JP5344808B2 - Method for producing cyclic olefin - Google Patents
Method for producing cyclic olefin Download PDFInfo
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- JP5344808B2 JP5344808B2 JP2007298236A JP2007298236A JP5344808B2 JP 5344808 B2 JP5344808 B2 JP 5344808B2 JP 2007298236 A JP2007298236 A JP 2007298236A JP 2007298236 A JP2007298236 A JP 2007298236A JP 5344808 B2 JP5344808 B2 JP 5344808B2
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- norbornene
- dicyclopentadiene
- tetracyclododecene
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- -1 cyclic olefin Chemical class 0.000 title abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 12
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 57
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 claims abstract description 48
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 38
- 239000012535 impurity Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005698 Diels-Alder reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- APYBVJQVVPJCEB-UHFFFAOYSA-N 1-cyclonona-1,3-dien-1-yl-2-methylcyclonona-1,3-diene Chemical compound C1CCCCC=CC(C)=C1C1=CC=CCCCCC1 APYBVJQVVPJCEB-UHFFFAOYSA-N 0.000 description 3
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- VGUXWSJVGWCTEC-UHFFFAOYSA-N bicyclo[2.2.1]hept-3-ene Chemical compound C1C(C2)CCC2=C1 VGUXWSJVGWCTEC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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Abstract
Description
本発明は、テトラシクロドデセン、ノルボルネン等の環状オレフィンの製造方法に関する。さらに詳しくは、塗料やポリマー等の原材料として有用なテトラシクロドデセンを安定してしかも効率よく製造する方法に関する。 The present invention relates to a method for producing cyclic olefins such as tetracyclododecene and norbornene. More specifically, the present invention relates to a method for stably and efficiently producing tetracyclododecene useful as a raw material for paints and polymers.
塗料やポリマー等の原材料として有用な化合物であるアルキルテトラシクロドデセンは、従来、オレフィンと、シクロペンタジエンまたはジシクロペンタジエンと、ノルボルネンとを加熱して、ディールズ・アルダー反応（Diels-Alder反応）により製造されている。 Alkyltetracyclododecene, a compound that is useful as a raw material for paints and polymers, is conventionally heated by olefin, cyclopentadiene or dicyclopentadiene, and norbornene, and then subjected to Diels-Alder reaction. It is manufactured.
特公平１−６００１１号公報には、炭素数２〜２２のオレフィン１〜２０モル、シクロペンタジエン１〜５モルまたはジシクロペンタジエン０.５〜２.５モル、およびノルボルネン１〜５モルを、１００〜４００℃、１００〜５,０００ｐｓｉおよび０.１〜５時間、反応器内に加熱・保持し、そして生成物からノルボルネン／テトラシクロドデセンのモル比が５／９５〜９５／５の混合物を製造する方法が開示されている(特許文献１)。
Japanese Patent Publication No. 1-60011 discloses 1 to 20 moles of an olefin having 2 to 22 carbon atoms, 1 to 5 moles of cyclopentadiene or 0.5 to 2.5 moles of dicyclopentadiene, and 1 to 5 moles of norbornene. Heat and hold in reactor at ~ 400 ° C, 100-5,000 psi and 0.1-5 hours, and mix product with norbornene /
この方法は、オレフィンとしてエチレンを用いた場合、沸点がテトラシクロドデセン以上の重質油を大量に副生する。この重質油の副生は、目的物であるテトラシクロドデセンの収率を著しく低下させる。しかしながらテトラシクロドデセンの製造上、重質油の効果的な抑制は現在のところ実現できていない。 In this method, when ethylene is used as the olefin, a large amount of heavy oil having a boiling point of tetracyclododecene or more is by-produced. This by-product of heavy oil significantly lowers the yield of the target tetracyclododecene. However, effective suppression of heavy oil has not been realized at present in the production of tetracyclododecene.
また、特開平３−１２８３３３号公報には、エチレン、シクロペンタジエンまたはジシクロペンタジエン、およびノルボルネンを、芳香族系溶剤と一緒に加熱反応させ、得られた反応混合物を精製塔より分離して塔底からテトラシクロドデセンを含む反応生成物を回収しそして塔頂から未反応のノルボルネン、シクロペンタジエンまたはジシクロペンタジエン、および芳香族系溶剤を回収して循環再使用するテトラシクロドデセンの製造法が開示されている(特許文献２)。 JP-A-3-128333 discloses that ethylene, cyclopentadiene or dicyclopentadiene, and norbornene are heated and reacted together with an aromatic solvent, and the resulting reaction mixture is separated from a purification tower to obtain a bottom of the tower. A process for producing tetracyclododecene is disclosed in which a reaction product containing tetracyclododecene is recovered from the reactor, and unreacted norbornene, cyclopentadiene or dicyclopentadiene, and an aromatic solvent are recovered from the top of the tower and recycled. (Patent Document 2).
特開昭５７−１５４１３３号公報、特開平６−９４３７号公報ではエチレンとジシクロペンタジエンとの熱反応によるテトラシクロドデセンの製造方法が開示されている(特許文献３，４)。 JP-A-57-154133 and JP-A-6-9437 disclose a method for producing tetracyclododecene by thermal reaction between ethylene and dicyclopentadiene (Patent Documents 3 and 4).
しかし、これらの技術では原料であるジシクロペンタジエンの保管方法やジシクロペンタジエンとエチレンとの熱反応の前におけるジシクロペンタジエンの予備処理については全く考慮されておらず、ジシクロペンタジエンの保管状態によってテトラシクロドデセンの製造における品質、収率などの点で大きく影響を受ける問題があった。
本発明の目的は、テトラシクロドデセン、ノルボルネン等の環状オレフィンを安定して、効率的に製造する方法を提供することにある。本発明の他の目的は、重質油の副生を抑制してテトラシクロドデセンまたはノルボルネンを効率良く製造する方法を提供することにある。本発明の他の目的は、工業的に取扱いが容易でありさらに経済性にも優れたテトラシクロドデセンまたはノルボルネン等の環状オレフィンの製造法を提供することにある。本発明のさらに他の目的および利点は、以下の説明から明らかとなろう。 An object of the present invention is to provide a method for stably and efficiently producing cyclic olefins such as tetracyclododecene and norbornene. Another object of the present invention is to provide a method for efficiently producing tetracyclododecene or norbornene by suppressing the by-product of heavy oil. Another object of the present invention is to provide a process for producing a cyclic olefin such as tetracyclododecene or norbornene which is industrially easy to handle and excellent in economic efficiency. Still other objects and advantages of the present invention will become apparent from the following description.
上記課題に鑑み鋭意検討した結果、温度３５℃未満、酸素濃度１０ｐｐｍ以下、安定剤２０ｐｐｍ〜１０，０００ｐｐｍ含む条件で保存されたジシクロペンタジエンを、蒸留により前記安定剤を１０ｐｐｍ以下に低減させ、エチレン及び必要によりノルボルネンを加えて加熱反応させることにより、安定的かつ効率的に高品質のテトラシクロドデセンまたはノルボルネンが得られることを見出し、本発明を完成した。 As a result of intensive studies in view of the above problems, dicyclopentadiene stored under conditions including a temperature of less than 35 ° C., an oxygen concentration of 10 ppm or less, and a stabilizer of 20 ppm to 10,000 ppm is reduced by distillation to 10 ppm or less of the stabilizer. Further, the present inventors have found that high-quality tetracyclododecene or norbornene can be obtained stably and efficiently by adding norbornene to the reaction by heating if necessary.
本発明によれば、テトラシクロドデセンまたはノルボルネン等の環状オレフィンを安定して、効率的に製造することができる。また本発明で得られるテトラシクロドデセンまたはノルボルネン等の環状オレフィンは副生物が少なくポリマー製造において高収率、高品質の重合体を得ることができる。 According to the present invention, a cyclic olefin such as tetracyclododecene or norbornene can be stably and efficiently produced. In addition, the cyclic olefin such as tetracyclododecene or norbornene obtained in the present invention has few by-products and can provide a polymer with high yield and high quality in polymer production.
ジシクロペンタジエンの保存方法
本発明のジシクロペンタジエンの保存とは融点以上の温度の融解状態から３５℃未満の固体状態とした後、1日以上、通常7日〜５年程度の期間の保存をいう。本発明のジシクロペンタジエンの保存は３５℃未満、好ましくは３３℃以下、より好ましくは０℃〜３０℃の温度で行われる。本発明のジシクロペンタジエンの保存は、ジシクロンペンタジエン中の酸素濃度が１０ｐｐｍ以下、好ましくは５ｐｐｍ以下、より好ましくは３ｐｐｍ以下で行われる。本発明のジシクロペンタジエンの保存は、安定剤を２０ｐｐｍ以上、好ましくは５０〜１０，０００ｐｐｍ、より好ましくは５０〜１，０００ｐｐｍ含む状態で行われる。本発明のジシクロペンタジエンの保存において含まれる安定剤の種類に特に制限はないが、ハイドロキノン、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−ブチルクレゾール、４−メトキシフェノール、４−ｔｅｒｔ−ブチルカテコールなどのフェノール系化合物、Ｎ，Ｎ−ジメチルヒドロキシルアミン、Ｎ，Ｎ−ジエチルヒドロキシルアミン、Ｎ−ニトロソ−Ｎ−フェニルベンゾアミン、フェノチアジンなどのアミン化合物などが好適に添加される。
Storage method of dicyclopentadiene The storage of dicyclopentadiene according to the present invention refers to storage of a solid state of less than 35 ° C. from a melting state at a temperature higher than the melting point, and then storage for a period of 1 day or more, usually about 7 days to 5 years. Say. The storage of the dicyclopentadiene of the present invention is carried out at a temperature of less than 35 ° C, preferably 33 ° C or less, more preferably 0 ° C to 30 ° C. The storage of dicyclopentadiene of the present invention is carried out at an oxygen concentration in dicyclone pentadiene of 10 ppm or less, preferably 5 ppm or less, more preferably 3 ppm or less. The storage of the dicyclopentadiene of the present invention is performed in a state containing 20 ppm or more, preferably 50 to 10,000 ppm, more preferably 50 to 1,000 ppm of the stabilizer. There are no particular limitations on the type of stabilizer included in the storage of dicyclopentadiene of the present invention, but hydroquinone, 2,6-di-tert-butylphenol, 2,6-di-tert-butylcresol, 4-methoxyphenol, Phenol compounds such as 4-tert-butylcatechol, amine compounds such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N-nitroso-N-phenylbenzoamine, and phenothiazine are preferably added. .
テトラシクロドデセンまたはノルボルネン等の環状オレフィンの製造方法
本発明のテトラシクロドデセンまたはノルボルネン等の環状オレフィンの製造方法では、まず上記のように保存されたジシクロペンタジエンを３５℃以上、好ましくは４０℃以上、より好ましくは４０℃〜１００℃の融解状態とした後、蒸留器において、好ましくは連続的に蒸留することで、ジシクロペンタジエン中に含まれる安定剤の濃度を１０ｐｐｍ以下に低減される。ジシクロペンタジエンの温度が３５℃未満では固体が析出し、搬送などの点で好ましくない。またジシクロペンタジエンの温度が１００℃を超えると、副反応などが進行し副生成物ができ易く好ましくない。上記のジシクロペンタジエンの蒸留は通常理論段数２〜５０段、好ましくは５〜２０段で行われる。蒸留時の圧力は、通常１０〜１００ｔｏｒｒ、好ましくは１０〜５０ｔｏｒｒで行われる。
Method for Producing Cyclic Olefin such as Tetracyclododecene or Norbornene In the method for producing a cyclic olefin such as tetracyclododecene or norbornene of the present invention, the dicyclopentadiene stored as described above is first 35 ° C. or more, preferably 40 ° C. The concentration of the stabilizer contained in dicyclopentadiene is reduced to 10 ppm or less by making the molten state at a temperature of ℃ or higher, more preferably from 40 ℃ to 100 ℃, and preferably continuously in a distiller. . If the temperature of dicyclopentadiene is less than 35 ° C., a solid precipitates, which is not preferable in terms of transportation. On the other hand, when the temperature of dicyclopentadiene exceeds 100 ° C., side reactions and the like proceed and a by-product is easily formed, which is not preferable. The dicyclopentadiene is usually distilled at 2 to 50 theoretical plates, preferably 5 to 20 plates. The pressure during distillation is usually 10 to 100 torr, preferably 10 to 50 torr.
ジシクロペンタジエンの蒸留は通常５０〜１００℃、好ましくは６０〜９０℃で行われる。ジシクロペンタジエンの蒸留中、系内の酸素濃度は１０ｐｐｍ以下であるのが好ましい。 Dicyclopentadiene is usually distilled at 50 to 100 ° C, preferably 60 to 90 ° C. During the distillation of dicyclopentadiene, the oxygen concentration in the system is preferably 10 ppm or less.
本発明の方法では、エチレンと純度が９５重量％を超える高純度のシクロペンタジエンとノルボルネンを加熱反応させる際には、主として
（Ａ）シクロペンタジエンとエチレンとの反応によりノルボルネンを生成する下記反応（１）
In the method of the present invention, when a high-purity cyclopentadiene having a purity of more than 95% by weight and norbornene are subjected to a heat reaction, (A) )
また、本発明に係るテトラシクロドデセンの製造方法において、高純度のシクロペンタジエンの代わりに高純度のジシクロペンタジエンを用いた場合には、さらに（Ｃ）ジシクロペンタジエンからシクロペンタジエンへの下記熱分解反応（３） In the method for producing tetracyclododecene according to the present invention, when high-purity dicyclopentadiene is used instead of high-purity cyclopentadiene, (C) the following heat from dicyclopentadiene to cyclopentadiene Decomposition reaction (3)
ここで反応（Ａ）および反応（Ｂ）はディールズ・アルダー反応であり、反応（Ｃ）は逆ディールズ・アルダー反応である。本発明方法では、高純度のシクロペンタジエンまたはジシクロペンタジエンとして、５重量％未満の不純物がプロペニルノルボルネンおよび／またはイソプロペニルノルボルネン等を含むものが有利に用いられる。不純物の含量は、好ましくは３重量％未満、特に好ましくは１重量％未満である。 Here, reaction (A) and reaction (B) are Diels-Alder reactions, and reaction (C) is a reverse Diels-Alder reaction. In the method of the present invention, highly pure cyclopentadiene or dicyclopentadiene is preferably used in which impurities of less than 5% by weight include propenyl norbornene and / or isopropenyl norbornene. The content of impurities is preferably less than 3% by weight, particularly preferably less than 1% by weight.
不純物としては、その他ビニルノルボルネン、メチルビシクロノナジエンおよびメチルジシクロペンタジエン等がある。これらの不純物は、例えばプロペニルノルボルネン４重量％以下、イソプロペニルノルボルネン２重量％以下、ビニルノルボルネン１重量％以下、メチルビシクロノナジエン１重量％以下、メチルジシクロペンタジエン１重量％以下の少なくとも１種からなる。
Examples of impurities include vinyl norbornene, methylbicyclononadiene, and methyldicyclopentadiene. These impurities include, for example, at least one of propenyl norbornene 4 wt% or less,
不純物含量が５重量％以上のシクロペンタジエンまたはジシクロペンタジエンを用いた場合には、出発原料であるシクロペンタジエン、ジシクロペンタジエンおよびノルボルネンの少なくとも１種あるいは目的物であるテトラシクロドデセンと上記の如き不純物との間にディールズ・アルダー反応が起こり副生物が生成し易くなる。それ故、不純物含量が５重量％以上の場合には、シクロペンタジエンあるいはジシクロペンタジエンの反応利用効率が著しく低下するようになる。 When cyclopentadiene or dicyclopentadiene having an impurity content of 5% by weight or more is used, at least one of cyclopentadiene, dicyclopentadiene and norbornene as a starting material or tetracyclododecene as a target product and A Diels-Alder reaction occurs between the impurities and a by-product is easily generated. Therefore, when the impurity content is 5% by weight or more, the reaction utilization efficiency of cyclopentadiene or dicyclopentadiene is significantly reduced.
本発明方法の反応を行なうに際しては、シクロペンタジエンは常温、常圧条件下では２量体のジシクロペンタジエンとして存在しており、このジシクロペンタジエンは反応条件下で分解してシクロペンタジエンを生成するため、通常、反応にはジシクロペンタジエンが用いられる。この際、未反応のノルボルネンは、蒸溜により回収してリサイクルされる。このため反応前後におけるノルボルネンの変化量（ΔＮＢ）は、ΔＮＢ＝０であることが好ましい。 In carrying out the reaction of the method of the present invention, cyclopentadiene exists as a dimeric dicyclopentadiene under normal temperature and normal pressure conditions, and this dicyclopentadiene decomposes under the reaction conditions to produce cyclopentadiene. Therefore, dicyclopentadiene is usually used for the reaction. At this time, unreacted norbornene is recovered by distillation and recycled. Therefore, the amount of change (ΔNB) of norbornene before and after the reaction is preferably ΔNB = 0.
本発明のテトラシクロドデセンまたはノルボルネンの製造方法において用いられるジシクロペンタジエンの純度は９９％以上、好ましくは９９．８％以上であることが望ましい。 The purity of dicyclopentadiene used in the process for producing tetracyclododecene or norbornene of the present invention is 99% or more, preferably 99.8% or more.
また、本発明に係るテトラシクロドデセンの製造方法において用いられる反応装置は、通常、アルキルテトラシクロドデセンの製造に使用されている装置をそのまま用いることができる。装置の概略は例えば特開平６−９４３７に開示されている。本発明において用いられる典型的な装置の概略図を図１に示す。 In addition, as a reaction apparatus used in the method for producing tetracyclododecene according to the present invention, an apparatus usually used for producing alkyltetracyclododecene can be used as it is. An outline of the apparatus is disclosed in, for example, JP-A-6-9437. A schematic diagram of a typical apparatus used in the present invention is shown in FIG.
このような反応装置を用いてテトラシクロドデセンまたはノルボルネン等の環状オレフィンを製造する際には、反応系に供給されるジシクロペンタジエンとノルボルネンは、混合機で所定の比率で混合される。エチレンと、この混合液はコンプレッサーあるいはポンプにより７００〜４,０００kPaまで昇圧されたのち、エチレンと所定の比率で混合される。混合物は、１５０〜１８０℃に加熱された予熱室へ送られて、反応温度付近まで予熱され、反応器へ供給される。この場合、供給される原料の量は、ジシクロペンタジエン１モルに対してノルボルネンが１.５〜６.０モル、エチレンが０.４〜２.０モルの範囲であることが好ましい。本発明に係るテトラシクロドデセンの製造方法では、反応は、反応温度１００〜４００℃、好ましくは２００〜３００℃、より好ましくは２００〜２８０℃、圧力７００〜４０,０００kPa、好ましくは３０００〜３０,０００kPa、反応器内での平均滞留時間は０.００１〜５時間、好ましく０．１〜１０分、より好ましくは０．２〜８分で行なわれる。上記の条件で反応を行うと、テトラシクロドデｓンの収率の点で好ましく、また副生成物の生成も少なく好ましい。 When producing a cyclic olefin such as tetracyclododecene or norbornene using such a reaction apparatus, dicyclopentadiene and norbornene supplied to the reaction system are mixed at a predetermined ratio by a mixer. Ethylene and this mixed solution are pressurized to 700 to 4,000 kPa by a compressor or a pump and then mixed with ethylene at a predetermined ratio. The mixture is sent to a preheating chamber heated to 150 to 180 ° C., preheated to near the reaction temperature, and supplied to the reactor. In this case, the amount of the raw material supplied is preferably in the range of 1.5 to 6.0 mol of norbornene and 0.4 to 2.0 mol of ethylene with respect to 1 mol of dicyclopentadiene. In the method for producing tetracyclododecene according to the present invention, the reaction is performed at a reaction temperature of 100 to 400 ° C, preferably 200 to 300 ° C, more preferably 200 to 280 ° C, and a pressure of 700 to 40,000 kPa, preferably 3000 to 30. The average residence time in the reactor is 0.001 to 5 hours, preferably 0.1 to 10 minutes, more preferably 0.2 to 8 minutes. When the reaction is carried out under the above conditions, it is preferable from the viewpoint of the yield of tetracyclododecone, and the production of by-products is also small.
精製工程反応により得られた混合物は、後処理工程に送られ、そこで冷却、脱圧分離されたのち、第１精製塔に供給される。その塔頂部より未反応のノルボルネンと、少量のシクロペンタジエンあるいはジシクロペンタジエンとの混合物が回収され、塔底部より重質油を含む粗製のテトラシクロドデセンがそれぞれ回収される。回収されたノルボルネンと少量のシクロペンタジエンあるいはジシクロペンタジエンとの混合物は、ノルボルネンがリザーバータンク内で凝固しないように、リザーバータンクへ送られて保存され、再び反応に使用される。また塔底部より分離された重質油を含む粗製のテトラシクロドデセンは、精製塔に送られて、その塔頂部より高純度のテトラシクロドデセンが回収され、塔底部より重質油がそれぞれ回収される。このような蒸留塔における運転条件は、第１精製塔においては塔底部温度１３０〜１８０℃、塔底部圧力１５〜７５kPa 、塔頂部温度５０〜１３０℃、塔頂部圧力１３.３〜７０kPaであることが好ましい。なお第２精製塔においては塔底部温度８０〜１５０℃、塔底部圧力１.３〜２０kPa、塔頂部温度６０〜１３０℃、塔頂部圧力０.１３〜１２kPaであることが好ましい。 The mixture obtained by the purification step reaction is sent to the post-treatment step, where it is cooled and depressurized and then supplied to the first purification column. A mixture of unreacted norbornene and a small amount of cyclopentadiene or dicyclopentadiene is recovered from the top of the column, and crude tetracyclododecene containing heavy oil is recovered from the bottom of the column. The recovered norbornene and a small amount of cyclopentadiene or a mixture of dicyclopentadiene are sent to the reservoir tank for storage so that the norbornene does not solidify in the reservoir tank, and used again for the reaction. The crude tetracyclododecene containing heavy oil separated from the bottom of the tower is sent to a purification tower, where high purity tetracyclododecene is recovered from the top of the tower, and heavy oil is recovered from the bottom of the tower. It will be collected. The operating conditions in such a distillation column are: tower bottom temperature 130-180 ° C., tower bottom pressure 15-75 kPa, tower top temperature 50-130 ° C., tower top pressure 13.3-70 kPa in the first purification tower. Is preferred. In the second purification tower, the tower bottom temperature is preferably 80 to 150 ° C., the tower bottom pressure is 1.3 to 20 kPa, the tower top temperature is 60 to 130 ° C., and the tower top pressure is 0.13 to 12 kPa.
本発明で製造されるテトラシクロドデセンまたはノルボルネン等の環状オレフィンは炭素数１〜２０のアルキル基、アルキレン基や極性基などの置換基を含んでいても良い。
また、本発明によれば、以下の態様も含む。
［１］温度３５℃未満、酸素濃度１０ｐｐｍ以下、安定剤２０ｐｐｍ〜１０，０００ｐｐｍ含む条件で保存されたジシクロペンタジエンを、蒸留により前記安定剤を１０ｐｐｍ以下に低減させ、エチレン及び必要によりノルボルネンを加えて加熱反応させることを特徴とするテトラシクロドデセンまたはノルボルネンの製造方法。
［２］反応器に供給されるジシクロペンタジエンの反応器内での平均滞留時間が０．００１〜５時間であり、ジシクロペンタジエンとエチレンおよびノルボルネンとを加熱反応させることを特徴とする［１］記載のテトラシクロドデセンの製造方法。
［３］［１］または［２］の方法で得られたテトラシクロドデセンまたはノルボルネン。
［４］温度３５℃未満、酸素濃度１０ｐｐｍ以下、安定剤２０ｐｐｍ〜１０，０００ｐｐｍ含む条件で保存されたジシクロペンタジエンを、蒸留により前記安定剤を１０ｐｐｍ以下に低減させたジシクロペンタジエン。
The cyclic olefin such as tetracyclododecene or norbornene produced in the present invention may contain a substituent such as an alkyl group having 1 to 20 carbon atoms, an alkylene group or a polar group.
Moreover, according to this invention, the following aspects are also included.
[1] Dicyclopentadiene stored under conditions including a temperature of less than 35 ° C., an oxygen concentration of 10 ppm or less, and a stabilizer of 20 ppm to 10,000 ppm is reduced to 10 ppm or less by distillation, and ethylene and, if necessary, norbornene is added. A process for producing tetracyclododecene or norbornene, wherein the reaction is carried out by heating.
[2] The average residence time of dicyclopentadiene supplied to the reactor in the reactor is 0.001 to 5 hours, and the dicyclopentadiene is reacted with ethylene and norbornene by heating [1] ] The manufacturing method of tetracyclododecene of description.
[3] Tetracyclododecene or norbornene obtained by the method of [1] or [2].
[4] Dicyclopentadiene obtained by distilling dicyclopentadiene stored under conditions including a temperature of less than 35 ° C., an oxygen concentration of 10 ppm or less, and a stabilizer of 20 ppm to 10,000 ppm by distillation.
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[実施例１]
安定剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾールを１００ｐｐｍ含み、酸素濃度が１０ｐｐｍ以下、３０℃以下の温度で１週間保存されたジシクロペンタジエンを６０℃で融解、搬送し、理論段数１０段、圧力２０ｔｏｒｒ、缶底温度７７℃、還流比３で蒸留した。蒸留後のジシクロペンタジエン中の安定剤の濃度は１ｐｐｍ以下、純度は９５％であった。
[Example 1]
Dicyclopentadiene containing 100 ppm of 2,6-di-tert-butylcresol as a stabilizer, oxygen concentration of 10 ppm or less and stored for 1 week at a temperature of 30 ° C. or less is melted and transported at 60 ° C. And distilled at a pressure of 20 torr, a bottom temperature of 77 ° C., and a reflux ratio of 3. The concentration of the stabilizer in the dicyclopentadiene after distillation was 1 ppm or less, and the purity was 95%.
図１に示した装置を用いてテトラシクロドデセンの生成反応を行なった。反応は、エチレンと、純度９９.８％の高純度のジシクロペンタジエンと、ノルボルネンとを用いて行なった。この高純度ジシクロペンタジエンはプロペニルノルボルネン０.２重量％の不純物を含有していた。反応装置に供給されたこれら混合物のモル比は、エチレン２２モル％、ジシクロペンタジエン２６モル％、ノルボルネン５２モル％であり、反応は、反応圧力４６００kPa、反応温度２６０℃、滞留時間７．４分で行なわれた。得られた混合物は、後処理工程で処理されたのち、精製工程に送られた。この際、精製工程の運転条件は、第１精製塔においては塔底部温度１６８℃、塔底部圧力１６.６kPa、塔頂部温度７０℃、塔頂部圧力１４.６kPaで行ない、精製塔においては塔底部温度１１５℃、塔底部圧力２.２６kPa、塔頂部温度８０℃、塔頂部圧力０.３３kPaで行なった。成績は、シクロペンタジエン転化率８２ｍｏｌ％、テトラシクロドデセン選択率８４ｍｏｌ％であり高収率でテトラシクロドデセンを得ることができた。 Tetracyclododecene production reaction was performed using the apparatus shown in FIG. The reaction was performed using ethylene, high-purity dicyclopentadiene having a purity of 99.8%, and norbornene. The high purity dicyclopentadiene contained 0.2% by weight of impurities of propenyl norbornene. The molar ratio of these mixtures fed to the reactor was 22 mol% ethylene, 26 mol% dicyclopentadiene, 52 mol% norbornene, and the reaction was performed at a reaction pressure of 4600 kPa, a reaction temperature of 260 ° C., and a residence time of 7.4 minutes. It was done in The obtained mixture was processed in the post-processing step and then sent to the purification step. At this time, the operating conditions of the purification process are as follows: in the first purification column, the column bottom temperature is 168 ° C., the column bottom pressure is 16.6 kPa, the column top temperature is 70 ° C., the column top pressure is 14.6 kPa. The temperature was 115 ° C., the tower bottom pressure was 2.26 kPa, the tower top temperature was 80 ° C., and the tower top pressure was 0.33 kPa. The results were a cyclopentadiene conversion rate of 82 mol% and a tetracyclododecene selectivity of 84 mol%, and tetracyclododecene could be obtained in a high yield.
[比較例１]
安定剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾールを１００ｐｐｍ含み、酸素濃度が１０ｐｐｍ以下、６０℃の温度で融解状態で１週間保存されたジシクロペンタジエンを、搬送し、理論段数１０段、圧力２０ｔｏｒｒ、缶底温度７７℃、還流比３で蒸留した。蒸留後のジシクロペンタジエン中の安定剤の濃度は１ｐｐｍ以下、純度は９２％であった。
[Comparative Example 1]
Dicyclopentadiene containing 100 ppm of 2,6-di-tert-butylcresol as a stabilizer, having an oxygen concentration of 10 ppm or less and stored in a molten state at 60 ° C. for 1 week, transported, 10 theoretical plates, pressure Distillation was performed at 20 torr, a bottom temperature of 77 ° C., and a reflux ratio of 3. The concentration of the stabilizer in the dicyclopentadiene after distillation was 1 ppm or less, and the purity was 92%.
テトラシクロドデセン生成反応は、エチレンと、上記のジシクロペンタジエンと、ノルボルネンとを用いて行ない、それ以外は実施例１と同様の操作条件で行った。なお、本比較例で用いられたジシクロペンタジエンは、不純物としてプロペニルノルボルネン３重量％、イソプロペニルノルボルネン１重量％、ビニルノルボルネン０.５重量％、メチルビシクロノナジエン０.３重量％およびその他不明物０.２重量％を含有していた。その結果、シクロペンタジエン転化率８２ｍｏｌ％、テトラシクロドデセン選択率６９ｍｏｌ％でテトラシクロドデセンが得られた。 The tetracyclododecene formation reaction was performed using ethylene, the above-mentioned dicyclopentadiene, and norbornene, and the other conditions were the same as in Example 1. The dicyclopentadiene used in this comparative example was 3% by weight of propenyl norbornene, 1% by weight of isopropenyl norbornene, 0.5% by weight of vinyl norbornene, 0.3% by weight of methylbicyclononadiene and other unknowns as impurities. Contained 0.2% by weight. As a result, tetracyclododecene was obtained with a cyclopentadiene conversion rate of 82 mol% and a tetracyclododecene selectivity of 69 mol%.
[比較例２]
比較例１において安定剤を含まない事以外は比較例１と同様にジシクロペンタジエンを保存した後、比較例１と同様にテトラシクロドデセン生成反応に用いた。その結果、シクロペンタジエン転化率７２ｍｏｌ％、テトラシクロドデセン選択率５８ｍｏｌ％でテトラシクロドデセンが得られた。
[Comparative Example 2]
In Comparative Example 1, except that the stabilizer was not included, dicyclopentadiene was preserved in the same manner as in Comparative Example 1, and then used in the tetracyclododecene formation reaction as in Comparative Example 1. As a result, tetracyclododecene was obtained with a cyclopentadiene conversion of 72 mol% and a tetracyclododecene selectivity of 58 mol%.
本発明に係るテトラシクロドデセンの製造方法では、従来技術に比較し安定して、効率的に且つ非常に経済的にテトラシクロドデセンを製造することができる。 In the method for producing tetracyclododecene according to the present invention, tetracyclododecene can be produced stably, efficiently and very economically as compared with the prior art.
１ ノルボルネンのリザーバータンク
２ ジシクロペンタジエンのリザーバータンク
３ エチレン供給ライン
４ 予熱器
５ 反応器
６ 第一精留塔
７ 第二精留塔
DESCRIPTION OF SYMBOLS 1
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| JPH0832642B2 (en) * | 1987-01-13 | 1996-03-29 | 日本ゼオン株式会社 | Purification method of dicyclopentadiene |
| JPH069437A (en) * | 1992-06-22 | 1994-01-18 | Mitsui Petrochem Ind Ltd | Production of tetracyclododecene |
| FR2771735B1 (en) * | 1997-12-02 | 2000-03-03 | Atochem Elf Sa | PROCESS AND REACTOR FOR THE MANUFACTURE OF NORBORNENE |
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