを合威できる。By the synthesis method of the present invention, COD can be synthesized with a high selectivity of 88 to 95% without using a special and expensive organic phosphorus compound such as an organic phosphorus compound having a silyl group.
本発明においては、２価のニッケル化合物及びトリアル
キルアルミニウムを添加した後にアルコール類を添加す
ることは、避けなくてはならない。In the present invention, it is necessary to avoid adding alcohol after adding the divalent nickel compound and the trialkylaluminum.
２価のニッケル化合物とトリアルキルアルごニウムがア
ルコール類の無い状態で反応するのを避けるためである
。This is to prevent the divalent nickel compound and trialkylargonium from reacting in the absence of alcohol.
有機燐化合物を加える時期は、２価のニッケル化合物や
アルコール類、トリアルキルアルミニウムを加えた後で
もよく、これらの化合物を加える，前でも加えている最
中でも良い。The organic phosphorus compound may be added after the divalent nickel compound, alcohol, or trialkylaluminum is added, or may be added before, during, or before adding these compounds.
反応系内には、２価のニッケル化合物やアルコール類、
トリアルキルアルミニウム、有機燐化合物を加える前に
、脱水した溶媒を、予め仕込んでおくことが好ましい。In the reaction system, divalent nickel compounds, alcohols,
It is preferable that a dehydrated solvent be charged in advance before adding the trialkylaluminum and the organic phosphorus compound.
反応系内で２価のニッケル化合物等の触媒威分が急激に
反応することを避けるためである。This is to prevent the catalyst component such as the divalent nickel compound from reacting rapidly in the reaction system.
触媒威分の添加は窒素或いはアルゴンガス等の不活性雰
囲気下で行うことが好ましい。It is preferable that the catalyst component is added under an inert atmosphere such as nitrogen or argon gas.
１．３−ブタジエンは、２価のニッケル化合物、アルコ
ール類、トリアルキルアルミニウム、及び有機燐化合物
を添加した後に仕込むことが好ましい。It is preferable to charge 1,3-butadiene after adding the divalent nickel compound, alcohol, trialkyl aluminum, and organic phosphorus compound.
本発明で使用される２価のニッケル化合物の量は、１．
３−ブタジエンに対して、モル比で０．００００５〜０
．０５であり、好ましくは０． ０ ０ ０ １〜０．
０１の範囲である。The amount of divalent nickel compound used in the present invention is 1.
0.00005 to 0 in molar ratio to 3-butadiene
．． 05, preferably 0.05. 0 0 0 1~0.
The range is 01.
トリアルキルアルミニウムの使用量は２価のニッケル化
合物に対してモル比で１〜１００であり、好ましくは２
〜５０である。The amount of trialkylaluminum used is 1 to 100 in molar ratio to the divalent nickel compound, preferably 2
~50.
アルコール類の使用量は、トリアルキルアル【ニウムに
対してモル比で０．１〜３であり、好ましくは０． ５
〜２．５である．
有機燐化合物の使用量は２価のニッケル化合物に対して
モル比で０． １−１ ０であり、好ましくは０．２〜
５である。The amount of alcohol used is 0.1 to 3 in molar ratio to trialkylal[ium], preferably 0.1 to 3. 5
~2.5. The amount of the organic phosphorus compound used is 0.00 molar ratio to the divalent nickel compound. 1-10, preferably 0.2~
It is 5.
２価のニッケル化合物としては、β−ジケトン化合物、
或いは有機カルボン酸塩等が好ましい。As divalent nickel compounds, β-diketone compounds,
Alternatively, organic carboxylic acid salts and the like are preferred.
具体的には、ニッケルアセチルアセトナート（ｎ）ビス
ベンゾイルアセトンニッケル、酢酸ニッケル、ナフテン
酸ニッケル、オクテン酸ニッケル、安息香酸ニッケル等
の２価のニッケル化合物を挙げることができる。Specifically, divalent nickel compounds such as nickel acetylacetonate (n) bisbenzoylacetone nickel, nickel acetate, nickel naphthenate, nickel octenoate, and nickel benzoate can be mentioned.
トリアルキルアルミニウムとしては、例えば、トリメチ
ルアルミニウム、トリエチルアルミニウム、トリプロピ
ルアル湾ニウム、トリイソプロビルアルミニウム、トリ
ブチルアルξニウム、トリペンチルアルミニウム、トリ
ヘキシルアルミニウム、トリシクロへキシルアル短ニウ
ム、トリへプチルアル≧ニウム、トリオクチルアルミニ
ウム、トリデシルアルミニウム、トリフェニルアルミニ
ウム、トリベンジルアルミニウム等が挙げられる。Examples of the trialkylaluminium include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminium, tributylaluminium, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, triheptylaluminum≧nium, Examples include trioctylaluminum, tridecylaluminum, triphenylaluminum, tribenzylaluminum, and the like.
アルコール類としては、炭素数１−１２のものが好まし
い。具体的には、メチルアルコール、エチルアルコール
、プロビルアルコール、イソプロビルアルコール、ブチ
ルアルコール、イソプチルアルコール、ｓｅｅ−ブチル
アルコール、ｔｅｒｔ−プチルアルコール、ｎ−アくル
アルコール、イソアミルアルコール、ヘキシルアルコー
ル、ヘプチルアルコール、オクチルアルコール、カプリ
ルアルコール、ノニルアルコール、デシルアルコール、
ウンデシルアルコール、ラウリルアルコール等が挙げら
れる。As alcohols, those having 1 to 12 carbon atoms are preferred. Specifically, methyl alcohol, ethyl alcohol, probyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, see-butyl alcohol, tert-butyl alcohol, n-alkyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol. Alcohol, octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol,
Examples include undecyl alcohol and lauryl alcohol.
有機燐化合物としては、３価の芳香族亜燐酸化合物が好
ましい。このようなものとしては、トリフェニルホスフ
ァイト、トリクレジルホルファイト、トリス（ノニルフ
ェニル）ホスファイト、トリス（２．４−ジーｔｅｒ
ｔ−プチルフエニルホスファイト、トリ（２−メトキシ
フェニル）ホスファイト、トリ（０−フエニルーフエニ
ル）ホスファイト等が例として挙げられる．
溶媒としては、芳香族炭化水素、脂肪族炭化水素、脂環
系炭化水素等が用いられる。具体的には、ベンゼン、ト
ルエン、キシレン、シクロヘキセン、ヘプタン等が用い
られる。As the organic phosphorus compound, a trivalent aromatic phosphorous acid compound is preferred. These include triphenyl phosphite, tricresyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-ter
Examples include t-butylphenyl phosphite, tri(2-methoxyphenyl) phosphite, and tri(0-phenylphenyl) phosphite. As the solvent, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, etc. are used. Specifically, benzene, toluene, xylene, cyclohexene, heptane, etc. are used.
本発明の製造法において、１．３−ブタジエンを二量化
する際の反応温度は５０〜１５０゜Ｃであり、より好ま
しくは８０〜１ ２ ０ ’Ｃである。又、回分式でも
よく連続式でもよい。In the production method of the present invention, the reaction temperature when dimerizing 1,3-butadiene is 50 to 150°C, more preferably 80 to 120°C. Further, it may be a batch method or a continuous method.
次に、本発明を実施例により具体的に説明する。 Next, the present invention will be specifically explained using examples.
尖益狙上
１．５１．ステンレス製オートクレープを窒素置換した
後、脱水トルエン３９５戚を仕込んだ。次いで、室温で
エタノール２５．６ｍｍｏｎ、トリエチルアル逅ニウム
２０．３ｍｍｏＣ， トリス（ノニルフェニル）ホス
ファイト４００ｍｍｏｌ、及ヒニッケルアセチルアセト
ナート（ＩＩ） １．８ １ｍｍｏ２を順次加えた。そ
の後、プタジエン１３２ｇを仕込み、１００゜Ｃに昇温
し、撹拌下で１時間反応させた．
反応終了後、水冷して、蒸留水５０ｍｌを添加し、触媒
を失活させた。次いで、内部標準試料としてテトラリン
を添加し、ガスクロマトグラフ分析をした。仕込み１，
３−ブタジエン量に対する、生成物である４−ＶＣＨ，
ＣＯＤ，ＣＤＴの合計量の割合を転化率とした。又、４
−ＶＣＨ，ＣＯＤ，ＣＤＴの各々の生戒割合を選択率と
した。Aiming for a sharp profit 1.51. After purging the stainless steel autoclave with nitrogen, dehydrated toluene 395 was charged. Next, 25.6 mmol of ethanol, 20.3 mmol of triethylaluminum, 400 mmol of tris(nonylphenyl)phosphite, and 1.8 mmol of acetylacetonate (II) were sequentially added at room temperature. Thereafter, 132 g of putadiene was charged, the temperature was raised to 100°C, and the reaction was allowed to proceed for 1 hour with stirring. After the reaction was completed, the mixture was cooled with water and 50 ml of distilled water was added to deactivate the catalyst. Next, tetralin was added as an internal standard sample, and gas chromatography analysis was performed. Preparation 1,
4-VCH, the product, relative to the amount of 3-butadiene,
The ratio of the total amount of COD and CDT was defined as the conversion rate. Also, 4
- The selection rate was defined as the proportion of each of VCH, COD, and CDT.
ガスクロマトグラフ分析により、１．３−ブタジエンの
転化率は９９．８％であり、４−ＶＣＨ，ＣＯＤ，ＣＤ
Ｔの選択率はそれぞれ４．０％、９３．７％、２．３％
であることが判った。結果を表１に示す。Gas chromatographic analysis showed that the conversion rate of 1,3-butadiene was 99.8%, and 4-VCH, COD, CD
The selection rates of T are 4.0%, 93.7%, and 2.3%, respectively.
It turned out to be. The results are shown in Table 1.
北較斑土
エタノールを添加しなかった以外は実施例１と同様にし
て反応を行った。１．３−ブタジエンの添加率は８５．
０％であり、４−ＶＣＨ，ＣＯＤ，ＣＤＴの選択率はそ
れぞれ３０．６％、５５．０％、１４．４％で、実施例
ｌに比べ、ＣＯＤの選択率が低く、４−ＶＣＨ及びＣＤ
Ｔが多く副生していた。The reaction was carried out in the same manner as in Example 1 except that Hokkaido Irregular ethanol was not added. The addition rate of 1.3-butadiene is 85.
The selectivity of 4-VCH, COD, and CDT was 30.6%, 55.0%, and 14.4%, respectively, and the selectivity of COD was lower than in Example 1, and the selectivity of 4-VCH and CDT was 30.6%, 55.0%, and 14.4%, respectively. CD
Many Ts were produced as by-products.
比較斑１
エタノールを使用せず、且つトリエチルアルξニウムに
換えてジエチルアルミニウムエトキサイドを使用した以
外は実施例ｌと同様に反応を行った。Comparative Spot 1 The reaction was carried out in the same manner as in Example 1, except that ethanol was not used and diethylaluminum ethoxide was used instead of triethylaluminum ξnium.
ブタジエンの転化率は９１．０％であり、４−ＶＣＨ，
ＣＯＤ，ＣＤＴの選択率は各々１０．５％、８１．５％
、８．０％で、実施例ｌに比べ、ＣＯＤの選択率が低か
った。The conversion rate of butadiene was 91.0%, 4-VCH,
The selectivity of COD and CDT was 10.5% and 81.5%, respectively.
, 8.0%, and the COD selectivity was lower than that in Example 1.
実益班斐
エタノール峠ニッケルアセチルアセトナート（Ｉｌ）４
トリエチルアルミニウム→トリス（ノニルフェニル）ホ
スファイトの順で、各触媒成分を加えた以外は実施例ｌ
と同様に反応を行った．プタジエンの転化率は９９．０
％で、４−ＶＣＨ、ＣＯＤＳＣＤＴの選択率は各々４．
２％、９２．９％、２．９％であった．
表１
ＴＥＡ・・・・・トリエチルアルミニウムＤＥＡＥ・・
ジエチルアルミニウムエトキシドＴＮＰ・・・・・トリ
ス（ノニルフェニル）ホスファイト
（Ｎｉ）ＡｃＡｃ
・・・ニッケルアセチルアセトナート（ＩＩ）実淘艷し
レΣＬ
エタノールをメタノールに換えて、その使用量を表１の
様に変えた以外は実施例ｌと同様に反応を行った。結果
を表２に示す。Jitsue Banhi Ethanol Pass Nickel Acetylacetonate (Il) 4
Example 1 except that each catalyst component was added in the order of triethylaluminum → tris(nonylphenyl)phosphite.
The reaction was carried out in the same way. The conversion rate of putadiene is 99.0
%, the selectivity of 4-VCH and CODSCDT is 4.
2%, 92.9%, and 2.9%. Table 1 TEA...Triethylaluminum DEAE...
Diethylaluminum ethoxide TNP...tris(nonylphenyl)phosphite (Ni)AcAc...Nickel acetylacetonate (II) actual selection ΣL Replace ethanol with methanol and calculate the amount used in Table 1 The reaction was carried out in the same manner as in Example 1 except for the following changes. The results are shown in Table 2.
表２
ＭｅＯ｝Ｉ・・・メタノール、
実１載ｕし一生
エタノールをイソプロパノール（実施例８）、或いはｎ
−オクタノール（実施例９）に換えた以外は、実施例ｌ
と同様に行った．結果を表３に示す。Table 2 MeO}I...methanol, 1 ounce of fruit and ethanol is isopropanol (Example 8), or n
- Example 1 except that octanol (Example 9) was substituted.
I did the same thing. The results are shown in Table 3.
実１０組Ｌ１−一ＬＬ
ニッケルアセチルアセトナート（Ｉｆ）を、オクテン酸
ニッケル（実施例１０）、或いはナフテン酸ニッケル（
実施例１１）に換えた以外は、実施例ｌと同様に行った
。結果を表３に示す。Example 10 sets L1-1LL Nickel acetylacetonate (If) was converted into nickel octate (Example 10) or nickel naphthenate (Example 10).
The same procedure as in Example 1 was carried out except that Example 11) was used. The results are shown in Table 3.
表３
ＮｉＯｃ・・・・オクテン酸ニッケル
ＮｉＮｐｔ・・・ナフテン酸ニッケル
裏施皿上ｉ一土主
トリス（ノニルフェニル）ホスファイトをトリフエニル
フォスファイト（実施例１２）或いはトリ一〇−クレジ
ルホスファイト（実施例１３）に換えた以外は、実施例
ｌと同様に行った。結果を表４に示す。Table 3 NiOc...Nickel octenoateNiNpt...Nickel naphthenate On a plate lined with The same procedure as in Example 1 was carried out except that Phytophyte (Example 13) was used. The results are shown in Table 4.
表４
〔本発明の効果〕
本発明のＣＯＤ合戒法により、シリル基を有する有機燐
化合物のような特殊で高価な有機燐化合物を電子供与体
として用いることなく、８８〜９５％の高い選択率でＣ
ＯＤを合成できる。Table 4 [Effects of the present invention] By the COD method of the present invention, a high selectivity of 88 to 95% can be achieved without using special and expensive organic phosphorus compounds such as those having silyl groups as electron donors. C at rate
Can synthesize OD.
又、ジアルキルアルミニウムアルコキシドを別途合成す
る必要がないので、そのための反応器が不要になる。従
って、製造設備が単純になり、且つ経済的でもある。Furthermore, since there is no need to separately synthesize dialkylaluminum alkoxide, a reactor for this purpose becomes unnecessary. Therefore, the manufacturing equipment becomes simple and economical.
Claims (1)
リアルキルアルミニウム化合物を、アルコール類の存在
下で反応させたものと、［２］有機燐化合物、 を用いて、１，３−ブタジエンを二量化する環状二量体
の製造法。(1) [1] Using (a) a divalent nickel compound and (b) a trialkylaluminum compound reacted in the presence of an alcohol, and [2] an organic phosphorus compound, 1, A method for producing a cyclic dimer by dimerizing 3-butadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1190565A JP2583128B2 (en) | 1989-07-25 | 1989-07-25 | Method for producing 1,5-cyclooctadiene by dimerizing 1,3-butadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1190565A JP2583128B2 (en) | 1989-07-25 | 1989-07-25 | Method for producing 1,5-cyclooctadiene by dimerizing 1,3-butadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0356427A true JPH0356427A (en) | 1991-03-12 |
| JP2583128B2 JP2583128B2 (en) | 1997-02-19 |
Family
ID=16260178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1190565A Expired - Fee Related JP2583128B2 (en) | 1989-07-25 | 1989-07-25 | Method for producing 1,5-cyclooctadiene by dimerizing 1,3-butadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2583128B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380368A (en) * | 2016-08-31 | 2017-02-08 | 山东广恒化工有限公司 | Method for preparation of 1,5-cyclooctadiene through cyclization of butadiene |
| CN108002970A (en) * | 2017-12-26 | 2018-05-08 | 濮阳盛华德化工有限公司 | A kind of preparation method of 1,5- cyclo-octadiene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5855434A (en) * | 1981-09-28 | 1983-04-01 | Mitsubishi Petrochem Co Ltd | Preparation of dimethylcyclooctadiene |
-
1989
- 1989-07-25 JP JP1190565A patent/JP2583128B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5855434A (en) * | 1981-09-28 | 1983-04-01 | Mitsubishi Petrochem Co Ltd | Preparation of dimethylcyclooctadiene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380368A (en) * | 2016-08-31 | 2017-02-08 | 山东广恒化工有限公司 | Method for preparation of 1,5-cyclooctadiene through cyclization of butadiene |
| CN108002970A (en) * | 2017-12-26 | 2018-05-08 | 濮阳盛华德化工有限公司 | A kind of preparation method of 1,5- cyclo-octadiene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2583128B2 (en) | 1997-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3957894A (en) | Catalytic dimerization of conjugated dienes | |
| Grubbs et al. | Carbon-carbon bond cleavage reactions in the decomposition of metallacycles | |
| JPH0329767B2 (en) | ||
| JP2550641B2 (en) | Method for dimerizing lower α-olefins | |
| US8759280B2 (en) | Method for producing trimethylcyclododecatriene | |
| Keim et al. | Control of regioselectivity in the palladium catalyzed telomerization of isoprene with diethylamine; synthesis of a new head-to-head terpene amine | |
| EP0009035B1 (en) | selective hydrogenation of cyclopentadiene to form cyclopentene | |
| JPH0356427A (en) | Production of cyclic dimer of 3-butadiene | |
| CA1106857A (en) | Process for the preparation of 3-(4-methyl-3- cyclohexen-1-yl) butyraldehyde | |
| CN113402554B (en) | PNSiNP ligand and preparation method thereof, ethylene oligomerization catalyst and application thereof | |
| US3686245A (en) | Halo(haloorgano)bis(triorganophosphine)nickel(ii) complexes for olefin dimerization | |
| CA1116185A (en) | Process for preparing 3-(4)-formyltricyclo-[5,2,1, 0 su2,6 xx]-decene-8 | |
| JPS59163326A (en) | Removal of certain kind of isoprene trimer from isoprene trimer mixture | |
| EP0542366B1 (en) | Process for the telomerization of conjugated alkadienes | |
| JP3458419B2 (en) | Method for dimerizing lower olefin and method for producing alcohol using the same | |
| JP3525461B2 (en) | Method for dimerizing butene and method for producing alcohol using the same | |
| US3644445A (en) | Cyclomatic metal carbonyls containing metal-metal bond | |
| RU2397174C2 (en) | 2,3,4,5-tetraalkylmagnesacyclopenta-2,4-diene synthesis method | |
| RU2191192C1 (en) | Method of synthesis of substituted 1-ethylalumo-cyclopentanes | |
| RU2348640C1 (en) | Method of obtaining 10-ethyl-11,12-dialkyl-10-aluminabicyclo [7,3,01,9]dodeca-8,11-dienes | |
| JPH024210B2 (en) | ||
| RU2342396C1 (en) | Method of diethyl[(2-ethyl-1,2-dialkylcyclopropyl)ethyl]alans production | |
| Yong et al. | Organotitanium chemistry: substituent effects on the dimerization of isoprene catalyzed by alkenyl-substituted cyclopentadienyl titanium complexes | |
| JPS5855434A (en) | Preparation of dimethylcyclooctadiene | |
| JPS6138175B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |