WO2015079957A1 - Procédé de production d'un composé d'oléfine cyclique - Google Patents

Procédé de production d'un composé d'oléfine cyclique Download PDF

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Publication number
WO2015079957A1
WO2015079957A1 PCT/JP2014/080405 JP2014080405W WO2015079957A1 WO 2015079957 A1 WO2015079957 A1 WO 2015079957A1 JP 2014080405 W JP2014080405 W JP 2014080405W WO 2015079957 A1 WO2015079957 A1 WO 2015079957A1
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cyclic olefin
dehydration
olefin compound
organic solvent
dehydration catalyst
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PCT/JP2014/080405
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English (en)
Japanese (ja)
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河辺正人
谷川博人
上原和浩
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株式会社ダイセル
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
    • C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a resin raw material excellent in heat resistance, hydrolysis resistance, weather resistance, transparency and the like and a method for producing an important cyclic olefin compound as an intermediate thereof.
  • a method for producing a cyclic olefin compound having a cyclohexene skeleton a method for producing by a dehydration reaction of alcohol is widely known.
  • a technology for producing a cyclic olefin compound by dehydration reaction of alcohol using an alkali metal hydrogen sulfate, which is an acidic salt see Patent Document 1, Patent Document 3, Non-Patent Document 2, and Non-Patent Document 3
  • concentrated sulfuric acid A technique for producing a cyclic olefin compound by dehydration of alcohol using an inorganic acid such as phosphoric acid as a catalyst (see Patent Document 2 and Non-Patent Document 1) is disclosed in the literature.
  • a hydrogenated biphenol represented by the following formula (3a) to (3f) can be produced as isomers (cyclic olefin compounds) represented by the following formulas (3a) to (3f). That is, when the compound represented by the formula (3a) (bicyclohexyl-3,3′-diene; colorless transparent liquid having boiling points of 260 ° C./760 Torr and 140 ° C./10 Torr) is used as the target compound, Living organisms can produce.
  • an alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group in its molecule is completely neutralized with sulfonic acids, phosphoric acid, sulfuric acid, sulfonic acids and organic bases, phosphoric acid and organic bases in an organic solvent.
  • a cyclic olefin compound that is heated to a temperature of 130 to 230 ° C.
  • Patent Document 4 A method (Patent Document 4) has been proposed. By this method, the ratio of the target cyclic olefin to the isomer is improved from 80/20 to 81/19 in the comparative example to 86/14 to 92/8. However, even an improved isomer ratio of 86/14 to 92/8 is not satisfactory, and further improvement of the isomer ratio is desired.
  • An object of the present invention is to provide a method for producing a cyclic olefin compound that can suppress side reactions such as isomerization reaction and can efficiently obtain a high-purity cyclic olefin compound having a small impurity content in a simple and high yield. There is.
  • the present inventor has studied in detail a side reaction such as isomerization in an intramolecular dehydration reaction of an alicyclic alcohol having two or more cyclohexane rings to which a hydroxyl group is bonded in the molecule. It was found that most of the side reactions such as crystallization occurred in the initial stage of the reaction, particularly in the temperature rising process.
  • the dehydration reaction proceeds even during the temperature rise, and the isomerization reaction of the formula (4) proceeds through the generated water.
  • the isomer concentration increases.
  • the present invention relates to a cyclic olefin compound having two or more cyclohexene rings in the molecule by intramolecular dehydration of an alicyclic alcohol having two or more cyclohexane rings bonded to a hydroxyl group in the molecule in the presence of a dehydration catalyst.
  • the dehydration catalyst is continuously or intermittently mixed with the mixture containing the alicyclic alcohol and the organic solvent under reflux of an organic solvent that azeotropes with water and separates from water at room temperature.
  • dehydration catalyst is composed of a plurality of components, dehydration is carried out while continuously or intermittently charging at least one of the components into the mixture containing the alicyclic alcohol and the organic solvent.
  • a method for producing a cyclic olefin compound characterized by carrying out a reaction.
  • a mixture of an acid component and a base component is used as the dehydration catalyst, and at least the acid component of the acid component and the base component, which are constituent components of the dehydration catalyst, is added to the alicyclic alcohol and the organic solvent under reflux of the organic solvent.
  • the dehydration reaction may be carried out while continuously or intermittently charged into the mixed solution containing.
  • an alicyclic alcohol (hereinafter sometimes referred to as “substrate”) having two or more cyclohexane rings to which hydroxyl groups are bonded is dehydrated in the molecule in the presence of a dehydration catalyst.
  • substrate an alicyclic alcohol having two or more cyclohexane rings to which hydroxyl groups are bonded is dehydrated in the molecule in the presence of a dehydration catalyst.
  • the alicyclic alcohol having two or more cyclohexane rings having hydroxyl groups bonded thereto is not particularly limited as long as the compound has two or more cyclohexane rings having hydroxyl groups bonded thereto.
  • a typical example of the alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group bonded thereto in the molecule is the alicyclic alcohol represented by the formula (1).
  • Y represents a straight or branched chain having 1 to 18 carbon atoms which may be substituted with a single bond, an oxygen atom, a sulfur atom, —SO—, —SO 2 —, or a halogen atom.
  • it represents a divalent group selected from divalent hydrocarbon groups having a cyclic skeleton, or a divalent group in which a plurality of these groups are bonded.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the divalent hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 18 carbon atoms include methylene, ethylene, methylmethylene, trimethylene, propylene, dimethylmethylene, tetramethylene, pentamethylene, hexa C1-C18 linear or branched alkylene groups such as methylene, heptamethylene, octamethylene, decamethylene, etc .; 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexene C3-C18 divalent alicyclic hydrocarbon group such as silene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclopentylidene, cyclohexylidene group; 1,2-phenylene, 1, C6-C18 divalent aromatic hydrocarbon groups such as 3-phenylene
  • Examples of the divalent hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 18 carbon atoms substituted with a halogen atom include, for example, —C (Br) 2 —, —C (CBr 3). ) 2- , -C (CF 3 ) 2- and the like.
  • Y in particular, a single bond, an oxygen atom, a sulfur atom, —SO—, —SO 2 —, —CH 2 —, —C (CH 3 ) 2 —, — (CH 2 ) 2 —, —C (Br 2 ), —C (CBr 3 ) 2 —, —C (CF 3 ) 2 —, a divalent hydrocarbon group having a linear, branched or cyclic skeleton having 3 to 18 carbon atoms is preferred.
  • alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group bonded thereto are, for example, hydrogenated biphenol, bis (cyclohexanol) methane, bis (dimethylcyclohexanol) methane, 1,2-bis ( Cyclohexanol) ethane, 1,3-bis (cyclohexanol) propane, 2,2-bis (cyclohexanol) propane, 1,4-bis (cyclohexanol) butane, 1,5-bis (cyclohexanol) pentane, , 6-bis (cyclohexanol) hexane, 2,2-bis (cyclohexanol) propane, bis (cyclohexanol) phenylmethane, 3,3-bis (cyclohexanol) pentane, 5,5-bis (cyclohexanol) heptane , 2,2-bis [4,4'-bis (sic He
  • a compound having two or more 4-hydroxycyclohexyl groups for example, 2 to 4, particularly 2), such as hydrogenated biphenol (for example, 4,4′-bicyclohexanol), bis (cyclohexanol).
  • Methane eg, bis (4-hydroxycyclohexyl) methane), etc.
  • 1,2-bis (cyclohexanol) ethane eg, 1,2-bis (4′-hydroxycyclohexyl) ethane), etc.
  • 2,2 -Bis (cyclohexanol) propane for example, 2,2-bis (4'-hydroxycyclohexyl) propane, etc.] and the like are suitable as a raw material in the production method of the present invention.
  • the alicyclic alcohol having two or more cyclohexane rings having a hydroxyl group bonded thereto can be used alone or in combination of two or more.
  • an acid component alone or a mixture of an acid component and a base component is used.
  • the acid component of the dehydration catalyst can be selected from, for example, phosphoric acid; sulfuric acid; sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid.
  • Examples of the base component of the dehydration catalyst include alkali metal hydroxides such as LiOH, NaOH, KOH, inorganic base compounds such as NH 3 , or 1,8-diazabicyclo [5.4.0] undecene-7 ( DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), piperidine, N-methylpiperidine, pyrrolidine, N-methylpyrrolidine, triethylamine, tributylamine, benzyldimethylamine, 4-dimethylaminopyridine Amines such as N, N-dimethylaniline (particularly tertiary amines); nitrogen-containing aromatic heterocyclic compounds such as pyridine, collidine, quinoline and imidazole; guanidines; organic base compounds such as hydrazines be able to.
  • alkali metal hydroxides such as LiOH, NaOH, KOH
  • inorganic base compounds such as NH 3 , or 1,8-diazabicy
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] nonene-5
  • triethylenediamine Tertiary amines such as triethylamine (particularly cyclic amines), guanidines and hydrazines
  • DBU, DBN, triethylenediamine and triethylamine are particularly preferable.
  • the acid component and the base component may be used alone or in combination of two or more.
  • the ratio of the acid component to the base component is preferably 0.01 to 1 mol, more preferably 0.1 to 1 mol, with respect to 1 mol of the acid component. 1 mole.
  • the base component is preferably 0.01 to 1 gram equivalent, more preferably 0.1 to 1 gram equivalent, relative to 1 gram equivalent of the acid component.
  • a corresponding salt is normally formed.
  • the amount of the acid component used in the dehydration catalyst is, for example, about 0.001 to 0.5 mol with respect to 1 mol of the alicyclic alcohol as a substrate.
  • the dehydration catalyst is continuously or intermittently charged into the mixed solution containing the alicyclic alcohol and the organic solvent under reflux of the organic solvent that azeotropes with water and separates from water at room temperature.
  • the dehydration catalyst is composed of a plurality of components (for example, a mixture of an acid component and a base component)
  • at least one of the components is The dehydration reaction is carried out while continuously or intermittently charged into the mixed solution containing the formula alcohol and the organic solvent.
  • the organic solvent is not particularly limited as long as it is an organic solvent that azeotropes with water and separates from water at room temperature (for example, 23 ° C.) and is inert under the reaction conditions.
  • organic solvents include, for example, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, tetramethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, Aliphatic hydrocarbons having 6 to 18 carbon atoms such as isopropylcyclohexane; benzene, toluene, xylene, trimethylbenzene (for example, pseudocumene), tetramethylbenzene, styrene, ethylbenzene, diethylbenzene, propylbenzene, cumene, indene, tetrahydronaphthalene, Aromatic hydrocarbons having 6 to 18 carbon atoms such
  • the amount of the organic solvent used can be appropriately selected in consideration of operability, reaction rate, etc., but is preferably about 0.1 to 10 parts by weight with respect to 1 part by weight of the alicyclic alcohol as a substrate. More preferably 0.5 to 5 parts by weight.
  • the reaction temperature can be selected from the range of 100 to 250 ° C., for example.
  • a low reaction temperature is selected.
  • a high reaction temperature is selected.
  • the dehydration catalyst As a method for preparing the dehydration catalyst, for example, when the dehydration catalyst is composed only of an acid component, the mixed liquid containing the alicyclic alcohol and the organic solvent is heated to a temperature at which the organic solvent is refluxed.
  • the dehydration catalyst is preferably charged continuously or intermittently.
  • the ratio of the dehydration catalyst charged continuously or intermittently after reflux of the mixed solution is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight, based on the total amount of the dehydration catalyst used. Above, particularly preferably 100% by weight. It is preferable that a dehydration catalyst is not present as much as possible before the mixture is refluxed.
  • the dehydration catalyst when the dehydration catalyst is composed of a mixture of an acid component and a base component, a mixed liquid containing the alicyclic alcohol and an organic solvent (or a component constituting the dehydration catalyst and the alicyclic alcohol and the organic solvent).
  • a mixture containing a part or all of the base component) is heated to a temperature at which the organic solvent is refluxed, and at least the acid component among the components constituting the dehydration catalyst is charged continuously or intermittently.
  • the ratio of the acid component charged continuously or intermittently after reflux of the mixed solution is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight with respect to the total amount of the acid component used. % Or more, particularly preferably 100% by weight. It is preferable that the acid component is not present as much as possible before the mixture is refluxed.
  • the dehydration catalyst is a mixture of an acid component and a base component
  • the acid component accelerates the dehydration reaction
  • the base component adjusts the acidity of the dehydration catalyst and suppresses side reactions such as isomerization. Therefore, at least the acid component in the dehydration catalyst is charged with the organic solvent refluxed as described above, and is prepared in a state in which the generated water is ready to be sequentially removed. Can be suppressed.
  • the reaction pressure may be normal pressure, reduced pressure, or increased pressure, and the pressure is selected so that the organic solvent is refluxed at the selected reaction temperature.
  • the reflux rate of the organic solvent is, for example, about 0.05 to 1 kg / hr with respect to 1 mol of the alicyclic alcohol.
  • reaction mixture After completion of the reaction, the reaction mixture is subjected to separation / purification means such as concentration, distillation, crystallization, extraction, column chromatography, etc. to thereby obtain a cyclic olefin compound having two or more cyclohexene rings in the molecule [for example, the above formula (2) Can be isolated.
  • separation / purification means such as concentration, distillation, crystallization, extraction, column chromatography, etc.
  • cyclic olefin compound represented by the formula (2) include bicyclohexyl-3,3′-diene, bis (3-cyclohexenyl) methane, 1,2-bis (3′-cyclohexenyl).
  • examples include ethane and 2,2-bis (3′-cyclohexenyl) propane.
  • Example 1 1,4 g of 4,4′-bicyclohexanol, 1,500 g of pseudocumene as an organic solvent, 69.1 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) as a base component of the dehydration catalyst, Were charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel, and heated at a pressure of 328 mmHg (absolute pressure), pseudocumene distilled at a can temperature of 150 ° C.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • the decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant.
  • the heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
  • As an acid component of the dehydration catalyst 55.6 g of sulfuric acid was charged in a catalyst dropping funnel, and sulfuric acid was continuously dropped at a constant rate over 1 hour. When the dropping of sulfuric acid was started, water accumulated in the lower phase of the decanter, and therefore the lower phase water was appropriately extracted into the lower phase liquid receiver.
  • the 4,4′-bicyclohexanol concentration was 0.05% by weight
  • the 4,4′-bicyclohexanol change rate was 99.87%
  • the bicyclohexyldiene concentration was 28.85% by weight.
  • the bicyclohexyldiene yield was 92.52%.
  • bicyclohexyl-2,3′-diene (isomer) was 5.84%, and the remainder was bicyclohexyl-3,3′-diene.
  • Example 2 1,000 g of 4,4′-bicyclohexanol and 1,500 g of pseudocumene as an organic solvent were charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel shown in FIG. 1, and a pressure of 328 mmHg.
  • pseudocumene distilled at a can temperature of 150 ° C.
  • the decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant.
  • the heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
  • Example 3 1,2-bis (4′-hydroxycyclohexyl) propane 1,000 g, pseudocumene 1,500 g as an organic solvent, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) 69 as a base component of a dehydration catalyst .1 g was charged into a 5 L glass four-necked flask equipped with a condenser, decanter, stirrer, and catalyst dropping funnel shown in FIG. 1 and heated at a pressure of 328 mmHg (absolute pressure). Distilled. The decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • the heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr.
  • As an acid component of the dehydration catalyst 55.6 g of sulfuric acid was charged in a catalyst dropping funnel, and sulfuric acid was continuously dropped at a constant rate over 1 hour.
  • the dropping of sulfuric acid was started, water accumulated in the lower phase of the decanter, and therefore the lower phase water was appropriately extracted into the lower phase liquid receiver.
  • the pressure was changed from 328 mmHg (absolute pressure) to 428 mmHg (absolute pressure), and the reaction was continued at a can temperature of 160 ° C. for 6 hours.
  • the decanter upper phase liquid was refluxed to the flask with a pump so that the liquid level of the decanter upper phase (pseudocumene phase) became constant. Since water accumulated in the lower phase of the decanter, the lower phase water was appropriately removed from the lower phase liquid receiver. The can temperature gradually increased and finally increased to 180 ° C. The heating amount of the heater was adjusted so that the reflux amount was 1,000 g / hr. Six hours after the start of distillation, the decanter lower phase water stopped increasing, and the reaction was stopped.
  • the 4,4′-bicyclohexanol concentration was 0.06% by weight
  • the 4,4′-bicyclohexanol conversion was 99.84%
  • the bicyclohexyldiene concentration was 27.55% by weight.
  • the bicyclohexyldiene yield was 88.37%.
  • bicyclohexyl-2,3′-diene (isomer) was 10.37% and the remainder was bicyclohexyl-3,3′-diene.
  • the bicyclohexyldiene yield is low and the production of isomers is increased.
  • a high-purity cyclic olefin compound having a small impurity content can be produced easily and efficiently at a high yield.
  • the high-purity cyclic olefin compound obtained by the production method of the present invention is useful as a resin raw material excellent in heat resistance, hydrolysis resistance, weather resistance, transparency and the like, and an intermediate thereof.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

　La présente invention concerne un procédé de production d'un composé d'oléfine cyclique qui rend possible la suppression des réactions d'isomérisation et autres réactions secondaires et qui permet d'obtenir efficacement un composé d'oléfine cyclique de haute pureté contenant peu d'impuretés, de façon simple et à haut rendement. Dans le procédé de production d'un composé d'oléfine cyclique de la présente invention, un composé d'oléfine cyclique ayant deux cycles cyclohexènes ou plus dans la molécule est produit par déshydratation intramoléculaire d'un alcool alicyclique ayant deux cycles cyclohexanes liés à un groupe hydroxyle ou plus dans la molécule en présence d'un catalyseur de déshydratation, le procédé étant caractérisé en ce qu'une réaction de déshydratation est conduite tout en introduisant le catalyseur de déshydratation en continu ou par intermittence dans une solution mixte contenant l'alcool alicyclique et un solvant organique à reflux d'un solvant organique qui est azéotrope avec de l'eau et qui se sépare de l'eau à des températures ordinaires, ou, lorsque le catalyseur de déshydratation est conçu à partir de composants multiples, tout en introduisant au moins un de ces composants en continu ou par intermittence dans une solution mixte contenant l'alcool alicyclique et un solvant organique.
PCT/JP2014/080405 2013-11-28 2014-11-17 Procédé de production d'un composé d'oléfine cyclique WO2015079957A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116217339A (zh) * 2023-05-10 2023-06-06 淄博华峰铝业有限公司 环己烯水合制备环己醇的方法及装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58103328A (ja) * 1981-12-11 1983-06-20 Taisho Pharmaceut Co Ltd Ｐ−プレニルスチレンおよびその製造法
WO2007119743A1 (fr) * 2006-04-18 2007-10-25 Daicel Chemical Industries, Ltd. Procédé pour la production d'oléfines cycliques
JP2008031424A (ja) * 2006-07-06 2008-02-14 Daicel Chem Ind Ltd 脂環式ジエポキシ化合物、エポキシ樹脂組成物及び硬化物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58103328A (ja) * 1981-12-11 1983-06-20 Taisho Pharmaceut Co Ltd Ｐ−プレニルスチレンおよびその製造法
WO2007119743A1 (fr) * 2006-04-18 2007-10-25 Daicel Chemical Industries, Ltd. Procédé pour la production d'oléfines cycliques
JP2008031424A (ja) * 2006-07-06 2008-02-14 Daicel Chem Ind Ltd 脂環式ジエポキシ化合物、エポキシ樹脂組成物及び硬化物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116217339A (zh) * 2023-05-10 2023-06-06 淄博华峰铝业有限公司 环己烯水合制备环己醇的方法及装置

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