TW202124339A - A method for producing vinylcycloalkanes compounds - Google Patents

Abstract

The present invention relates to a method for producing vinylcycloalkanes compounds represented by the general formula (5) highly selectively and economically, which comprises hydrogenation and dehydration. Hydrogenation step: hydrogenating the compounds represented by the general formula (1) or/and (2) or/and (3) or/and (4) with hydrogen to prepare the corresponding primary or secondary alcohols in the presence of hydrogenation catalyst with min. 0.1 part by wight. Dehydration step: dehydrating the corresponding primary or secondary alcohols prepared by the above-mentioned hydrogenation step to prepare vinylcycloalkanes compounds represented by the general formula (5) in the presence of dehydration catalyst.

R ¹ -CH ₂ -CH ₂ -OH (1)

Wherein R¹ of the general formula (1)~(4) is hydrocarbyl (hydrocarbon functional group) having aromatic rings.

R ² -CH=CH ₂ (5)

Wherein R² of the general formula (5) is cycloalkyl or cycloalkyl-substituted alkyl.

Description

Preparation method of vinyl naphthenic compounds

The present invention relates to a method for producing vinylcycloalkanes compounds with high selectivity and economy.

As everyone knows, aromatic compounds are a class of compounds with a benzene ring structure, which are stable in structure, difficult to decompose, and highly toxic. They can cause serious pollution to the environment and are extremely harmful to the human body. In contrast, the toxicity of cloalkanes compounds is greatly reduced. For example, compared with polystyrene (PS) and polycarbonate (PC), polycyclohexyl ethylene (PVCH) has environmental friendliness, food packaging safety, and is conducive to maintaining human health and recycling resources.

The EP 1004564 patent relates to a method for preparing hydroxyethylcyclohexane by catalytically hydrogenating the corresponding hydroxyethylbenzene with the help of ruthenium (Ru) as a catalyst. The catalyst has been treated with a reducing agent before use; the method is at the boiling point. It is carried out with paraffins above 70°C as the solvent.

CN1351001A patent discloses a method for preparing cyclohexyl ethanol. Cyclohexyl ethanol is prepared by hydrogenating phenethyl alcohol as a raw material. The catalyst used in the reaction process is nickel-aluminum-titanium alloy powder; the method disclosed in the present invention is used for benzene The conversion rate of ethanol can reach 100%, the selectivity of cyclohexyl ethanol can reach 93~98%, the catalyst price is low, the process conditions are mild, and the operation is easy.

KR Registration No.: 1007105590000 discloses a method for preparing 1-ring by continuously hydrogenating 1-methylbenzyl alcohol and/or acetophenone on a ruthenium catalyst supported on _{silica gel (SiO 2} ) with a ruthenium content of 1 to 5 wt% In the hexyl-1-ethanol method, the silica gel carrier has an "acid activity index" of less than 10%.

CN 101165035A patent discloses a method for synthesizing 1-cyclohexyl-1-ethanol: using acetophenone As the raw material, the catalyst used in the hydrogenation reaction is rhodium carbon (Rh/C), the solvent used in the reaction is ethanol, and the hydrogen pressure required for the reaction is 3~4atm. Start stirring and maintain the temperature at 40~50℃ until no more hydrogen is absorbed. Leave it to cool and filter out the catalyst. The filtrate recovers ethanol under normal pressure to obtain the crude product, which is distilled under reduced pressure to obtain the product. The invention has the advantages of low-pressure hydrogenation and high reaction yield of 1-cyclohexyl-1-ethanol.

The WO2010079035A2 patent relates to a method for preparing alkyl-substituted cyclohexyl methanol, especially 4-alkyl, by catalytically hydrogenating the corresponding aldehyde or ketone in the presence of hydrogen and in the presence of a catalyst containing ruthenium applied to a support as an active metal. A continuous process for isopropylcyclohexylmethanol, wherein the carrier contains Al ₂ O ₃ and/or SiO ₂ , and the catalyst is used in a hydrogenation reactor or a plurality of hydrogenation reactors connected in series in the form of a fixed bed catalyst middle.

The CN101238082A patent relates to a method for dehydrating alcohols, polyols or alcoholates having at least one CH group at the α position relative to alcoholates or alcohol functional groups to produce olefins or ethers, wherein the dehydration is in the general formula K ⁺ A ^- in the ionic liquid.

The CN102513080A patent discloses that the preparation methods of cyclohexane ethylene homopolymers and copolymers mainly include the following: (1) monomer polymerization: cyclohexane ethylene homopolymers and copolymers can be polymerized by monomer free radicals, Obtained by anion, cation, coordination polymerization and other methods. However, cyclohexane-based ethylene monomer is not easy to obtain, and there are no literature reports on the synthesis of this monomer, (2) heterogeneous catalytic hydrogenation of polystyrene and styrene copolymers; and the existing preparation of cyclohexane-based ethylene through catalytic hydrogenation The method of homopolymer or copolymer has defects such as slow hydrogenation rate, large amount of hydrogenation catalyst, and easy breakage of polymer chain. Cyclohexane-based ethylene homopolymers and copolymers have broad application prospects in daily life, optical instruments, transportation tool manufacturing, optoelectronic information, and aerospace fields, and their preparation has important practical and economic value.

The object of the present invention is to provide a method for producing vinyl naphthenic compounds with high selectivity and economy.

The present invention relates to a method for producing a vinyl cycloalkane compound represented by the following general formula (5) through the following two steps of hydrogenation reaction and dehydration reaction.

R ² -CH=CH ₂ (5)

In formula (5), R ² represents a cycloalkyl group or an alkyl group substituted with a cycloalkyl group.

Hydrogenation reaction step: in the presence of 0.1 parts by weight (based on the total weight of the reaction raw material liquid as 100 parts by weight) hydrogenation catalyst, the following general formulas (1) and/or (2) and/or ( 3) and/or the step of reacting the compound shown in (4) with hydrogen to prepare the corresponding first-stage alcohol or second-stage alcohol reaction liquid.

R ¹ -CH ₂ -CH ₂ -OH (1)

In formulas (1)~(4), R ¹ represents a hydrocarbon group containing an aromatic ring,

Dehydration reaction step: in the presence of a dehydration catalyst, the reaction solution corresponding to the first-stage alcohol or the second-stage alcohol produced by the above-mentioned hydrogenation reaction step is dehydrated to obtain the vinyl cycloalkanes represented by the following general formula (5) Compound steps.

R ² -CH=CH ₂ (5)

In formula (5), R ² represents a cycloalkyl group or an alkyl group substituted with a cycloalkyl group.

The method for producing a vinyl cycloalkane compound represented by the following general formula (5) of the present invention includes the following two steps of a hydrogenation reaction and a dehydration reaction.

R ² -CH=CH ₂ (5)

In formula (5), R ² represents a cycloalkyl group or an alkyl group substituted with a cycloalkyl group.

Hydrogenation reaction step: in the presence of 0.1 parts by weight (based on the total weight of the reaction raw material liquid as 100 parts by weight) hydrogenation catalyst, the following general formulas (1) and/or (2) and/or ( 3) and/or the step of reacting the compound shown in (4) with hydrogen to prepare the corresponding first-stage alcohol or second-stage alcohol reaction liquid.

R ¹ -CH ₂ -CH ₂ -OH (1)

In formulas (1)~(4), R ¹ represents a hydrocarbon group containing an aromatic ring,

Dehydration reaction step: in the presence of a dehydration catalyst, the reaction solution corresponding to the first-stage alcohol or the second-stage alcohol prepared by the above-mentioned hydrogenation reaction step is dehydrated to obtain the vinyl cycloalkane compound represented by the above-mentioned general formula (5)的步。 The steps.

Hydrogenation reaction steps:

^{R 1} in the compounds represented by the above general formulas (1) to (4) is a hydrocarbon group containing an aromatic ring, which is selected from aryl groups with 6 to 20 carbon atoms and aralkyls with 7 to 20 carbon atoms The group formed by the base.

The aryl group having 6 to 20 carbon atoms is selected from the group consisting of phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2, 5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethyl Phenyl, 2,3,6-methylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethyl Phenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, 2-ethylphenyl, 2,3-diethyl Phenyl, 2,3,4-triethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-n-butyl Phenyl, 2-second butyl phenyl, 2-tert butyl phenyl, 2-n-pentyl phenyl, 2-neopentyl phenyl, 2-n-hexyl phenyl, 2-n-octyl benzene Group, 2-n-decylphenyl, 2-n-dodecylphenyl, 2-n-tetradecylphenyl, naphthyl and anthracenyl groups.

The aralkyl group having 7 to 20 carbon atoms is selected from benzyl (i.e. benzyl), (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methyl) Phenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, ( 2,6-Dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl, (2,3,4-trimethyl) Phenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylbenzene) Group) methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethyl Phenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (2-ethylphenyl)methyl, (2-normal Propylphenyl) methyl, (2-isopropylphenyl) methyl, (2-n-butylphenyl) methyl, (2-second butylphenyl) methyl, (2-third Butylphenyl)methyl, (2-n-pentylphenyl)methyl, (2-neopentylphenyl)methyl, (2-n-hexylphenyl)methyl, (2-n-octylbenzene) Yl)methyl, (2-n-decylphenyl)methyl, (2-n-decylphenyl)methyl, (2-n-tetradecylphenyl)methyl, naphthylmethyl, anthracenyl Methyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, diphenylmethyl, 2,2-diphenylethyl, 3,3-diphenylpropyl and The group consisting of 4,4-diphenylbutyl.

The compounds represented by the above general formulas (1)~(4) are such as 2-phenylethanol, 1-phenylethanol, 1-benzylethanol, 4-phenyl-2-butanol, acetophenone, 1-phenyl -2-acetone, phenylacetaldehyde, etc. In terms of the practicality of the prepared vinyl cycloalkane compounds represented by the above general formula (5), 2-phenylethanol, 1-phenylethanol, acetophenone, and phenylacetaldehyde are preferred.

Regarding the compounds represented by the above general formulas (1) to (4), one can be used alternatively, and a mixture of two or more of them (including) can also be used.

The choice of hydrogen: pure hydrogen can be used, or hydrogen containing inert gas such as methane can be used. The purity of hydrogen is preferably 99.9% or more, preferably 99.99% or more.

The choice of hydrogenation catalyst: as long as it is a catalyst that can hydrogenate the compounds represented by the general formulas (1) to (4) in the reaction process of the compounds represented by the general formulas (1) to (4) and hydrogen , Is selected from the group consisting of nickel, rhodium, ruthenium, palladium, iron, iron, molybdenum, copper and chromium. Among them, from the viewpoint of the yield of the hydrogenation reaction, metals of Group 8 of the Periodic Table of Elements are preferred. In addition, the above-mentioned metals can also be loaded on a carrier for use as a hydrogenation catalyst, such as silica, aluminum oxide, titanium dioxide, diatomaceous earth, activated carbon, and various zeolites.

Implementation of hydrogenation reaction:

Solvent usage: The hydrogenation reaction can be carried out with or without solvents. Suitable solvents include aliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, and decane.

Reaction conditions: The reaction temperature is usually between 60~200℃, preferably between 80~160℃. The reaction pressure is usually between 0.5 and 10 MPa, preferably between 1.5 and 7 MPa. The reaction time is usually 0.5 to 20 hours.

Examples of suitable hydrogenation reaction types:

1. Batch, semi-continuous or continuous slurry process tank reactor: Generally speaking, one-stage or multi-stage mixing tanks can be used.

2. Tubular reactor: For example, a single tube or a multi-tube heat exchange type structure with multiple tubes arranged side by side can be connected in a single or multiple fixed-bed reactors.

The amount of hydrogenation catalyst used:

The amount of hydrogenation catalyst used is more than 0.1 parts by weight (based on 100 parts by weight of the total weight of the reaction raw material liquid containing the compounds represented by the above general formulas (1) to (4) and the solvent used in the reaction as required) . If the amount of the hydrogenation catalyst used is less than 0.1 parts by weight, the hydrogenation reaction rate is slow and uneconomical, and the amount used is 0.5 parts by weight or more. As for the upper limit of the amount of hydrogenation catalyst used, it is not particularly limited, but in consideration of economy, it is preferably 90 parts by weight or less.

In the case of batch tank reactors, the amount of hydrogenation catalyst used can be calculated by the following formula:

Hydrogenation catalyst added weight/(Compounds shown in general formula (1)~(4) and as required Weight of solvent added for reaction) x 100

In the case of using a semi-continuous or continuous slurry tank reactor, the amount of hydrogenation catalyst used can be calculated by the following formula:

Weight of hydrogenation catalyst in reactor/weight of liquid in reactor x 100

In the case of using a continuous fixed-bed tubular reactor, the amount of hydrogenation catalyst used can be calculated by the following formula:

Hydrogenation catalyst filling amount / (the compound represented by the general formula (1) ~ (4) and the solvent supply flow rate used for the reaction as needed) / residence time) x 100

According to the hydrogenation reaction step of the present invention, the first grade alcohol and the second grade alcohol corresponding to the above general formulas (1) to (4) can be prepared.

Dehydration reaction steps:

In the presence of a dehydration catalyst, the first-stage and second-stage alcohols corresponding to the above general formulas (1) to (4) produced by the hydrogenation reaction step are dehydrated to produce ethylene with the above general formula (5) Cycloalkanes, where R ² represents a cycloalkyl group or an alkyl group substituted by a cycloalkyl group.

The preferred cycloalkyl group has 6-20 carbon atoms and is selected from cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, norbornyl, 2,3- Dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5- Dimethylcyclohexyl, 2,3,4-trimethylcyclohexyl, 2,3,5-trimethylcyclohexyl, 2,3,6-trimethylcyclohexyl, 2,4,6-trimethyl Cyclohexyl, 3,4,5-trimethylcyclohexyl, 2,3,4,5-tetramethylcyclohexyl, 2,3,4,6-tetramethylcyclohexyl, 2,3,5, 6-tetramethylcyclohexyl, pentamethylcyclohexyl, 2-ethylcyclohexyl, 2,3-diethylcyclohexyl, 2,3,4-triethylcyclohexyl, 2-n-propylcyclohexyl , 2-isopropylcyclohexyl, 2-n-butylcyclohexyl, 2-second butylcyclohexyl, 2-tertiary butylcyclohexyl, 2-n-pentylcyclohexyl, adamantyl, 2-new Pentylcyclohexyl, 2-n-hexylcyclohexyl, 2-n-octylcyclohexyl, 2-n-decylcyclohexyl, 2-n-dodecylcyclohexyl, 2-n-tetradecylcyclohexyl, decahydro The group consisting of naphthyl and tetradecahydroanthryl.

Preferred alkyl substituted by cycloalkyl has 7-20 carbon atoms, and is selected from cyclohexylmethyl, (2-methylcyclohexyl)methyl, (3-methylcyclohexyl)methyl, ( 4-methylcyclohexyl)methyl, (2,3-dimethylcyclohexyl)methyl, (2,4-dimethylcyclohexyl)methyl, (2,5-dimethylcyclohexyl)methyl Group, (2,6-dimethylcyclohexyl)methyl, (3,4-dimethylcyclohexyl)methyl, (4,6-dimethylcyclohexyl)methyl Group, (2,3,4-trimethylcyclohexyl)methyl, (2,3,5-trimethylcyclohexyl)methyl, (2,3,6-trimethylcyclohexyl)methyl, (3,4,5-trimethylcyclohexyl)methyl, (2,4,6-trimethylcyclohexyl)methyl, (2,3,4,5-tetramethylcyclohexyl)methyl, (2,3,4,6-tetramethylcyclohexyl)methyl, (2,3,5,6-tetramethylcyclohexyl)methyl, (methylcyclohexyl)yl, (2-ethyl ring Hexyl)methyl, (2-n-propylcyclohexyl)methyl, (2-isopropylcyclohexyl)methyl, (2-n-butylcyclohexyl)methyl, (2-second butylcyclohexyl) )Methyl, (2-tert-butylcyclohexyl)methyl, (2-n-pentylcyclohexyl)methyl, (2-neopentylcyclohexyl)methyl, (2-n-hexylcyclohexyl)methyl Group, (2-n-octylcyclohexyl)methyl, (2-n-decylcyclohexyl)methyl, (2-n-decylcyclohexyl)methyl, (2-n-tetradecylcyclohexyl)methyl Base, decahydronaphthylmethyl, tetradecahydroanthracenemethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, 4-cyclohexylbutyl, dicyclohexylmethyl, 2,2-dicyclohexylethyl Group, 3,3-dicyclohexylpropyl and 4,4-dicyclohexylbutyl.

The vinyl cycloalkane compound represented by the above general formula (5) of the present invention should have 6 or more carbon atoms, such as but not limited to vinyl cyclobutane, vinyl cyclopentane, and vinyl-3- Methylcyclopentane, vinylcyclohexane, vinyl-2-methylcyclohexane, vinyl-3-methylcyclohexane, vinylnorbornane, allylcyclohexane and 4-ring Hexyl-1-butene, etc., preferably having 8 or more carbon atoms.

Selection of dehydration catalyst: as long as the first-stage and second-stage alcohols corresponding to the above general formulas (1) to (4) prepared by the hydrogenation reaction step can be dehydrated, the above general formula (5) can be obtained The catalyst of the vinyl cycloalkane compound is selected from the group consisting of aluminum oxide, zirconium dioxide, silicon dioxide, titanium dioxide and ion exchange resin. Among them, aluminum oxide and zirconium dioxide are preferred in terms of high selectivity and economic efficiency.

Implementation of dehydration reaction:

Solvent use method: The dehydration reaction can be carried out with the use of a solvent. Suitable solvents include (1) aliphatic hydrocarbons: for example, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, decane, etc., and (2) aromatic hydrocarbons: for example Benzene, toluene, ethylbenzene, xylene, and cumene, etc. The above-mentioned reaction solvents may be used alone, or two or more kinds (including) may be mixed and used.

Reaction conditions: The reaction temperature is usually between 120 and 500°C, preferably between 250 and 450°C. The reaction pressure is usually between normal pressure and 1MPa. The reaction time is usually 0.5 to 12 hours.

Examples of suitable dehydration reaction types:

1. It can be used for liquid or gas phase reaction.

2. Batch, semi-continuous or continuous slurry tank reactor: Generally speaking, one-stage or multi-stage mixing tanks can be used.

3. Continuous fixed-bed tube type reactor: For example, a single tube or a multi-tube heat exchange type structure with multiple tubes arranged side by side can be connected in a single or multiple fixed bed reactors.

4. For large-scale industrial operations, in terms of operability and economy, the fixed bed method is preferred.

The vinyl cycloalkane compound represented by the above general formula (5) prepared according to the present invention can be used as a monomer of homopolymer and a comonomer of copolymer, especially vinyl cyclohexane can be used for high transparency It is a monomer of resistance, heat resistance, rigidity and electrical insulation polymer and a comonomer of olefin copolymer.

Examples: The present invention can be explained in more detail by the following examples. Among them, the conversion rate of 2-cyclohexylethanol and 1-cyclohexylethanol and the selectivity of vinylcyclohexane can be determined by the reaction supply flow rate and the gas chromatography composition analysis value, and the liquid flow rate after the reaction and the gas chromatography composition analysis value Find.

Example 1

In the batch reactor, 1.5 parts by weight of hydrogenation catalyst (containing 5 parts by weight of ruthenium and 95 parts by weight of silicon dioxide, relative to 100 parts by weight of liquid containing 2-phenylethanol (general formula (1))) was added, Immediately supply pure hydrogen. After reacting for 7.5 hours at a liquid temperature of 80°C and a reaction pressure of 3MPa, the reaction conditions were changed to a liquid temperature of 105°C and a reaction pressure of 2.5MPa. The reaction was continued for 3.5 hours to obtain a concentration of 94% by weight. -Cyclohexyl ethanol reaction solution. A tube reactor with a cross-sectional area of 4.5 square centimeters was filled with 48 grams of aluminum oxide catalyst with a length of 10 cm, and the above-mentioned 2-cyclohexyl ethanol reaction solution was supplied at 330 grams per hour to control the amount of the aluminum oxide catalyst layer. The temperature is between 380~405℃. The conversion rate of 2-cyclohexylethanol at the outlet of the reactor was 55%, and the selectivity of vinylcyclohexane was 92%.

Comparative example 1

In Example 1, the above-mentioned 2-cyclohexylethanol was supplied at 340 g/hour, and the temperature of the aluminum oxide catalyst layer was increased from 380 to 405°C to 380 to 410°C. The remaining reaction conditions were the same as those in the examples. 1 phase At the same time, as a result, the conversion rate of 2-cyclohexylethanol at the outlet of the reactor was 58%, and the selectivity of vinylcyclohexane was 91%.

Example 2

In a batch reactor, 1.5 parts by weight of hydrogenation catalyst (containing 5 parts by weight of rhodium and 95 parts by weight of aluminum oxide, relative to 100 parts by weight of liquid containing 1-phenylethanol (general formula (2))) , Then supply pure hydrogen. After reacting for 7 hours under the conditions of liquid temperature of 80℃ and reaction pressure of 3MPa, change the reaction conditions to liquid temperature of 100℃ and reaction pressure of 2MPa. Continue the reaction for 4.5 hours to obtain a concentration of 94% by weight. -Cyclohexyl ethanol reaction solution. A tubular reactor with a cross-sectional area of 4.5 square centimeters was filled with 55 grams of zirconium dioxide catalyst with a length of 10 centimeters, and the above-mentioned 1-cyclohexylethanol reaction solution was supplied at 335 grams per hour to control the temperature of the zirconium dioxide catalyst layer. At 375~400℃. The 1-cyclohexylethanol conversion rate at the reactor outlet was 48%, and the vinylcyclohexane selectivity was 85%.

Comparative example 2

In Example 2, the above-mentioned 1-cyclohexylethanol was supplied at 345 g/hour, and the temperature of the zirconium dioxide catalyst layer was increased from 375~400°C to 375~405°C. The remaining reaction conditions were the same as those in Example 2. In the same way, the conversion rate of 1-cyclohexylethanol at the outlet of the reactor was 50%, and the selectivity of vinylcyclohexane was 80%.

Industrial applicability: According to the present invention, the vinyl cycloalkane compound with the above general formula (5) can be prepared with high selectivity and economy, and it is suitable for high transparency, heat resistance, rigidity, and electrical insulation. And the monomer of environmentally friendly polymer.

Claims (5)

The preparation method of the vinyl cycloalkane compound represented by the following general formula (5) includes the following two steps of hydrogenation reaction and dehydration reaction, wherein the hydrogenation reaction step: 0.1 parts by weight (based on 100 parts by weight of the total weight of the reaction raw material liquid) ) In the presence of the above hydrogenation catalyst, the following general formula (1) or/and the following general formula (2) or/and the following general formula (3) or/and the following general formula (4) are represented The reaction raw material liquid of the compound reacts with hydrogen to prepare the corresponding first-stage alcohol or the second-stage alcohol reaction solution; dehydration reaction step: in the presence of a dehydration catalyst, the corresponding first-stage reaction step is prepared by the above hydrogenation reaction step The alcohol or the second-stage alcohol reaction liquid is dehydrated to obtain the vinyl cycloalkane compound represented by the following general formula (5). R ¹ -CH ₂ -CH ₂ -OH (1)

In the above formulas (1)~(4), R ¹ represents a hydrocarbon group containing an aromatic ring, R ² -CH=CH ₂ (5) In the above formula (5), R ² represents a cycloalkyl group or an alkyl group substituted by a cycloalkyl group. The method for preparing vinyl cycloalkanes as described in item 1 of the scope of patent application, wherein R ¹ of the general formulas (1) to (4) has 6 or more carbon atoms containing aromatic ring hydrocarbon groups. The method for preparing vinyl cycloalkane compounds as described in item 1 or item 2 of the scope of patent application, wherein the hydrogenation catalyst is rhodium, ruthenium, palladium, and nickel. For example, the method for preparing vinyl cycloalkane compounds described in item 1 or item 2 of the scope of patent application, wherein The water catalyst is aluminum oxide and zirconium dioxide. For example, the method for preparing vinyl cycloalkane compounds described in item 1 or item 2 of the scope of patent application, wherein the dehydration reaction temperature is between 250 and 450°C.