KR20220083269A - Method for preparation of cyclododecanone - Google Patents

Abstract

The present invention relates to a method for producing cyclododecanone, and more particularly, it is possible to prevent wastage of hydrogen peroxide, and to provide a new method for producing cyclododecanone capable of producing cyclododecanone with significantly improved conversion and selectivity will do
The present invention is a method for preparing epoxidized cyclododecanone by continuously adding hydrogen peroxide to cyclododecene under a catalyst system containing a tungsten compound, a phosphoric acid compound and an amine compound, and rearranging it to prepare cyclododecanone. , characterized in that the input of hydrogen peroxide is added in a reduced amount as the reaction time elapses.

Description

Method for preparing cyclododecanone {Method for preparation of cyclododecanone}

The present invention relates to a method for producing cyclododecanone, and more particularly, it is possible to prevent wastage of hydrogen peroxide, and to provide a new method for producing cyclododecanone capable of producing cyclododecanone with significantly improved conversion and selectivity will do

Cyclododecanone (CDON, cyclododecanone) is used for the production of laurolactam, and the laurolactam is used to produce polyamide (eg, nylon-12, nylon 6-12, etc.), which is one of engineering plastics. It is an organic compound used as a monomer for

The preparation of cyclododecanone can generally be carried out starting from cyclododecatriene (CDT, cyclododecanone). Specifically, cyclododecanone can be prepared by preparing cyclododecene (CDEN, cyclododecene) by selective hydrogenation in cyclododecatriene and then oxidizing cyclododecene. However, according to the above-described method for producing cyclododecanone, there is a problem in that a significant amount of by-products (eg, cyclododecanol, cyclododecadiol, etc.) are generated.

Accordingly, the above-mentioned problems of the prior art have a disadvantageous effect on the establishment of an entire process system for laurolactam production, and thus, research to find a more efficient method is still needed.

In order to solve the problems of the prior art, in Korean Patent Application Laid-Open No. 10-2020-00762370, previously applied by the applicant, in the introduction of an intermediate step using epoxidized cyclododecene as an intermediate, the addition form of hydrogen peroxide is controlled. method was studied.

However, as hydrogen peroxide is continuously injected into the reactor at a certain injection rate, after a certain reaction time, a large amount of hydrogen peroxide is supplied compared to the required hydrogen peroxide, so there is a problem in that hydrogen peroxide is wasted. The downside was that it was time consuming.

Accordingly, the present inventors intensified the study of an efficient method for the preparation method of cyclododecanone. As a result, it was confirmed that cyclododecanone can be produced with high conversion and selectivity within a short time by controlling the injection rate of hydrogen peroxide to decrease step by step according to the reaction time in the intermediate step using epoxidized cyclododecene as an intermediate. was completed.

It is an object of the present invention to provide a production method capable of producing cyclododecanone with high conversion and selectivity within a shorter period of time.

It is also an object of the present invention to provide a method for producing cyclododecanone capable of increasing the selectivity of hydrogen peroxide by effectively suppressing the decomposition and waste of hydrogen peroxide.

It is also an object of the present invention to provide an economical method for producing cyclododecanone with a more simplified process configuration.

In the method for producing cyclododecanone of the present invention, hydrogen peroxide is continuously added to cyclododecene under a catalyst system containing a tungsten compound, a phosphoric acid compound, and an amine compound to prepare an epoxidized cyclododecanone, and rearrangement is performed to cyclododecanone. In the method for producing dodecanone, the hydrogen peroxide is added in a reduced amount as the reaction time elapses.

In the method for producing cyclododecanone according to an embodiment of the present invention, the hydrogen peroxide may be added in a reduced amount according to a unit time.

In the method for producing cyclododecanone according to an embodiment of the present invention, the hydrogen peroxide may be added according to a step satisfying the following relational expression (1).

[Relational Expression 1]

S _n = n T _unit

1 ≤ n ≤ 10

ΔIn S _n ≥ ΔIn S _n+1

(In the above relation, S _n is the nth step, n is a natural number, T _unit is unit time, and ΔIn S _n is the rate of change in the injection flow rate (μl/min) per minute of hydrogen peroxide from S _n-1 step to S _n step ( %), ΔIn S _n+1 represents the rate of change (%) of the hydrogen peroxide injection flow rate (μl/min) per minute from the S _n step to the S _n+1 step)

In the method for producing cyclododecanone according to an embodiment of the present invention, the hydrogen peroxide may be added by satisfying the following relational expression (2).

[Relational Expression 2]

50 ≤ In S ₀ ≤ 150

30 ≤ ΔIn S ₁ ≤ 80

5 ≤ ΔIn S ₂ ≤ 40

0 ≤ ΔIn S ₃ ≤ 5

(In the above relation, In S ₀ is the initial injection flow rate per minute (μl/min) of hydrogen peroxide.)

In the method for producing cyclododecanone according to an embodiment of the present invention, the hydrogen peroxide may be introduced at a position of 1/5 to 4/5 of the height of the inside of the reactor based on the bottom of the reactor.

In the method for producing cyclododecanone according to an embodiment of the present invention, the tungsten compound may be tungstic acid, a salt of tungstic acid, or a mixture thereof.

In the method for producing cyclododecanone according to an embodiment of the present invention, the phosphoric acid compound may be inorganic phosphoric acid, inorganic phosphoric acid, organic phosphoric acid, or a mixture thereof.

In the method for preparing cyclododecanone according to an embodiment of the present invention, the amine compound may be a tertiary amine, a quaternary ammonium salt, or a mixture thereof.

In the method for producing cyclododecanone according to an embodiment of the present invention, the catalyst system may be included in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the cyclododecene.

In the method for producing cyclododecanone according to an embodiment of the present invention, the temperature condition performed when preparing the epoxidized cyclododecanone may be 50 to 120°C.

In the method for producing cyclododecanone according to an embodiment of the present invention, in the presence of an alkali metal halide catalyst, preparing cyclododecanone through a rearrangement reaction without separation of the reaction mixture containing the epoxidized cyclododecanone; may include more.

In the method for producing cyclododecanone according to an embodiment of the present invention, the conversion rate of the cyclododecene and the conversion rate of the epoxidized cyclododecanone may be 95% or more.

In addition, the present invention is a cyclododecanone composition prepared by the above-described method.

According to the present invention, by controlling the injection amount of hydrogen peroxide to decrease over time, it is possible to effectively suppress hydrogen peroxide self-decomposition, increase the selectivity of hydrogen peroxide, and prevent wastage of hydrogen peroxide. Accordingly, the present invention has the advantage of preventing an explosive reaction caused by decomposition of hydrogen peroxide and efficiently controlling the heat of reaction by this, thereby increasing process convenience.

In addition, according to the present invention, cyclododecanone can be prepared with high conversion and high selectivity within a short time.

Hereinafter, the manufacturing method of cyclododecanone according to the present invention will be described in detail, but unless otherwise defined in the technical and scientific terms used at this time, the meaning commonly understood by those of ordinary skill in the art to which this invention belongs In the following description, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted.

The present invention aims to propose a method for producing cyclododecanone that can prevent wastage of hydrogen peroxide and realize high conversion and selectivity within a short time in a very economical way, paying attention to the problems of the prior art described above.

According to the present invention, it is possible to implement a high conversion rate and to manufacture cyclododecanone with a minimized hydrogen peroxide consumption, thereby simplifying the process configuration. In addition, according to the present invention, it is possible to provide a stable manufacturing process that maximizes catalytic activity and does not have the risk of explosion due to hydrogen peroxide.

Accordingly, according to the present invention, it can have a very advantageous advantage to be applied to actual industry with a simplified process configuration that can be operated continuously as well as exhibiting high conversion rate and selectivity within a short time.

As mentioned above, the present invention confirms unexpectedly high conversion rate and improvement in selectivity as the amount of hydrogen peroxide is reduced over time, and efficient cyclododeca through a rearrangement reaction performed under an alkali metal halide catalyst. I would like to suggest this by confirming that it is possible to manufacture rice paddy.

Hereinafter, the method for producing cyclododecanone of the present invention will be described in detail.

In the method for producing cyclododecanone according to an embodiment of the present invention, hydrogen peroxide is continuously added to cyclododecene under a catalyst system including a tungsten compound, a phosphoric acid compound and an amine compound to prepare an epoxidized cyclododecanone, and rearranged In the method for producing cyclododecanone by rearrangement, it is characterized in that the amount of hydrogen peroxide is added in a reduced amount as the reaction time elapses.

Specifically, in the method for producing cyclododecanone according to the present invention, the hydrogen peroxide is added continuously in a reactor including a mixture of 10 parts by weight or less of hydrogen peroxide based on 100 parts by weight of the cyclododecene. In the form of additional input, it is input in a reduced amount according to the unit time.

It is noted that the improvement of the conversion rate and the selectivity according to the present invention is according to the above-described form of addition of hydrogen peroxide, and the effect is surprisingly improved by adjusting the hydrogen peroxide flow rate according to the lapse of reaction time.

In the method for producing cyclododecanone according to an embodiment of the present invention, the additionally injected hydrogen peroxide is characterized in that it follows the above-described addition form, and when injected to satisfy the following relation 1, the conversion rate and selectivity are surprisingly improved. can be implemented

[Relational Expression 1]

S _n = n T _unit

1 ≤ n ≤ 10

ΔIn S _n ≥ ΔIn S _n+1

In the above relation, S _n is the nth step, n is a natural number, T _unit is a unit time, and ΔIn S _n is the rate of change (%) of the injection flow rate per minute (μl/min) of hydrogen peroxide from the S _n-1 step to the S _n step ), ΔIn S _n+1 represents the rate of change (%) of the hydrogen peroxide injection flow rate (μl/min) per minute from the S _n step to the S _n+1 step.

That is, Relation 1 is a non-limiting example, and in the first step (S 1 ), in which the unit time has elapsed from the start of the hydrogen peroxide input, the first step (S ₁ ) may be injected at a flow rate reduced by 50% compared to the initial hydrogen peroxide input amount, and in the first step, the unit Step 2 (S ₂ ) over which time has elapsed may indicate that the injection is performed at a flow rate reduced by 30% compared to step 1.

Specifically, the unit time (T _unit ) may be 10 minutes to 4 hours, specifically 30 minutes to 3 hours, more specifically 40 minutes to 1 hour and 30 minutes, but is not limited thereto.

For example, the additionally injected hydrogen peroxide may be injected into the reactor including the reaction solution at the above-described flow rate through a pump.

For example, the hydrogen peroxide may be pure hydrogen peroxide or an aqueous hydrogen peroxide solution, and the aqueous hydrogen peroxide solution may have a concentration of 30 wt%, 34.5 wt%, 50 wt%, or the like.

If the above-mentioned relational expression is not satisfied, excessive reaction by-product generation is caused, decomposition of hydrogen peroxide is accelerated, and the selectivity for epoxidation (selectivity of hydrogen peroxide) is lowered, which is undesirable, showing unfavorable efficiency. In addition, excessive supply of hydrogen peroxide increases the interface temperature of the two liquid phase systems during the process to rapidly generate peroxidized reaction by-products, which is undesirable.

When the above-mentioned relational expression is satisfied, surprisingly improved conversion of cyclodecene and selectivity of epoxidized cyclododecane can be realized, and hydrogen peroxide self-decomposition can be effectively suppressed, and the selectivity of hydrogen peroxide can be increased. waste can be avoided. Accordingly, it is possible to prevent an explosive reaction caused by decomposition of hydrogen peroxide and efficiently control the heat of reaction by this, thereby increasing process convenience.

In the method for producing cyclododecanone according to an embodiment of the present invention, hydrogen peroxide may be added by further satisfying the following Relational Expression 2.

[Relational Expression 2]

50 ≤ In S ₀ ≤ 150

30 ≤ ΔIn S ₁ ≤ 80

5 ≤ ΔIn S ₂ ≤ 40

0 ≤ ΔIn S ₃ ≤ 5

(In the above relation, In S ₀ is the initial injection flow rate per minute (μl/min) of hydrogen peroxide.)

The In S ₀ may specifically satisfy a flow rate of 90 to 110 μl/min, more specifically 70 to 120 μl/min. In this case, the In S ₀ is a flow rate based on a 0.1L reactor, and may follow a flow rate of a quantitatively increased value according to an increase in the capacity of the reactor.

When the above-mentioned relational expression is satisfied, cyclododecanone can be prepared with a very high conversion rate and selectivity of 95% or more, more specifically 99%, of the cyclododecene conversion rate and the epoxidized cyclododecane selectivity.

In the method for producing cyclododecanone according to an embodiment of the present invention, hydrogen peroxide is at a position of 1/5 to 4/5 of the reactor inner height, specifically 1/4 to 3/4, based on the bottom surface of the reactor interior. can be placed in the position of

For example, hydrogen peroxide may be introduced through a dip-tube to be introduced at the reactor location, but is not limited thereto.

When hydrogen peroxide is added at the position of the reactor within the above range, the higher conversion rate of cyclododecene and the efficiency of hydrogen peroxide are lower than when hydrogen peroxide is added at the top of the reactor.

In the method for producing cyclododecanone according to an embodiment of the present invention, based on 100 parts by weight of cyclododecene, 1 to 10 parts by weight of hydrogen peroxide may be mixed, specifically 1 to 8 parts by weight, more specifically 1 to 5 parts by weight of hydrogen peroxide may be mixed with the cyclododecene, but is not limited thereto. However, hydrogen peroxide is not used as an oxidizing agent, but for maximizing catalytic activity, and when the amount of hydrogen peroxide contained is out of the above-mentioned range, catalytic activity is lowered, which is not preferable.

In the method for producing cyclododecanone according to an embodiment of the present invention, the tungsten compound that may be included in the catalyst system may be one or a mixture of two or more selected from tungstic acid and a salt of tungstic acid.

Examples of the tungsten compound include tungstic acid in the form of monohydrate or dihydrate of tungsten trioxide; tungstate salts such as sodium tungstate, potassium tungstate, calcium tungstate, ammonium tungstate; and the like.

For example, when the tungsten compound included in the catalyst system includes the above-described tungstic acid, it may have a heterogeneous catalyst system.

For example, when the tungsten compound included in the catalyst system includes one or a mixture of two or more selected from the above-described tungstates, it may have a homogeneous catalyst system.

For example, when the catalyst system contains the above-mentioned tungstic acid and the above-mentioned tungstate at the same time, it is possible to realize a more improved conversion rate.

In the method for producing cyclododecanone according to an embodiment of the present invention, the phosphoric acid compound that may be included in the catalyst system may be one or a mixture of two or more selected from inorganic phosphoric acid, inorganic phosphoric acid, organic phosphoric acid, and the like.

Examples of the phosphoric acid compound include inorganic phosphoric acid such as phosphoric acid, polyphosphoric acid, and pyrophosphoric acid; inorganic phosphates such as sodium phosphate, potassium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and calcium dihydrogen phosphate; organic phosphoric acids such as monomethyl phosphoric acid, dimethyl phosphoric acid, trimethyl phosphoric acid, triethyl phosphoric acid, and triphenyl phosphoric acid; and the like.

In the method for producing cyclododecanone according to an embodiment of the present invention, the amine compound that may be included in the catalyst system may be one or a mixture of two or more selected from a tertiary amine, a quaternary ammonium salt, and the like.

The amine compound is trimethylamine, dimethylethylamine, diethylmethylamine, butyldimethylamine, dimethylisopropylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, triisoamylamine, trihexylamine, a tertiary amine selected from trihepylamine, trioctylamine, and tri-(2-ethylhexyl)amine; and quaternary ammonium salts selected from dodecyltrimethylammonium salts, hexadecyltrimethylammonium salts, octadecyltrimethylammonium salts, methyltributylammonium salts and methyltrioctylammonium salts; and the like.

Specifically, when preparing the epoxidized cyclododecane, oxidation is performed in two liquid phase systems consisting of a liquid phase containing cyclododecene and another liquid phase containing an aqueous hydrogen peroxide solution, and after completion of the reaction, the two liquid phase systems rapidly It is good for the phase separation to occur. Accordingly, the amine compound included in the catalyst system preferably includes a long-chain alkyl having 7 or more carbon atoms.

In the method for producing cyclododecanone according to an embodiment of the present invention, the catalyst system may be included in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the cyclododecene, specifically 0.01 to 5 parts by weight, More specifically, it may be included in an amount of 0.1 to 1.0 parts by weight.

In the method for producing cyclododecanone according to an embodiment of the present invention, the tungsten compound (a), the phosphoric acid compound (b) and the amine compound (c) of the catalyst system are in a weight ratio of 1:0.1 to 2.0:0.1 to 5.0 ( a:b:c) may be mixed. The weight ratio (a:b:c) may be specifically 1:0.5-1.5:0.5-3.0, and more specifically 1:0.8-1.0:1.0-2.5.

In the method for producing cyclododecanone according to an embodiment of the present invention, the temperature condition performed when preparing the epoxidized cyclododecanone may be 50 to 120°C.

For example, the step of preparing epoxidized cyclododecane by adding hydrogen peroxide may be performed at a temperature of 60 to 100° C. for 0.5 to 12 hours.

For example, the step may be performed for 2 to 8 hours at a temperature condition of 70 to 90 ℃.

In addition, in the method for producing cyclododecanone according to an embodiment of the present invention, after the step (1) of preparing the epoxidized cyclododecanone, the step (2) of preparing cyclododecanone through a rearrangement reaction is included. can do. The step (2) may be performed under an alkali metal halide catalyst.

Examples of the alkali metal halide catalyst include KI, NaI, LiI, NaCl, KCl, LiCl, NaBr, KBr and LiBr, and may be used as one or a mixture of two or more selected from these.

The step (2) of preparing cyclododecanone through the rearrangement reaction may be performed without a solvent. In addition, the above step is preferably performed under an inert gas atmosphere.

The inert gas is not limited as long as it is a conventional gas, and as an example, it may be one or a mixture of two or more selected from helium gas, argon gas, nitrogen gas, neon gas, and the like.

In addition, the step (2) of preparing cyclododecanone through the rearrangement reaction may be to use the crude reaction mixture containing the epoxidized cyclododecanone obtained from the above-mentioned step (1). Through this, the step (2) can implement an improved conversion rate and selectivity.

The reaction mixture comprising the epoxidized cyclododecane obtained from step (1) has a favorable effect on the conversion and selectivity of the subsequent step (2).

For example, in step (1), the conversion rate of the cyclododecene may be 90% or more, specifically 95% or more and 99.9% or less, and more specifically 98% or more and 99.99% or less.

For example, the reaction mixture containing the epoxidized cyclododecane obtained from step (1) does not involve an additional separation/purification process after step (1) is completed, and the subsequent step (2) is a continuous process can proceed. Accordingly, the present invention can provide a more simplified process.

The step (2) of preparing cyclododecanone through the rearrangement reaction may include 0.01 to 10 parts by weight based on 100 parts by weight of the epoxidized cyclododecanone. Specifically, the alkylimetal halide catalyst is preferably included in an amount of 0.1 to 5 parts by weight, more specifically 0.5 to 3 parts by weight.

In the method for producing cyclododecanone according to an embodiment of the present invention, the step (2) of preparing cyclododecanone through the translocation reaction may be performed at a temperature of 100 to 300°C.

For example, step (2) may be performed at a temperature of 120 to 250° C. for 0.5 to 8 hours.

For example, step (2) may be performed at a temperature of 150 to 230° C. for 0.5 to 6 hours.

As described above, the method for producing cyclododecanone according to the present invention provides high conversion and selectivity as an intermediate step for the production of laurolactam. Specifically, the conversion rate for cyclododecanone through the cyclododecene reaches at least 90% or more, and such a high conversion rate may correspond to a significant conversion rate compared to the prior art. Due to the remarkable effect of this, the method for producing cyclododecanone according to the present invention is expected to be usefully applied to a process system for commercialization of laurolactam.

Hereinafter, an aspect employing the manufacturing method of the present invention described above will be described in detail.

In one aspect, the above-described method for preparing cyclododecanone may be employed as an intermediate step in the reaction when preparing laurolactam.

Specifically, in the method for producing laurolactam, (1) hydrogen peroxide is continuously added to cyclododecene under a catalyst system containing a tungsten compound, a phosphoric acid compound, and an amine compound, but in a reduced amount as the reaction time elapses, and heat is applied to prepare an epoxidized cyclododecane; and (2) preparing cyclododecanone through a rearrangement reaction from the reaction mixture containing the epoxidized cyclododecane under an alkali metal halide catalyst; (3) preparing cyclododecanone oxime by ammoxidation reaction in the cyclododecanone; and (4) preparing laurolactam through the Beckman rearrangement reaction in the cyclododecanone oxime;

The method for producing laurolactam according to an embodiment of the present invention provides an excellent effect on the conversion rate up to the final step by employing the method for producing cyclododecanone of the present invention as described above. In this case, the conversion rate to the final step means the conversion rate in the total step including the steps (1) to (4).

Specifically, in the method for producing laurolactam according to an embodiment of the present invention, the conversion rate up to the final step is 95% or more, which can provide the desired laurolactam with a significantly improved conversion rate.

Step (3) for preparing the cyclododecanone oxime is ammonia in a solvent containing ethanol; hydrogen peroxide; catalysts including titanium silicalite and the like; and a reactive active agent including ammonium acetate and the like; may be prepared by reacting with cyclododecanone.

As an example, in step (3), cyclododecanone, a catalyst, and a reaction activator are mixed in a solvent containing ethanol in a reactor, and then ammonia gas may be injected until it becomes 1.3 to 2.5 bar in the reactor. Thereafter, hydrogen peroxide in the reactor may be injected through a pump at a flow rate of 0.5 to 3.5 ml/min.

For example, step (3) may be performed for 15 to 70 minutes at a temperature of 50 to 100°C.

In the method for producing laurolactam according to an embodiment of the present invention, in the step (3) of preparing cyclododecanone oxime, the conversion rate from cyclododecanone may be 99% or more, specifically, 99 to 99.99%. can

The step (4) of preparing the laurolactam may be prepared through a conventional Beckman rearrangement reaction using the cyclododecanone oxime prepared by the above-described method.

The Beckman rearrangement reaction may be performed using a catalyst system in which a main catalyst including cyanuric chloride and the like and a cocatalyst including zinc chloride are mixed.

For example, step (4) may be performed in a solvent containing isopropylcyclohexane or the like at a temperature of 70 to 130° C. for 1 to 20 minutes.

In the method for producing laurolactam according to an embodiment of the present invention, in the step (4) of preparing the cyclododecanone oxime, the conversion rate from the cyclododecanone oxime may be 99% or more, specifically, 99 to 99.99% can be

In addition, in the method for producing laurolactam according to an embodiment of the present invention, the selectivity of the laurolactam may be 99% or more, specifically, it may be 99 to 99.99%.

The present invention refers to a cyclododecanone composition prepared by the above-described method, and refers to a high-purity cyclododecanone prepared by the above method. As the cyclododecanone composition of the present invention is prepared by the above method, when used in the laurolactam manufacturing process, laurolactam can be prepared with a conversion rate of 99% or more and a selectivity of 99% or more.

A novel method for preparing laurolactam including an intermediate step of using the epoxidized cyclododecane of the present invention as an intermediate will be described in more detail through the following examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

In addition, the unit of the amount not specifically described in the specification may be g.

(Example 1)

Step 1. Method for preparing epoxidized cyclododecane

25 g of cyclododecene, 0.075 g of H ₂ WO ₄ , 0.06 g of H ₃ PO ₄ , 0.105 g of tri-n-octyl amine in a high-speed stirring batch reactor (100 ml), 1.4 g of H ₂ O and 1.02 g of 50wt% H ₂ O ₂ were added. Thereafter, the reaction was allowed to proceed at 80° C. for a total of 4 hours. During the reaction, while stirring the reactor contents at 1500 rpm, hydrogen peroxide (50wt% in water) was additionally injected through a pump step by step. In step 1 (S ₁ ), which is until 1 hour has elapsed after the initial hydrogen peroxide injection, hydrogen peroxide was added at an injection rate of 100 μl per minute, and after step 1, until 1 hour has elapsed, step 2 (S) In ₂ ), hydrogen peroxide was injected at an injection rate of 40 μl per minute, and hydrogen peroxide was injected at an injection rate of 5 μl per minute in step 3 (S ₃ ), which is 1 hour after step 2, until 1 hour has elapsed. After step 3, in step 4 (S ₄ ), which is until 1 hour has elapsed, hydrogen peroxide was added at an injection rate of 40 μl per minute. At this time, hydrogen peroxide was introduced at 2/3 of the height of the reactor from the bottom of the reactor through the dip-tube.

Step 2. Method for preparing cyclododecanone

5 g of the reaction mixture containing the epoxidized cyclododecane obtained in step 1 and 0.085 g of lithium bromide (LiBr) were placed in a 50 ml round flask under inert conditions using a glovebox. After that, a nitrogen balloon was made and connected to the flask, and then placed in an oil bath containing silicone oil, and the reaction was allowed to proceed at 200° C. for a total of 2 hours.

Cyclododecene conversion, epoxidation cyclododecane selectivity, and yield efficiency were measured and shown in Table 1 below.

Cyclododecene conversion, epoxidation cyclodocene selectivity, and yield efficiency were calculated through the following formulas 1 to 3, respectively.

(Formula 1)

) X 100Cyclododecene conversion (%) = (1-

) X 100

(Formula 2)

Epoxidation cyclododecane selectivity (%) =

(Formula 3)

X 100Fruiting efficiency (%) =

X 100

Conversion rate % Selectivity % Fruiting efficiency % 1 hours 70.06 98.62 82.81 2 hours 92.89 98.74 85.61 4 hours 99.45 99.72 86.19

(Comparative Example 1)

It was carried out in the same manner as in Example 1, except that the same amount of hydrogen peroxide was injected at a flow rate of 85 μl per minute for 4 hours of the reaction in Example 1.

Cyclododecene conversion, epoxidation cyclododecane selectivity, and yield efficiency were measured and are shown in Table 2 below.

Conversion rate % Selectivity % Fruiting efficiency % 1 hours 58.07 97.63 88.33 2 hours 96.96 98.63 63.62 4 hours 97.37 98.26 34.26

(Comparative Example 2)

It was carried out in the same manner as in Example 1, but hydrogen peroxide was added from the top of the reactor without using a dip-tube.

Cyclododecene conversion, epoxidation cyclododecane selectivity, and yield efficiency were measured and shown in Table 3 below.

Conversion rate % Selectivity % Fruiting efficiency % Surface injection of fruit tree (4 hours) 50.58 94.29 43.86

Tables 1 to 3 show the results of measurement of cyclododecene conversion, epoxidation cyclododecane selectivity, and fruiting efficiency according to Examples and Comparative Examples of the present invention. Specifically, Table 1 shows the conversion rate, selectivity, and fruiting efficiency measurement results according to Examples of the present invention, and Tables 2 to 3 show the conversion ratio, selectivity and fruiting efficiency measurement results according to Comparative Examples 1 and 2, respectively. .

Referring to Tables 1 and 3, it was confirmed that, according to the present invention, cyclododecanone can be prepared from cyclododecene with high conversion and selectivity. In particular, it can be confirmed that, when additionally injected hydrogen peroxide is injected to satisfy the above-described relational expression, a surprisingly improved effect of high conversion and selectivity within a short time is exhibited.

In short, according to the present invention, it is possible to provide cyclododecanone with high conversion and selectivity with a simplified process configuration and an optimized hydrogen peroxide input amount under very economical conditions. It is expected to be useful for

As described above, the present invention has been described by specific matters and limited examples, but these are provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the field to which the present invention belongs Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (13)

In a method for producing cyclododecanone by continuously introducing hydrogen peroxide to cyclododecene under a catalyst system containing a tungsten compound, a phosphoric acid compound, and an amine compound, and rearranging the epoxidized cyclododecanone,
The method for producing cyclododecanone, characterized in that the input of the hydrogen peroxide is added in a reduced amount as the reaction time elapses.
The method of claim 1,
The hydrogen peroxide is added in a reduced amount according to the unit time, the method for producing cyclododecanone.
3. The method of claim 2,
The hydrogen peroxide is added according to a step satisfying the following relational formula 1, a method for producing cyclododecanone.
[Relational Expression 1]
S _n = n T _unit
1 ≤ n ≤ 10
ΔIn S _n ≥ ΔIn S _n+1
(In the above relation, S _n is the nth step, n is a natural number, T _unit is unit time, and ΔIn S _n is the rate of change in the injection flow rate (μl/min) per minute of hydrogen peroxide from S _n-1 step to S _n step ( %), ΔIn S _n+1 represents the rate of change (%) of the hydrogen peroxide injection flow rate (μl/min) per minute from the S _n step to the S _n+1 step)
4. The method of claim 3,
The hydrogen peroxide is added to satisfy the following relational formula 2, a method for producing cyclododecanone.
[Relational Expression 2]
50 ≤ In S ₀ ≤ 150
30 ≤ ΔIn S ₁ ≤ 80
5 ≤ ΔIn S ₂ ≤ 40
0 ≤ ΔIn S ₃ ≤ 5
(In the above relation, In S ₀ is the initial injection flow rate per minute (μl/min) of hydrogen peroxide.)
The method of claim 1,
The method for producing cyclododecanone, wherein the hydrogen peroxide is input at a position of 1/5 to 4/5 of the height of the reactor interior, based on the bottom surface of the reactor.
The method of claim 1,
The tungsten compound is
Tungstic acid, a salt of tungstic acid, or a mixture thereof, a method for producing cyclododecanone.
The method of claim 1,
The phosphoric acid compound is
Inorganic phosphoric acid, inorganic phosphate, organic phosphoric acid, or a mixture thereof, a method for producing cyclododecanone.
The method of claim 1,
The amine compound is
Tertiary amines, quaternary ammonium salts, and mixtures thereof, a method for preparing cyclododecanone.
The method of claim 1,
The catalyst system is
Based on 100 parts by weight of the cyclododecene,
A method for producing cyclododecanone, which is included in an amount of 0.001 to 10 parts by weight.
The method of claim 1,
The temperature condition performed when preparing the epoxidized cyclododecanone is 50 to 120°C, the method for producing cyclododecanone.
The method of claim 1,
under an alkali metal halide catalyst,
Preparing cyclododecanone through a rearrangement reaction without separation of the reaction mixture containing the epoxidized cyclododecanone; further comprising, a method for producing cyclododecanone.
The method of claim 1,
The conversion rate of the cyclododecene and the conversion rate of the epoxidized cyclododecane are 95% or more, the method for producing cyclododecanone.
The cyclododecanone composition prepared by the method of any one of claims 1 to 12.