KR20170010663A

KR20170010663A - Continuous production method of norbornene derivative

Info

Publication number: KR20170010663A
Application number: KR1020150102607A
Authority: KR
Inventors: 이현직; 장용희; 이원재
Original assignee: 주식회사 엘지화학
Priority date: 2015-07-20
Filing date: 2015-07-20
Publication date: 2017-02-01
Also published as: KR102004517B1

Abstract

The present invention relates to a continuous process for preparing norbornene derivatives.

Description

[0001] The present invention relates to a continuous production method of a norbornene derivative,

The cyclic olefin polymer is a polymer composed of a cyclic monomer such as norbornene. It has excellent transparency, heat resistance, chemical resistance and very low birefringence and water absorption rate compared to conventional olefin polymers. Thus, CD, DVD, POF It can be widely applied to medical materials such as optical materials such as optical materials, capacitor films, information electronic materials such as low dielectric materials, low absorbency syringes, and blister packaging. The cyclic olefin polymerization technique related to this is performed by ROMP (Ring Opening Metathesis Polymerization), HROMP (ring opening metathesis polymerization followed by hydrogenation), copolymerization with ethylene and homopolymerization. Of these, norbornene polymers are polymers that have been widely applied to the above-mentioned fields. Then, dicyclopentadiene or cyclopentadiene is reacted with an olefin as a monomer to introduce a double bond, and polymerization is carried out to prepare a norbornene polymer.

Since the synthesis of norbornene was first described in LMJoshel and LW Butz, J. Am. Chem., 63, 3350, 1941, US Pat. No. 2,340,908 discloses a process for the preparation of The reaction of dicyclopentadiene with ethylene at the temperature is disclosed, wherein the final yield of norbornene is reported to be 45%. In order to prepare the norbornene polymer, it is essential to use dicyclopentadiene in a high purity, but it is necessary to convert the cyclopentadiene to cyclopentadiene under temperature and pressure conditions, or to cause a cyclization reaction between dicyclopentadiene and cyclopentadiene, ) Or by-products such as trimer. Furthermore, in the case of dicyclopentadiene, distillation purification is difficult, and it is difficult to produce pure norbornene.

US 2340908

J. Am. Chem., 63, 3350

Generally, a batch reactor is used in the production of norbornene derivatives, which makes it difficult to operate the reactor in commercial production, and there is a problem that the investment cost and the operating ratio increase. In addition, the operation using a batch reactor usually requires a series of operations such as heating, reactant injection, reaction, cooling, and product discharge. Therefore, since the productivity per batch operation is low, there is a problem that the volume of the reactor or the number of the reactors must be increased for mass production.

Accordingly, it is an object of the present invention to provide a process for producing a norbornene derivative excellent in yield, exo ratio and productivity even in a continuous reactor.

In order to achieve the above object, cyclopentadiene, dicyclopentadiene or a mixture thereof; And a compound represented by the following general formula (1) are continuously introduced into a tubular reactor including a static mixer to carry out a reaction, and the molar ratio of the cyclopentadiene to the compound represented by the general formula (1) is 1: 1 To 1:10, or the molar ratio of the dicyclopentadiene to the compound represented by the formula (1) is 1: 2 to 1:20, and the reaction pressure is 1 to 20 bar.

[Chemical Formula 1]

CH ₂ = CH- (CH ₂ ) _n -C (= O) OR

In Formula 1, n is an integer of 0 to 10, and R is an alkyl group having 1 to 20 carbon atoms.

According to a preferred embodiment of the present invention, the tubular reactor may be a PFR reactor. According to a preferred embodiment of the present invention, the space time of the reaction solution introduced into the reactor may be 0.1 to 30 min, preferably 0.1 to 10 min, more preferably 0.1 to 1 min. And the reaction temperature may be 170 to 300 ° C.

According to a preferred embodiment of the present invention, the reaction solution is a mixture of 2,6-di-tert-butyl-4-methylphenol, 2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl), aniline, cyclohexane, phenol, 4-ethoxyphenol, nitrobenzene, The polymerization inhibitor may further comprise at least one polymerization inhibitor selected from the group consisting of hydroquinone, benzoquinone, copper dichloride, and iridox. The polymerization inhibitor may be at least one selected from the group consisting of cyclopentadiene, dicyclopentadiene, 1 to 100 parts by weight of the total amount of the compounds represented by the general formula (1).

The present invention can provide a process for producing a norbornene derivative using a continuous reactor. The present invention increases the contrast, yield and exo ratio when using conventional batch reactors. Compared to CSTR, it has an equivalent yield and exo ratio, but since the space time is significantly lower than CSTR, the amount that can be produced per hour is very high. That is, the present invention can exhibit high norbornene derivative yield and exo ratio even if the space time is short and the pressure is low. In addition, since only the reaction liquid is reacted without using a separate solvent, a high-purity norbornene derivative can be produced by a simple method without a separate complex purification apparatus.

Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

Generally, in the production of norbornene derivatives, a batch reactor has been used up to now, and it is difficult to operate the reactor in commercial production, and there is a problem that the investment cost and the operation ratio are increased.

Therefore, the inventors of the present invention have found that it is possible to solve the above-mentioned problems by using a continuous-type reactor while taking effort to improve productivity.

That is, the present invention relates to a cyclopentadiene, dicyclopentadiene or a mixture thereof; And a compound represented by the following general formula (1) are continuously introduced into a tubular reactor including a static mixer to carry out a reaction, and the molar ratio of the cyclopentadiene to the compound represented by the general formula (1) is 1: 1 To 1:10, or the molar ratio of the dicyclopentadiene to the compound represented by the formula (1) is 1: 2 to 1:20, and the reaction pressure is 1 to 20 bar.

[Chemical Formula 1]

CH ₂ = CH- (CH ₂ ) _n -C (= O) OR

In the above formula (1), n is an integer of 0 to 10, preferably 0 to 4, and R is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms.

According to a preferred embodiment of the present invention, the tubular reactor may be a PFR reactor. The static mixer may be of any type as long as it is commonly used, and may include at least one, preferably one to four, in the tubular reactor.

According to a preferred embodiment of the present invention, the space time of the reaction solution introduced into the reactor may be 0.1 to 30 min, preferably 0.1 to 10 min, more preferably 0.1 to 1 min. If the space time of the reaction solution is less than 0.1 min, the yield may be lowered. If the time exceeds 30 minutes, the side reaction may proceed and the yield may be lowered and the exo ratio may be lowered. Therefore, the space time in the above range may be preferable.

On the other hand, the space time is a value obtained by dividing the volume of the reaction solution by the volume flow rate of the reactant. In the case of a tubular reactor, for example PFR, the volume of the reactor equals the volume of the reaction liquid.

Cyclopentadiene is generally unstable at room temperature and easily changes to dicyclopentadiene, making it very difficult to be present as a pure cyclopentadiene. However, dicyclopentadiene can be used at high temperatures It is decomposed into two molecules of cyclopentadiene and participates in norbornene formation reaction. Therefore, in the present invention, it is possible to use as a raw material for the reaction regardless of cyclopentadiene or dicyclopentadiene.

Further, according to a preferred embodiment of the present invention, the reaction liquid is a mixture of a) converting dicyclopentadiene to cyclopentadiene in the reactor; And b) Diels-Alder Reaction of the cyclopentadiene with a compound represented by the following formula (1) to produce a norbornene derivative.

Specifically, the conversion of dicyclopentadiene to cyclopentadiene (or mono-quantification) in step a) is an endothermic reaction and is carried out under suitable temperature and pressure conditions. Preferably, the conversion step is carried out at a temperature of from 170 to 300 DEG C and / or from 1 to 20 bar. If the temperature is outside the above range, the conversion of dicyclopentadiene is reduced, or the decomposition product is converted to an oligomer and the yield of cyclopentadiene is lowered.

In step b), the cyclopentadiene converted in step a) may be reacted with a compound represented by formula (1) to produce a norbornene derivative. The Diels-Alder cyclization reaction of the above reaction is carried out after the conversion of dicyclopentadiene into cyclopentadiene and is carried out at a temperature of 170 to 300 ° C and / or a pressure of 1 to 20 bar under the same reactor as in step a) Or the like.

Therefore, according to a preferred embodiment of the present invention, the reaction temperature may be 170 to 300 ° C, preferably 190 to 280 ° C.

The pressure in the reactor may be increased due to the vaporization of the reactants at a high temperature during the reaction, and the reaction may be carried out under a pressure of preferably 1 to 20 bar, more preferably 1 to 10 bar.

The reaction rate of the cyclization reaction in the step b) depends on the substituent R of the compound represented by the formula 1, and the reaction rate increases as the electron withdrawing group is present. At this time, the content of the compound represented by the formula (1) may be determined in consideration of the conversion rate of dicyclopentadiene initially injected.

That is, according to a preferred embodiment of the present invention, the molar ratio of the cyclopentadiene to the compound represented by Formula 1 in the reactants is in the range of 1: 1 to 1:10, preferably 1: 1 to 1: 5 And more preferably in the range of 1: 1 to 1: 2. The molar ratio of dicyclopentadiene to the compound represented by the formula (1) may be in the range of 1: 2 to 1:20, preferably 1: 2 to 1:10, more preferably 1 : 2 to 1: 4. This is because it relates to the extent and selectivity of the reaction. If the molar ratio is less than the above range, the yield of desired norbornene can not be achieved, side reactions such as the cyclization reaction of unreacted cyclopentadiene or dicyclopentadiene and norbornene proceed, Can not do it. If the molar ratio exceeds the above range, the unreacted compound represented by the general formula (1) will remain and the purification efficiency will be lowered. On the other hand, it is preferable to perform quick cooling to prevent the conversion of cyclopentadiene to dicyclopentadiene after completion of the reaction. Thus, the step of converting dicyclopentadiene to cyclopentadiene and the cyclization step of the cyclopentadiene and the compound represented by Formula 1 can be suitably controlled to produce a high-purity norbornene with high yield. Furthermore, the above reactions can be carried out without using a solvent, so that norbornene can be obtained by a simple purification process.

Further, in the production process of the present invention, it is preferable to further add a polymerization inhibitor during the reaction in order to prevent the phenomenon that the reactants and products are polymerized and decomposed or decomposed during the reaction.

According to a preferred embodiment of the present invention, the reaction solution is a mixture of 2,6-di-tert-butyl-4-methylphenol, 2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl), aniline, cyclohexane, phenol, 4-ethoxyphenol, nitrobenzene, And may further include at least one polymerization inhibitor selected from the group consisting of hydroquinone, benzoquinone, copper dichloride, and iridox, and the polymerization inhibitor is not limited thereto.

Specific examples of the Irganox include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1081, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1520, Irganox 1726 and Irganox 245.

In the norbornene derivative producing method of the present invention, the polymerization inhibitor may be contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of cyclopentadiene, dicyclopentadiene or a mixture thereof and the compound represented by the formula And preferably 0.01 to 0.3 part by weight. If the amount of the polymerization inhibitor is less than 0.01 parts by weight, the polymerization of the reactant (Cp or DCPD) itself can not be effectively prevented. If the amount of the polymerization inhibitor is more than 1 part by weight, There is a problem that the polymerization inhibitor must be removed after synthesis is completed. Therefore, it is preferable to include it in the above range. However, the addition of the polymerization inhibitor is not essential in the present invention.

The norbornene derivatives prepared in the present invention are formed of two isomers, exo and endo. When the substituent is spatially close to the longest chain, the endo isomer is referred to as the exo isomer when the substituent is formed in a part farthest from the longest chain. Thus, the Exo ratio means the ratio of exo isomers in norbornene derivatives.

(2)

On the other hand, in the conventional norbornene derivative production method, a batch reactor is used, and therefore, it is difficult to operate the reactor during commercial production, and the investment cost and the operating ratio increase.

However, the present invention is a production method using a tubular reactor including a static mixer, in which a significantly smaller amount of reactant is charged than the conventional method, and the yield of the norbornene derivative is 80 to 95% , And the exo ratio may be 20 to 70, preferably 40 to 70. [ That is, in the present invention, by using the tubular reactor including the static mixer, the norbornene derivative yield, the exo ratio, and the productivity can be remarkably increased compared with the case of using the batch reactor. In addition, the norbornene derivative yield and exo ratio are similar to those of the CSTR reactor, but the productivity can be increased. The Exo ratio is an important factor in securing the physical properties of the final product.

Further, since the present invention is carried out by reacting only the reaction solution without using a separate solvent, a high purity norbornene derivative can be produced by a simple method without any complicated purification device.

The reaction apparatus according to the present invention comprises a pump (LC pump) for introducing a reaction solution containing cyclopentadiene, dicyclopentadiene or a mixture thereof, a compound represented by the formula (1) and a polymerization inhibitor at a constant rate, A tubular reactor connected to the pump, an electric heater and a thermocouple surrounding the tubular reactor, and a cooling tank connected to the tubular reactor for cooling the produced norbornene derivative, A water bath, and a back pressure regulator for regulating the pressure in the reaction apparatus. And at least one static mixer in the tubular reactor.

The production process of the norbornene derivative using the above reaction apparatus will be described below.

Firstly, cyclopentadiene, dicyclopentadiene or mixtures thereof as starting materials in the reactor; And a compound represented by the following formula (1) are injected at a constant molar ratio, and then a reaction liquid having the same molar ratio as the starting material is continuously introduced into the reactor by using a pump. The reactor is heated to a temperature of 170 to 300 ° C. by a heating tank and maintained at a pressure of 1 to 20 bar by a pressure regulator so that the reaction liquid is uniformly mixed by a static mixer in the tubular reactor, To prepare a norbornene derivative according to the present invention.

On the other hand, it is advantageous that the CSTR reactor is well mixed so that the temperature distribution of the internal reaction liquid is constant. However, when the CSTR reactor is used, the reaction time is prolonged because the concentration of the reactant in the reaction liquid is lower than that of the PFR reactor, and the productivity is lowered.

However, in the present invention, by using a tubular reactor including a static mixer, preferably a PFR reactor, it has a high yield and an exo ratio even if the space time is short. At this time, the size of the reactor may be varied depending on the content of the reaction solution including cyclopentadiene, dicyclopentadiene or a mixture thereof, and a compound represented by the following formula (1). The PFR reactor having a diameter as small as possible is advantageous for thermal efficiency, uniform temperature distribution and instant cooling after reaction. Then, the norbornene derivative prepared in the reactor is passed through a cooling bath and quenched to terminate the reaction, thereby recovering the norbornene derivative of high purity. Next, the cooled norbornene derivative is purified by a conventional purification method.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Example One

A 3-neck round bottom flask was charged with a molar ratio of 96% purity 96% dicyclopentadiene and 99.5% purity butyl acrylate to 0.5: 1.3, and then 1.0 wt% of dicyclopentadiene 2,6-di-tert-butyl-4-methylphenol was added as a polymerization inhibitor to prepare a feed. The prepared feed was fed into a 7.2-ml PFR reactor equipped with a static mixer using a LC pump at a rate of 2.4 g / min (space time: 3 min), and a heat band was used to feed the tubular reactor The internal temperature of the PFR was maintained at 260 占 폚. A back pressure regulator (BPR) was installed at the downstream of the tubular reactor to maintain the internal pressure at 10 bar. In order to prevent the danger due to high temperature during discharging, the water was passed through a water bath to keep the discharge temperature below 50 ° C.

Example 2 to Example 5

The reaction was carried out in the same manner as in Example 1, except that the reaction temperature and space time in Table 1 were used.

Comparative Example One

As a reaction apparatus, a 1 L high-pressure reactor of Autoclave was used. First, in a high-pressure reactor, 153.1 g of dicyclopentadiene having a purity of 96%, 368.4 g of butyl acrylate having a purity of 99.5% and 368.4 g of a polymerization inhibitor (butyl acrylate) were added so that the molar ratio of dicyclopentadiene and butyl acrylate was 0.5: 1.5 g of 2,6-di-tert-butyl-4-methylphenol was charged into the flask, and the flask was replaced with an electric heater five times using nitrogen. The internal temperature was raised to 230 캜. After a reaction time of 1 hour from the point at which the temperature reached 230 캜, a mixture having exactly the same composition as that charged into a CSTR reactor was introduced at a rate of 8.6 g / ml (space time 1 h) using a LC pump of Hitachi, The same amount was discharged using a peristaltic pump of Masterflex. In order to prevent the danger due to high temperature during discharge, the discharge temperature was kept below 50 ℃ by passing through a water bath. The internal pressure was maintained at 10 bar.

Comparative Example 2 to Comparative Example 4

The reaction was carried out in the same manner as in Comparative Example 1, except that the reaction temperature and space time were as shown in Table 1 below.

division Reaction temperature (캜) Space time Example 1 260 3 min Example 2 260 1 min Example 3 210 30 min Example 4 210 10 min Example 5 190 30 min Comparative Example 1 230 1hr Comparative Example 2 230 1.5hr Comparative Example 3 210 1.5hr Comparative Example 4 210 1hr

Comparative Example 5

As a reaction apparatus, a batch reaction was carried out using a 1 L high-pressure reactor of Autoclave. First, in a high-pressure reactor, 83.5 g of dicyclopentadiene having a purity of 96% and 200.9 g of butyl acrylate having a purity of 99.5% were poured in such a manner that the molar ratio of dicyclopentadiene to methyl acrylate was 0.5: 1.3, 0.8 g of 2,6-ditert-butyl-4-methylphenol was added as an antioxidant, and the mixture was replaced with nitrogen five times, and then an electric heater was used And the internal temperature was raised to 210 ° C to react. The internal pressure was maintained at 10 bar and the reaction time was 1 hour.

Experimental Example One

(1) The results of quantitative analysis of the samples of Examples 1 to 5 after the stabilization of the continuous reaction by gas chromatography using the following equation are shown in Table 2.

* Yield = (DCPD consumption + BA consumption) X GC factor X BENB area X GC sample weight X 100 / (BENB theoretical quantity X STD area)

- BENB theoretical amount = DCPD usage X 2 X BENB M.W. / DCPD M.W.

- GC factor = percentage of area when the amount of BENB and internal standard on GC is the same

- BA = butyl acrylate

- DCPD = dicyclopentadiene

- BENB = norbornene formed by the reaction of DCPD and BA

- STD = internal standard used for GC measurement

Exo ratio = exo GC peak area / (exo GC peak area + endo GC peak area)

division Exo ratio (%) yield(%) Example 1 52 87.4 Example 2 51 91.1 Example 3 51 88.4 Example 4 51.5 91.6 Example 5 46 93.7

(2) The products obtained through the above Comparative Examples 1 to 4 were quantitatively analyzed by gas chromatography every hour, and the yield and EXO ratio were calculated by the above equations, Table 3 shows the results.

Elapsed time (hr) after continuous injection Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Exo ratio (%) yield(%) Exo ratio (%) yield(%) Exo ratio (%) yield(%) Exo ratio (%) yield(%) 0 52.5 89.1 52.8 86.7 45.3 89.1 43.5 88.0 One 49.2 87.1 50.4 83.5 45.0 85.5 41.1 86.4 2 49.1 87.0 50.2 86.5 44.1 91.4 40.2 86.3 3 49.1 86.7 50.6 78.6 43.8 90.7 40.6 85.8 3.7 - - - - - - 39.4 86.1 4 - - 50.3 85.1 - - - -

Referring to Tables 2 and 3, it can be seen that the yield and Exo ratio of a CSTR reactor having a long space time and a PFR reactor having a short space time are similar.

(3) After the batch reaction of Comparative Example 5, samples were obtained at intervals of 30 minutes, and quantitative analysis was carried out by gas chromatography. The results are shown in Table 4 as follows.

Elapsed time after injection (hr) Comparative Example 5 Exo ratio (%) yield(%) 0.5 38.9 81.6 1.0 45.0 83.0 1.5 48.7 78.8

In Comparative Example 5, as a result of the batch reaction, the yield and the exo ratio are lower than those of Example 4, which is the same reaction time as 83.0% and 45.0%, respectively, at a reaction time of 1 hour, which is an optimal condition.

Claims

Cyclopentadiene, dicyclopentadiene, or mixtures thereof; And a compound represented by the following formula (1) are continuously introduced into a tubular reactor including a static mixer to perform a reaction,
The molar ratio of the cyclopentadiene to the compound represented by Formula 1 is 1: 1 to 1:10 or the molar ratio of the compound represented by Formula 1 is 1: 2 to 1:20, A process for producing a norbornene derivative having a pressure of 1 to 20 bar;
[Chemical Formula 1]
CH ₂ = CH- (CH ₂ ) _n -C (= O) OR
In Formula 1,
n is an integer of 0 to 10, and R is an alkyl group having 1 to 20 carbon atoms.

The method according to claim 1,
Wherein the tubular reactor is a PFR reactor. &Lt; RTI ID = 0.0 > 21. < / RTI >

The method according to claim 1,
Wherein the space time of the reaction solution introduced into the reactor is 0.1 to 30 min.

The method according to claim 1,
Wherein the space time of the reaction solution introduced into the reactor is 0.1 to 10 min.

The method according to claim 1,
Wherein the space time of the reaction solution introduced into the reactor is 0.1 to 1 min.

The method according to claim 1,
The temperature of the reaction is
Lt; RTI ID = 0.0 > 300 C. < / RTI >

The method according to claim 1,
The reaction solution
a) converting dicyclopentadiene to cyclopentadiene; And
b) Diels-Alder Reaction of the cyclopentadiene with a compound represented by the following formula (1) to produce a norbornene derivative.

The method according to claim 1,
The reaction solution
2,6-di-tert-butyl-4-methylphenol, 2,2-di (4-tert-octylphenyl) But are not limited to, 2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl), aniline, cyclohexane, phenol, 4-ethoxyphenol, nitrobenzene, hydroquinone, benzoquinone, &Lt; / RTI > further comprising at least one polymerization inhibitor selected from the group consisting of < RTI ID = 0.0 >

The method of claim 8,
Wherein the polymerization inhibitor is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of cyclopentadiene, dicyclopentadiene or a mixture thereof and the compound represented by the formula (1).

The method according to claim 1,
Wherein the norbornene derivative has a yield of 80 to 95%.

The method according to claim 1,
Wherein the norbornene derivative has an exo ratio of 20 to 70. The norbornene derivative according to claim 1,