JP2005097274A - Method for producing high purity olefinic compound - Google Patents
Method for producing high purity olefinic compound Download PDFInfo
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本発明は、高純度のビシクロヘキシル−３，３'ジエンの製造方法に関し、詳しくは水添ビフェノールを無溶媒で分子内脱水させることによる高純度のビシクロヘキシル−３，３'ジエンの製造方法に関する。 The present invention relates to a method for producing high-purity bicyclohexyl-3,3′-diene, and more particularly to a method for producing high-purity bicyclohexyl-3,3′-diene by intramolecular dehydration of hydrogenated biphenol without solvent. .
シクロヘキセン骨格を有する種々のオレフィン化合物の製造については、アルコール化合物の脱水反応により製造する方法が広く知られている。濃硫酸やリン酸等の無機酸を用いたアルコールの脱水反応によるオレフィン化合物の製造技術（非特許文献１参照）や、広く用いられている酸性塩である硫酸水素カリウム（KHSO4）を用いたアルコールの脱水反応によりオレフィン化合物を製造する技術が開示されている（特許文献１、非特許文献２、非特許文献３参照）。しかし、これら公知の濃硫酸やリン酸等の無機酸や硫酸水素カリウムを用いたアルコール化合物の脱水反応で得られるオレフィン化合物は必ずしも満足の行くものではなかった。すなわち、濃硫酸を用いると酸性度が高すぎるために、望みのオレフィン化合物以外に好ましくない副反応が生じ、収率を低下させるという問題があった。その一方で、リン酸や硫酸水素カリウム等の弱酸を用いた場合には酸性度が弱い為に反応時間の長時間化が生じ、反応温度の高温化が必要とされ、やはり副反応が生じ収率を低下させ、望みのオレフィン化合物から分離不可能な着色成分や異性体成分が生じるという問題があった。
ビスシクロヘキセン骨格を有する２，２−ビス（３'−シクロヘキセニル）プロパンの製造方法は、特許文献１に開示されている。同公報の実施例に記載の条件では、水添ビスフェノールＡの脱水反応は、原料の水添ビスフェノールＡ、脱水触媒、目的物質の２，２−ビス（３'−シクロヘキセニル）プロパン及び副生水とが共存する条件であるため、脱水反応のみならず二重結合部位への水の付加反応が進行し、式１に示すような異性化反応によって式２に示すような副生成物が生じる。副生成物は目的物と物理的性状がよく似ているため通常一般的な蒸留などでは分離困難であり、副生成物の生成を抑制することが、２，２−ビス（３'−シクロヘキセニル）プロパン製造の課題であった。一方、特許文献１の実施例には減圧反応に言及した箇所も見受けられるが、２，２−ビス（３'−シクロヘキセニル）プロパン製造時に反応中間体として生成する式３に記載の化合物についての記載は無い。この式３に示す反応中間体は、反応装置に付随の蒸留塔内部に固着し、蒸留塔を閉塞させる恐れがあった。そのため、減圧下で反応蒸留を実施するためには反応中間体の性状を考慮し、安全なプロセスを設計する必要があるが、同文献にはそれらについて開示されていない。 A method for producing 2,2-bis (3′-cyclohexenyl) propane having a biscyclohexene skeleton is disclosed in Patent Document 1. Under the conditions described in the examples of the publication, the dehydration reaction of hydrogenated bisphenol A is performed using raw hydrogenated bisphenol A, a dehydration catalyst, target substances 2,2-bis (3′-cyclohexenyl) propane and by-product water. Therefore, not only a dehydration reaction but also a water addition reaction to the double bond site proceeds, and an isomerization reaction as shown in Formula 1 produces a by-product as shown in Formula 2. Since the by-product is similar in physical properties to the target product, it is usually difficult to separate by general distillation, etc., and suppressing the formation of the by-product is 2,2-bis (3′-cyclohexenyl). ) Propane production issue. On the other hand, although the part which referred to the pressure reduction reaction can also be seen in the Example of patent document 1, about the compound of Formula 3 produced | generated as a reaction intermediate at the time of 2,2-bis (3'- cyclohexenyl) propane manufacture. There is no description. The reaction intermediate represented by the formula 3 may stick to the inside of the distillation column attached to the reaction apparatus and may block the distillation column. For this reason, in order to carry out reactive distillation under reduced pressure, it is necessary to design a safe process in consideration of the properties of the reaction intermediate, which is not disclosed in the same document.
本発明者は、鋭意検討の結果、ビシクロヘキシル−３，３'−ジエンの異性体の副生が抑制され、高純度のビシクロヘキシル−３，３'−ジエンが得られる特定の製造方法を見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventor has found a specific production method in which the by-product of the isomer of bicyclohexyl-3,3′-diene is suppressed and high-purity bicyclohexyl-3,3′-diene is obtained. The present invention has been completed.
すなわち、本発明の第一は、水添ビフェノールを、硫酸水素アルカリ金属の存在下に無溶媒で分子内脱水させて、ビシクロヘキシル−３，３'−ジエンを製造するにあたり、
（１）水添ビフェノールを硫酸水素アルカリ金属の存在下に１５０から２２０℃の温度で加熱し、分子内脱水により生じた反応中間体、副生水、未反応の水添ビフェノール、および、硫酸水素アルカリ金属を含む反応液から副生水を留出させ、（２）上記工程に引き続いて、副生水を留出させた反応液を５〜２０Ｔｏｒｒの減圧下、１５０から２２０℃の温度で加熱し、反応液から、ビシクロヘキシル−３，３'−ジエンと副生水を留出させることを特徴とするビシクロヘキシル−３，３'−ジエンの製造方法を提供するものである。また、本発明の第二は、硫酸水素アルカリ金属を水添ビフェノール１モルに対して、０．０８モルから０．２５モル使用することを特徴とする前記ビシクロヘキシル−３，３'−ジエンの製造方法を提供するものである。また、本発明の第三は、前記の製造方法によって製造されたビシクロヘキシル−３，３'−ジエンを提供するものである。
That is, in the first aspect of the present invention, hydrogenated biphenol is subjected to intramolecular dehydration without solvent in the presence of an alkali metal hydrogen sulfate to produce bicyclohexyl-3,3′-diene.
(1) A hydrogenated biphenol is heated at a temperature of 150 to 220 ° C. in the presence of an alkali metal hydrogen sulfate, and a reaction intermediate, by-product water, unreacted hydrogenated biphenol, and hydrogen sulfate generated by intramolecular dehydration By-product water is distilled from the reaction solution containing alkali metal. (2) Following the above step, the reaction solution from which the by-product water is distilled is heated at a temperature of 150 to 220 ° C. under a reduced pressure of 5 to 20 Torr. In addition, the present invention provides a method for producing bicyclohexyl-3,3′-diene, characterized by distilling bicyclohexyl-3,3′-diene and by-product water from a reaction solution. In the second aspect of the present invention, the bicyclohexyl-3,3′-diene is characterized in that an alkali metal hydrogen sulfate is used in an amount of 0.08 mol to 0.25 mol per 1 mol of hydrogenated biphenol. A manufacturing method is provided. The third aspect of the present invention is to provide bicyclohexyl-3,3′-diene produced by the above production method.
本発明の製造方法によれば、高純度のビシクロヘキシル−３，３'−ジエンを製造することができる。 According to the production method of the present invention, high-purity bicyclohexyl-3,3′-diene can be produced.
以下、本発明の高純度ビシクロヘキシル−３，３'ジエンの製造方法を詳細に説明する。 Hereinafter, the manufacturing method of the high purity bicyclohexyl-3,3 'diene of this invention is demonstrated in detail.
原料の水添ビフェノールを、分子内脱水させる際に用いる脱水触媒としては、硫酸水素アルカリ金属が望ましい。好ましい硫酸水素アルカリ金属としては、硫酸水素カリウム、硫酸水素ナトリウムなどが挙げられる。脱水触媒の使用量は原料の水添ビフェノールに対して１０〜２０ｍｏｌ％が望ましい。１０ｍｏｌ％未満であると、反応が進まず、未反応の水添ビフェノールが回収される。２０ｍｏｌ％を超えると、異性化反応が生じ純度の低下が見られる。 As the dehydration catalyst used for intramolecular dehydration of the raw hydrogenated biphenol, alkali metal hydrogen sulfate is desirable. Preferred examples of the alkali metal hydrogen sulfate include potassium hydrogen sulfate and sodium hydrogen sulfate. The amount of the dehydration catalyst used is desirably 10 to 20 mol% with respect to the raw hydrogenated biphenol. If it is less than 10 mol%, the reaction does not proceed and unreacted hydrogenated biphenol is recovered. When it exceeds 20 mol%, an isomerization reaction occurs and a decrease in purity is observed.
本発明の水添ビフェノールの分子内脱水反応は無溶媒で実施する。反応は、高純度の水添ビフェノールを融点近傍で融解させて行うのが好ましい。水添ビフェノールは室温で固体であるため、その取扱を容易にするために、メタノール、エタノール、ｎ−プロパノール、イソプロパノールなどのアルコール系有機溶液中に溶解させて取り扱うことも可能であるが、脱水反応を開始する前にあらかじめ反応系よりメタノール、エタノール、ｎ−プロパノール、イソプロパノールなどのアルコール系溶剤を除去する必要がある。さもなければ、分子内脱水反応中にアルコール系溶剤が脱水触媒と反応し、低分子量で常温で気体の性質を有するオレフィン化合物が生成し、反応容器内部の圧力上昇や脱水触媒の活性低下の原因となるため好ましくない。 The intramolecular dehydration reaction of the hydrogenated biphenol of the present invention is carried out without solvent. The reaction is preferably performed by melting high-purity hydrogenated biphenol near the melting point. Since hydrogenated biphenol is a solid at room temperature, it can be handled by dissolving it in an alcoholic organic solution such as methanol, ethanol, n-propanol, or isopropanol in order to facilitate its handling. Before starting, it is necessary to remove alcohol solvents such as methanol, ethanol, n-propanol and isopropanol from the reaction system in advance. Otherwise, during the intramolecular dehydration reaction, the alcoholic solvent reacts with the dehydration catalyst to produce an olefin compound having a low molecular weight and gaseous properties at room temperature, which causes the pressure inside the reaction vessel to increase and the dehydration catalyst activity to decrease. Therefore, it is not preferable.
本発明の目的物であるビシクロヘキシル−３，３'−ジエンは沸点２６０℃／７６０Ｔｏｒｒ、１４０℃／１０Ｔｏｒｒの無色透明の液体である。 Bicyclohexyl-3,3′-diene, which is the object of the present invention, is a colorless and transparent liquid having boiling points of 260 ° C./760 Torr and 140 ° C./10 Torr.
分子内脱水反応の中間体（式３）は、沸点３８０℃／７６０Ｔｏｒｒ、２３０℃／１０Ｔｏｒｒの昇華性を有する常温では白色の固体である。 The intermediate of the intramolecular dehydration reaction (Formula 3) is a white solid at room temperature having sublimation properties of boiling points of 380 ° C./760 Torr and 230 ° C./10 Torr.
本発明における反応温度は、実質的に脱水触媒による分子内脱水反応が起こる温度であればよいが、好ましくは１５０〜２２０℃である。反応温度が１５０℃未満であれば反応速度が著しく遅く工業的に不利である。反応温度が２２０℃を超えると原料物質の着色や異性化反応を促進する結果を招き、本発明の目的に反する。 The reaction temperature in the present invention may be a temperature at which an intramolecular dehydration reaction is substantially caused by a dehydration catalyst, but is preferably 150 to 220 ° C. If reaction temperature is less than 150 degreeC, reaction rate will be remarkably slow and disadvantageous industrially. When the reaction temperature exceeds 220 ° C., the result of promoting the coloring and isomerization reaction of the raw material is brought about, which is contrary to the object of the present invention.
本発明における反応時の圧力は最初の（１）水添ビフェノールを硫酸水素アルカリ金属の存在下に１５０から２２０℃の温度で加熱し、分子内脱水により生じた反応中間体、副生水、未反応の水添ビフェノール、および、硫酸水素アルカリ金属を含む反応液から副生水を留出させる工程と、次の（２）副生水を留出させた反応液を５〜２０Ｔｏｒｒの減圧下、１５０から２２０℃の温度で加熱し、反応液から、ビシクロヘキシル−３，３'−ジエンと副生水を留出させる工程で異なる。最初の（１）の工程においては、副生水を留出させるが、この時反応中間体を留出させることは以下の点から望ましくない。
１）反応中間体の留出により、目的物の収率の低下を招く。
２）反応中間体は昇華性の固体であるため、副生水の留出経路に固体が析出することによって、留出経路の閉塞により反応容器内部の圧力上昇を招き、反応容器破裂、破損、反応溶液の飛散の原因となる。
The pressure during the reaction in the present invention is as follows: (1) Hydrogenated biphenol is heated at a temperature of 150 to 220 ° C. in the presence of alkali metal hydrogensulfate, and the reaction intermediate, byproduct water, The step of distilling by-product water from the reaction solution containing hydrogenated biphenol and alkali metal hydrogen sulfate, and the following (2) reaction solution from distilling by-product water under reduced pressure of 5 to 20 Torr, It differs in the process of heating at a temperature of 150 to 220 ° C. and distilling bicyclohexyl-3,3′-diene and by-product water from the reaction solution. In the first step (1), by-product water is distilled, but it is not desirable to distill the reaction intermediate at this time from the following points.
1) The distillation of the reaction intermediate causes a decrease in the yield of the target product.
2) Since the reaction intermediate is a sublimable solid, the precipitation of by-product water in the distillation path causes the pressure inside the reaction container to increase due to the blockage of the distillation path, and the reaction container ruptures and breaks. It causes scattering of the reaction solution.
よって、最初の（１）の工程においては、反応圧力（反応容器内の圧力）は減圧にせず、常圧にして反応中間体の留出を防ぐ。次の（２）の工程においては、反応圧力は５〜２０Ｔｏｒｒの減圧にする。この工程（２）において、反応圧力を１００Ｔｏｒｒ以上にすることは、目的物の留出に時間を要すため、ビシクロヘキシル−３，３'−ジエンの異性化の原因となるため好ましくない。 Therefore, in the first step (1), the reaction pressure (pressure in the reaction vessel) is not reduced, but is reduced to normal pressure to prevent distillation of the reaction intermediate. In the next step (2), the reaction pressure is reduced to 5 to 20 Torr. In this step (2), it is not preferable to set the reaction pressure to 100 Torr or more because it takes time to distill the target product and causes isomerization of bicyclohexyl-3,3′-diene.
尚、反応時間の目安であるが、反応開始後約３〜４時間が（１）の工程で、それ以降は（２）の工程となる。 In addition, although it is a standard of reaction time, about 3 to 4 hours after a reaction start are processes of (1), and after that, it becomes the process of (2).
本発明の（２）の工程で留出により得られたビシクロヘキシル−３，３'−ジエンは微量の水を含む。ビシクロヘキシル−３，３'−ジエンと水は両者の比重差を利用しても容易に分離できるが、蒸留による分離精製が望ましい。 Bicyclohexyl-3,3′-diene obtained by distillation in the step (2) of the present invention contains a trace amount of water. Bicyclohexyl-3,3′-diene and water can be easily separated using the difference in specific gravity between them, but separation and purification by distillation are desirable.
尚、本発明のビシクロヘキシル−３，３'−ジエンの製造に使用する反応器に付随する蒸留装置は、オールダショー型蒸留装置など一般に使用されている蒸留装置でよい。 The distillation apparatus associated with the reactor used for the production of the bicyclohexyl-3,3′-diene of the present invention may be a distillation apparatus generally used such as an Oldershaw type distillation apparatus.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。尚、「％」及び「部」は、特に示す場合を除くほか「重量％」及び「重量部」を示す。
（実施例１）
［ビシクロヘキシル−３，３'−ジエンの合成］
攪拌器、２０段の蒸留塔、温度計を備えている１０リットルの４つ口フラスコに水添ビフェノール６ｋｇと硫酸水素カリウム６２０ｇを加えた。続いて、フラスコを１８０℃に加熱し、水添ビフェノールを融解させ、攪拌を開始した。蒸留塔の塔頂より副生水を留出させながら反応を続け、３時間経過後、反応系内を１０Ｔｏｒｒに減圧し、水とビシクロヘキシル−３，３'−ジエンを蒸留塔の最上段より連続的に系外に留出させた。系外に留去させた水とビシクロヘキシル−３，３'−ジエンはデカンターで二層に分離させ上層液のみを取り出した。その後、４時間かけて反応温度を２２０℃にし、水とビシクロヘキシル−３，３'−ジエンの留去がなくなった時点で反応終了とした。ビシクロヘキシル−３，３'−ジエンの留出粗液の収量は４５０７ｇであり、ガスクロマトグラフで測定した純度は９８％であった。
（参考例１）
［ビシクロヘキシル−３，３'−ジエンの精製］
実施例１で得られた、ビシクロヘキシル−３，３'−ジエンの留出粗液４５００ｇを攪拌器、２０段の蒸留塔、温度計を備えている５リットルの４つ口フラスコに入れ、オイルバスで１８０℃に昇温した。その後反応系内を１０Ｔｏｒｒに減圧し、水を留去してから蒸留塔の最上段の温度を１４５℃に維持し、還流比１で５時間かけてビシクロヘキシル−３，３'−ジエンを精製し、無色透明の液体を得た。得られたビシクロヘキシル−３，３'−ジエンの精製物の収量は４３５３ｇであった。また、ガスクロマトグラフで測定した純度は９９．６％、ヨウ素価は３１２（Ｉ2・ｇ／１００ｇ）、ＡＰＨＡは１０以下であった。
（比較例１）
攪拌器、温度計、上部にジムロート式コンデンサーの取り付けられたディーンスターク（ＤＥＡＮ−ＳＴＡＲＫ）を備えた１５リットルの４つ口フラスコに水添ビフェノール６ｋｇと触媒として硫酸水素カリウム４９０ｇ、溶媒としてソルベッソ１５０（エクソン化学製）６ｋｇを加えて、反応系内部を窒素で置換した。続いて、１８０℃で脱水反応を実施した。水の留出が無くなった時点で反応を終了した。反応液をガスクロマトグラフィーで分析したところ、９６％の収率でビシクロヘキシル−３，３'−ジエンが生成していた。得られた反応液を分液漏斗を用いて６ｋｇの水で洗浄し、触媒を除去した後、有機層を減圧蒸留し無色透明液状のビシクロヘキシル−３，３'−ジエンを得た。得られたビシクロヘキシル−３，３'−ジエンの精製物の収量は４２３５ｇであった。一方、純度をガスクロマトグラフで測定したところ、ビシクロヘキシル−３，３'−ジエンの純度は７０％であった。ガスクロマトグラフ質量分析計による測定では、１，１'−ビシクロヘキセン、２，２'−ビシクロヘキセン等のシグナルピークを確認した。これらの副生成物は、脱水反応し生成した二重結合に水が再付加し、その後再脱水することにより二重結合の位置が異なる異性体が生じたと考えられる。又、ヨウ素価は２９０（Ｉ2・ｇ／１００ｇ）、ＡＰＨＡは５０であった。
（比較例２）
溶媒として、メタノール１０００ｍｌを加えた他は実施例１と同様にして、ビシクロヘキシル−３，３'−ジエンの合成を試みた。しかし、系内を減圧にしようとすると、反応系内が安定せず、反応を続けることができなかった。
（比較例３）
触媒として、硫酸水素カリウム１６５０ｇを加えた他は、実施例１と同様にして、ビシクロヘキシル−３，３'−ジエンの合成を試みた。得られた反応粗液は、参考例１の［ビシクロヘキシル−３，３'−ジエンの精製］と同様の操作で精製した。その結果、得られた精製物の純度は７５．０％、ヨウ素価は２８０（Ｉ2・ｇ／１００ｇ）、ＡＰＨＡは６０であった。
（比較例４）
触媒として、硫酸水素カリウム２ｇを加えた他は、実施例１と同様にして、ビシクロヘキシル−３，３'−ジエンの合成を試みた。しかし、６時間加熱を続けても反応は進行せず実験を中止した。
（比較例５）
反応を開始して３時間経過後に、反応系内を２５０Ｔｏｒｒに減圧した他は、実施例１と同様にして、ビシクロヘキシル−３，３'−ジエンの合成を試みた。しかし、系内を２５０Ｔｏｒｒに減圧しても、水が留出しただけでビシクロヘキシル−３，３'−ジエンは系外に留出せず実験を中止した。
（比較例６）
反応を開始して３時間経過後に、反応系内を０．０５Ｔｏｒｒに減圧した他は、実施例１と同様にして、ビシクロヘキシル−３，３'−ジエンの合成を試みた。しかし、蒸留塔に反応中間体が析出し蒸留塔内部が閉塞したため、実験を中止した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. “%” And “part” indicate “% by weight” and “part by weight”, unless otherwise specified.
(Example 1)
[Synthesis of Bicyclohexyl-3,3′-Diene]
6 kg of hydrogenated biphenol and 620 g of potassium hydrogen sulfate were added to a 10-liter four-necked flask equipped with a stirrer, a 20-stage distillation column, and a thermometer. Subsequently, the flask was heated to 180 ° C. to melt the hydrogenated biphenol, and stirring was started. The reaction was continued while distilling by-product water from the top of the distillation column, and after 3 hours, the pressure in the reaction system was reduced to 10 Torr, and water and bicyclohexyl-3,3′-diene were added from the top of the distillation column. Distilled out of the system continuously. The water and bicyclohexyl-3,3′-diene distilled off outside the system were separated into two layers with a decanter, and only the upper layer liquid was taken out. Thereafter, the reaction temperature was raised to 220 ° C. over 4 hours, and the reaction was completed when water and bicyclohexyl-3,3′-diene were not distilled off. The yield of the distillate crude liquid of bicyclohexyl-3,3′-diene was 4507 g, and the purity measured by gas chromatography was 98%.
(Reference Example 1)
[Purification of bicyclohexyl-3,3′-diene]
4500 g of the dicyclohexyl-3,3′-diene distillate obtained in Example 1 was placed in a 5-liter four-necked flask equipped with a stirrer, a 20-stage distillation column and a thermometer, The temperature was raised to 180 ° C. with a bath. Thereafter, the pressure in the reaction system is reduced to 10 Torr, water is distilled off, the temperature at the top of the distillation column is maintained at 145 ° C., and bicyclohexyl-3,3′-diene is purified at a reflux ratio of 1 over 5 hours. A colorless and transparent liquid was obtained. The yield of the obtained purified product of bicyclohexyl-3,3′-diene was 4353 g. The purity measured by gas chromatography was 99.6%, the iodine value was 312 (I 2 · g / 100 g), and APHA was 10 or less.
(Comparative Example 1)
A 15-liter four-necked flask equipped with a stirrer, a thermometer, and a DEAN-STARK equipped with a Dimroth condenser at the top, 6 kg of hydrogenated biphenol, 490 g of potassium hydrogen sulfate as a catalyst, and Solvesso 150 (as a solvent) 6 kg of Exxon Chemical) was added, and the inside of the reaction system was replaced with nitrogen. Subsequently, a dehydration reaction was performed at 180 ° C. The reaction was terminated when there was no water distilling. When the reaction solution was analyzed by gas chromatography, bicyclohexyl-3,3′-diene was produced in a yield of 96%. The obtained reaction solution was washed with 6 kg of water using a separatory funnel to remove the catalyst, and then the organic layer was distilled under reduced pressure to obtain a colorless and transparent liquid bicyclohexyl-3,3′-diene. The yield of the obtained purified product of bicyclohexyl-3,3′-diene was 4235 g. On the other hand, when the purity was measured with a gas chromatograph, the purity of bicyclohexyl-3,3′-diene was 70%. In the measurement with a gas chromatograph mass spectrometer, signal peaks of 1,1′-bicyclohexene, 2,2′-bicyclohexene and the like were confirmed. It is considered that these by-products produced isomers having different positions of the double bond by re-adding water to the double bond generated by the dehydration reaction and then re-dehydrating. The iodine value was 290 (I 2 · g / 100 g), and APHA was 50.
(Comparative Example 2)
Synthesis of bicyclohexyl-3,3′-diene was attempted in the same manner as in Example 1 except that 1000 ml of methanol was added as a solvent. However, when the pressure in the system was reduced, the reaction system was not stable and the reaction could not be continued.
(Comparative Example 3)
Synthesis of bicyclohexyl-3,3′-diene was attempted in the same manner as in Example 1 except that 1650 g of potassium hydrogen sulfate was added as a catalyst. The obtained reaction crude liquid was purified in the same manner as in [Purification of bicyclohexyl-3,3′-diene] in Reference Example 1. As a result, the purity of the obtained purified product was 75.0%, the iodine value was 280 (I 2 · g / 100 g), and the APHA was 60.
(Comparative Example 4)
The synthesis of bicyclohexyl-3,3′-diene was attempted in the same manner as in Example 1 except that 2 g of potassium hydrogen sulfate was added as a catalyst. However, even if heating was continued for 6 hours, the reaction did not proceed and the experiment was stopped.
(Comparative Example 5)
Three hours after starting the reaction, synthesis of bicyclohexyl-3,3′-diene was attempted in the same manner as in Example 1 except that the pressure in the reaction system was reduced to 250 Torr. However, even if the pressure in the system was reduced to 250 Torr, the experiment was stopped without distilling bicyclohexyl-3,3′-diene out of the system only by distilling water.
(Comparative Example 6)
Three hours after starting the reaction, synthesis of bicyclohexyl-3,3′-diene was attempted in the same manner as in Example 1 except that the pressure in the reaction system was reduced to 0.05 Torr. However, the reaction was deposited in the distillation column and the inside of the distillation column was blocked, so the experiment was stopped.
Claims (3)
（１）水添ビフェノールを硫酸水素アルカリ金属の存在下に１５０から２２０℃の温度で加熱し、分子内脱水により生じた反応中間体、副生水、未反応の水添ビフェノール、および、硫酸水素アルカリ金属を含む反応液から副生水を留出させ、（２）上記工程に引き続いて、副生水を留出させた反応液を５〜２０Ｔｏｒｒの減圧下、１５０から２２０℃の温度で加熱し、反応液から、ビシクロヘキシル−３，３'−ジエンと副生水を留出させることを特徴とするビシクロヘキシル−３，３'−ジエンの製造方法。 In producing bicyclohexyl-3,3′-diene by intramolecular dehydration of hydrogenated biphenol in the presence of an alkali metal hydrogen sulfate without solvent.
(1) A hydrogenated biphenol is heated at a temperature of 150 to 220 ° C. in the presence of an alkali metal hydrogen sulfate, and a reaction intermediate, by-product water, unreacted hydrogenated biphenol, and hydrogen sulfate generated by intramolecular dehydration By-product water is distilled from the reaction solution containing alkali metal. (2) Following the above step, the reaction solution from which the by-product water is distilled is heated at a temperature of 150 to 220 ° C. under a reduced pressure of 5 to 20 Torr. And bicyclohexyl-3,3′-diene and by-product water are distilled from the reaction solution.
Bicyclohexyl-3,3'-diene produced by the production method according to claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007119743A1 (en) | 2006-04-18 | 2007-10-25 | Daicel Chemical Industries, Ltd. | Process for production of cyclic olefins |
| WO2008004504A1 (en) | 2006-07-06 | 2008-01-10 | Daicel Chemical Industries, Ltd. | Alicyclic diepoxy compound, epoxy resin composition, and cured product |
| WO2008143003A1 (en) * | 2007-05-24 | 2008-11-27 | Sumitomo Bakelite Co., Ltd. | Transparent composite sheet |
| WO2013153957A1 (en) * | 2012-04-09 | 2013-10-17 | 株式会社ダイセル | Method for producing hydrogenated biphenol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004346007A (en) * | 2003-05-22 | 2004-12-09 | Mitsui Chemicals Inc | Method for producing 3,3'-bicyclohexenyl |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004346007A (en) * | 2003-05-22 | 2004-12-09 | Mitsui Chemicals Inc | Method for producing 3,3'-bicyclohexenyl |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007119743A1 (en) | 2006-04-18 | 2007-10-25 | Daicel Chemical Industries, Ltd. | Process for production of cyclic olefins |
| US8115043B2 (en) | 2006-04-18 | 2012-02-14 | Daicel Chemical Industries, Ltd. | Method for producing cyclic olefin compound |
| US7989523B2 (en) | 2006-06-07 | 2011-08-02 | Daicel Chemical Industries, Ltd. | Alicyclic diepoxy compound, epoxy resin composition comprising the same, and cured article therefrom |
| WO2008004504A1 (en) | 2006-07-06 | 2008-01-10 | Daicel Chemical Industries, Ltd. | Alicyclic diepoxy compound, epoxy resin composition, and cured product |
| KR101394835B1 (en) | 2006-07-06 | 2014-05-13 | 가부시끼가이샤 다이셀 | Alicyclic diepoxy compound, epoxy resin composition, and cured product |
| WO2008143003A1 (en) * | 2007-05-24 | 2008-11-27 | Sumitomo Bakelite Co., Ltd. | Transparent composite sheet |
| JPWO2008143003A1 (en) * | 2007-05-24 | 2010-08-05 | 住友ベークライト株式会社 | Transparent composite sheet |
| JP4655248B2 (en) * | 2007-05-24 | 2011-03-23 | 住友ベークライト株式会社 | Transparent composite sheet |
| WO2013153957A1 (en) * | 2012-04-09 | 2013-10-17 | 株式会社ダイセル | Method for producing hydrogenated biphenol |
| CN104220404A (en) * | 2012-04-09 | 2014-12-17 | 株式会社大赛璐 | Method for producing hydrogenated biphenol |
| US9206099B2 (en) | 2012-04-09 | 2015-12-08 | Daicel Corporation | Method for producing hydrogenated biphenol |
| JPWO2013153957A1 (en) * | 2012-04-09 | 2015-12-17 | 株式会社ダイセル | Method for producing hydrogenated biphenol |
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