WO2016072818A1 - Continuous production method for norbornene derivative - Google Patents

Abstract

The present invention relates to a method for producing a norbornene derivative having a molar ratio of 1:1 to 1:10 for cyclopentadiene and a compound expressed by the chemical formula 1, or a molar ratio of 1:2 to 1:20 for dicyclopentadiene and a compound expressed by the chemical formula 1, the method comprising continuously adding and reacting, in a continuous reactor, a reaction solution comprising cyclopentadiene, dicyclopentadiene or a mixture thereof and a compound expressed by the chemical formula 1. [Chemical formula 1] CH₂=CH-(CH₂)_n-C(=O)OR where n is an integer 1-10 and R is an alkyl group of 1-20 carbon atoms

Description

Continuous production process of norbornene derivatives

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0154508 filed November 07, 2014 and Korean Patent Application No. 10-2015-0156012 filed November 06, 2015, All content disclosed in is included as part of this specification.

The present invention relates to a continuous production method of norbornene derivatives, and relates to a continuous production method of norbornene derivatives in which the yield, exo ratio and productivity are significantly increased as compared to using a conventional batch reactor.

Cyclic olefin polymer is a polymer composed of cyclic monomers such as norbornene, and has excellent transparency, heat resistance, and chemical resistance, and has very low birefringence and water absorption rate compared to existing olefinic polymers. It can be applied to various medical materials such as optical materials, capacitor films, information electronic materials such as low dielectric materials, low absorbing syringes, blister packaging, and the like. In this regard, the cyclic olefin polymerization technology includes ring opening metathesis polymerization (ROMP), ring opening metathesis polymerization followed by hydrogenation, copolymerization with ethylene, and homopolymerization. The norbornene polymer is a polymer that is variously applied to the above fields. The dicyclopentadiene (cyclopentadiene) or cyclopentadiene (cyclopentadiene) is reacted with an olefin as a monomer to introduce a double bond, and polymerized it to produce a norbornene polymer.

Since the synthesis of norbornene was first described in 1941 by LMJoshel and LWButz (J. Am. Chem., 63, 3350), U.S. Pat.No. 2,340,908 discloses about 200 under a pressure of 50 to about 100 bar. The reaction of dicyclopentadiene and ethylene is initiated at a temperature of < RTI ID = 0.0 > C, < / RTI > where the final yield of norbornene is described as 45%. It is essential to use dicyclopentadiene in high purity to prepare the norbornene polymer, but it is converted to cyclopentadiene under temperature and pressure conditions, or dicyclopentadiene and cyclopentadiene cause a cyclization reaction to dimer ) Or by-products such as trimers. Moreover, in the case of the dicyclopentadiene, it is difficult to produce pure norbornene due to difficulty in distillation purification.

In general, a batch reactor is used in the production of norbornene derivatives, which is difficult to operate the reactor in commercial production, and there is a problem in that the investment cost and operation cost increase. In addition, operation with a batch reactor usually requires repeating a series of operations such as elevated temperature, reactant injection, reaction, cooling and product discharge. Therefore, there is a problem in that the reactor volume or the number of reactors needs to be increased for mass production because the productivity per batch operation is low.

Accordingly, an object of the present invention is to provide a method for producing a norbornene derivative having excellent 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 Formula 1; The reaction solution containing the reaction is continuously added to the continuous reactor, the molar ratio of cyclopentadiene and the compound represented by the formula (1) is 1: 1 to 1:10, or dicyclopentadiene represented by the formula (1) It provides a method for producing a norbornene derivative having a molar ratio of 1: 2 to 1:20.

[Formula 1]

CH ₂ = CH- (CH ₂ ) _n -C (= O) OR

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

According to a preferred embodiment of the present invention, the continuous reactor is any one selected from a continuous stirred tank reactor, a tubular reactor, and a semi-batch reactor. Can be.

According to a preferred embodiment of the present invention, the space velocity of the reaction solution introduced into the reactor may be 0.05 ~ 5h ^-1 , the reaction temperature may be 170 to 300 ℃, the reaction pressure is 1 to 20 bar Can be.

According to a preferred embodiment of the present invention, the reaction solution is 2,6-di-tert-butyl-4-methylphenol ((2,6-di-tert-butyl-4-methylphenol), 2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl (2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl), aniline, cyclohexane, phenol, 4-ethoxyphenol, nitrobenzene, It may further comprise at least one polymerization inhibitor selected from the group consisting of hydroquinone, benzoquinone, copper dichloride, and iganox, wherein the polymerization inhibitor is cyclopentadiene, dicyclopentadiene or a mixture thereof and the above formula. 0.01 to 1 part by weight based on 100 parts by weight of the total of the compound represented by 1.

The present invention can provide a method for producing a norbornene derivative using a continuous reactor. It is an object of the present invention to provide a production method in which the yield, exo ratio and productivity are significantly increased compared to the case of using a conventional batch reactor.

In addition, since the present invention is made by reacting only the reaction solution without using a separate solvent, a high purity norbornene derivative can be prepared by a simple method without a separate complex purification device.

1 is a schematic diagram of a reaction apparatus including a CSTR reactor according to a preferred embodiment of the present invention.

2 is a schematic diagram of a reactor including a tubular reactor according to a preferred embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. The following detailed description is for the description of one embodiment of the present invention, although not limited to the scope of the claims defined by the claims.

In general, in the production of norbornene derivatives, a batch reactor has been used so far, and thus, it is difficult to operate the reactor in commercial production, and there is a problem in that the investment cost and operation cost increase.

The present inventors have made diligent efforts to improve productivity, and found that the above problems can be solved by using a continuous reactor.

That is, the present invention is cyclopentadiene, dicyclopentadiene or a mixture thereof; And a reaction solution containing a compound represented by Chemical Formula 1 is continuously added to a continuous reactor for reaction, and a molar ratio of cyclopentadiene and the compound represented by Chemical Formula 1 is 1: 1 to 1:10, or dicyclopenta Provided is a method for preparing a norbornene derivative in which a molar ratio of diene to a compound represented by Chemical Formula 1 is 1: 2 to 1:20.

[Formula 1]

CH ₂ = CH- (CH ₂ ) _n -C (= O) OR

In Formula 1, n is an integer of 0 to 10, preferably an integer of 0 to 4, R is an alkyl group of 1 to 20 carbon atoms, preferably an alkyl group of 1 to 8 carbon atoms.

According to a preferred embodiment of the present invention, the continuous reactor is not particularly limited to the type of reactor if the reaction can be continuously added to the reaction proceeds. However, preferably, the reactor may be any one selected from a continuous stirred tank reactor, a tubular reactor, and a semi-batch reactor, and more preferably, a continuous stirred tank reactor. It may be a continuous stirred tank reactor.

According to a preferred embodiment of the present invention, the space velocity of the reaction solution introduced into the reactor may be 0.05 ~ 5h ^-1 , preferably 0.1 ~ 3h ^-1 . If the space velocity of the reaction solution is less than 0.05h ^-1 , the reaction is not completed, there may be a problem that the yield and exo ratio is lowered, if it exceeds 5h ^-1 , there may be a problem that the yield is lowered. Therefore, the space velocity in the above range may be preferable.

Meanwhile, the space velocity is a value obtained by dividing the volume flow rate (cm ³ / hr) of the liquid phase reactant by the reactor volume (cm ³ ).

Cyclopentadiene is generally unstable at room temperature and is easily changed into dicyclopentadiene, making it very difficult to exist as pure cyclopentadiene. Dicyclopentadiene, however, Since it decomposes into two molecules of cyclopentadiene and participates in the norbornene production reaction, in the present invention, either cyclopentadiene or dicyclopentadiene can be used as a raw material for the reaction.

In addition, according to a preferred embodiment of the present invention, the reaction solution a) converting dicyclopentadiene to cyclopentadiene in the reactor; And b) Diels-Alder Reaction with the cyclopentadiene compound represented by Chemical Formula 1 below. A norbornene derivative may be prepared.

Specifically, the conversion reaction of dicyclopentadiene to cyclopentadiene (or monomerization) in step a) is an endothermic reaction, and is performed at appropriate temperature and pressure conditions. Preferably, the conversion step is carried out at a temperature of 170 to 300 ° C. and / or a pressure of 1 to 20 bar. If it is out of the above range, the conversion rate of dicyclopentadiene is reduced, or the decomposition product is converted into an oligomer, and the yield of cyclopentadiene is lowered.

In the step b), the norbornene derivative may be prepared by reacting the cyclopentadiene converted in step a) with the compound represented by Chemical Formula 1. The Diels-Alder cyclization reaction of the reaction takes place after the dicyclopentadiene is converted to cyclopentadiene and is the same reactor as in step a) under a temperature of 170 to 300 ° C. and / or a pressure of 1 to 20 bar. Can be performed continuously within.

Therefore, according to a preferred embodiment of the present invention, the reactor may be carried out at a temperature of 170 ~ 300 ℃, preferably may be carried out at 190 ~ 280 ℃.

The pressure in the reactor may appear to increase in pressure due to the vaporization of the reactants at a high temperature during the reaction, preferably carried out under a pressure of 1 to 20 bar, more preferably 2 to 15 bar.

The reaction rate of the cyclization reaction of step b) depends on the substituent R of the compound represented by Formula 1, and the reaction rate increases as the electron withdrawing group is present. In this case, the content of the compound represented by Chemical Formula 1 may be determined in consideration of the conversion rate of dicyclopentadiene first injected.

That is, according to a preferred embodiment of the present invention, the molar ratio of the cyclopentadiene and the compound represented by the formula (1) in the reactant is in the range of 1: 1 to 1:10, preferably 1: 1 to 1: 5 It may be more preferably in the range of 1: 1 to 1: 2. The molar ratio of dicyclopentadiene and the compound represented by Chemical Formula 1 may be in the range of 1: 2 to 1:20, preferably in the range of 1: 2 to 1:10, and more preferably 1 It may range from 2: 2 to 4: 4. This is because the degree of reaction progression and the selectivity are related. If the molar ratio is less than the above range, the desired norbornene yield cannot be achieved, and side reactions such as cyclization of unreacted cyclopentadiene or dicyclopentadiene and norbornene proceed to generate by-products, which is undesirable. Can not do it. In addition, when the molar ratio exceeds the above range, the unreacted compound represented by the formula (1) remains, which leads to lower purification efficiency. On the other hand, in order to prevent the conversion of cyclopentadiene to dicyclopentadiene after completion of the reaction, cooling is preferably performed quickly. As such, by controlling the conversion of dicyclopentadiene to cyclopentadiene and the cyclization step of the cyclopentadiene and the compound represented by Formula 1, high purity norbornene can be produced in high yield. Furthermore, the reactions can be carried out without the use of solvents to obtain norbornene with a simple purification process.

In addition, in the preparation method of the present invention, it is preferable to further add a polymerization inhibitor during the reaction in order to prevent the reactants and products from polymerizing and polymerizing or decomposing during the reaction.

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

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

In addition, in the method for preparing norbornene derivatives of the present invention, the polymerization inhibitor may be contained in an amount of 0.01 to 1 parts by weight based on 100 parts by weight of the total of the compound represented by the following formula (1): cyclopentadiene, dicyclopentadiene, It may be, preferably 0.01 to 0.3 parts by weight. If the polymerization inhibitor is less than 0.01 part by weight, the polymerization of the reactant (Cp or DCPD) itself can not be effectively prevented, and if it exceeds 1 part by weight, it does not affect the polymerization prevention effect any more, and if a large amount is used There is a problem that the polymerization inhibitor must be removed after the synthesis is completed. Therefore, it is preferable to include 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 of exo and endo. Referring to the following Formula 2, the substituent is formed when the substituent is formed in the space closest to the longest chain, the exo isomer is formed when the substituent is formed in the part far from the longest chain. Therefore, Exo ratio means the ratio occupied by the exo isomer among norbornene derivatives.

[Formula 2]

On the other hand, the conventional norbornene derivative manufacturing method used a batch reactor, it is difficult to operate the reactor during commercial production, there is a problem that the investment cost and operating costs increase.

However, in the present invention, by using a continuous reactor, it is possible to significantly increase the norbornene derivative yield, exo ratio and productivity compared to when using a batch reactor. The Exo ratio is an important factor in securing the physical properties of the final product.

According to the characteristics of the present invention as described above, the yield of the norbornene derivative prepared by the production method of the present invention is 80 to 95%, the exo ratio may be 20 to 70%.

In addition, when the yield of the norbornene derivative prepared by the production method of the present invention is 85 to 95%, the exo ratio of the norbornene derivative may be preferably 40 to 70, more preferably 45 to 70 , Most preferably 50 to 70.

In addition, since the present invention is made by reacting only the reaction solution without using a separate solvent, it is possible to produce a high purity norbornene derivative by a simple method without a separate complicated purification device.

1 is a schematic diagram of a continuous reactor including a CSTR reactor used in the method for producing norbornene derivatives according to the present invention.

Referring to Figure 1, the reaction apparatus according to the present invention is a cyclopentadiene, dicyclopentadiene or a mixture thereof, the starting material, the reaction solution containing the compound represented by the formula (1) and the polymerization inhibitor at a constant rate LC pump (11), CSTR reactor 12 connected to the pump, an electric heater (13) mounted to the bottom of the reactor to heat the reactor to react the reaction liquid, the reactor ( A cooling bath (Water bath) 14 connected with 12) for cooling the prepared norbornene derivatives; And a peristaltic pump 15 for recovering the produced norbornene derivative from the reactor. In the case of the CSTR reactor, the pressure regulation is controlled by an N ₂ regulator.

Figure 2 is a schematic diagram of a reaction apparatus including a PFR reactor used in the method for producing a norbornene derivative according to the present invention.

 Referring to Figure 2, the reaction apparatus according to the present invention is a cyclopentadiene, dicyclopentadiene or a mixture thereof, the starting material, the reaction solution containing the compound represented by the formula (1) and the polymerization inhibitor at a constant rate LC pump 21: A tubular reactor 23 connected to the pump, an electric heater 22 and a thermocouple surrounding the tubular reactor, and the tubular reactor 23. A cooling bath (Water bath, 24) connected to the to cool the produced norbornene derivatives; And a back pressure regulator 25 for regulating the pressure in the reactor.

 Looking at the process for producing a norbornene derivative using the above reaction device is as follows.

 First, cyclopentadiene, dicyclopentadiene or mixtures thereof as starting materials in the reactors 12 and 22; And a compound represented by Formula 1 below; After the injection of the reaction solution containing a constant molar ratio, using the pump (11, 21) to continuously input the reaction liquid of the same molar ratio as the starting material into the reactor (12, 23). The reactors 12 and 23 are heated to a temperature of 170 to 300 ° C. by the heating tanks 13 and 22, and maintained at a pressure of 1 to 20 bar by the pressure regulator 25 to thereby maintain the pressures of the reactors 12 and 23. The reaction solution in the reaction to produce a norbornene derivative according to the present invention.

The reactors 12 and 23 may be used in various forms, but a CSTR or PFR reactor that is a continuous reactor is preferable. More preferably, the CSTR reactor is well mixed, so that the temperature distribution of the internal reaction solution is constant. It is advantageous for PFR reactors to have as small a diameter as possible for thermal efficiency, uniform temperature distribution and instant cooling after the reaction. At this time, the size of the reactor (12, 23) is used cyclopentadiene, dicyclopentadiene or mixtures thereof and the compound represented by the following formula (1); It may vary depending on the content of the reaction solution containing.

 Subsequently, the norbornene derivatives prepared in the reactors 12 and 23 pass through the cooling tanks 14 and 24 and quench to terminate the reaction, thereby recovering the high purity norbornene derivatives.

Next, the cooled norbornene derivative is purified by conventional purification methods.

Hereinafter, the present invention will be described in more detail with reference to Examples, but embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a basis of weight unless there is particular notice.

Example 1

As the reactor, an autoclave 1 L high pressure reactor was used. First, the molar ratio of dicyclopentadiene and butyl acrylate is 0.5: 1.3 in the high pressure reactor. 153.1 g of dicyclopentadiene with 96% purity and 368.4 g of butyl acrlyate with 99.5% purity and 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor (2,6- 1.5 g of di-tert-butyl-4-methylphenol) was added thereto, and after 5 substitutions using nitrogen, the internal temperature was raised to 230 ° C. using an electric heater. After 1 hour of reaction from the time of reaching 230 ℃, a mixture of exactly the same composition as that introduced into the reactor using a Hitachi LC pump is introduced at a rate of 8.6 g / min (space velocity 1h ^-1 ). The same amount was discharged using a peristaltic pump from Masterflex. In order to prevent the risk of high temperature during discharge, the water was passed through a water bath to maintain the discharge temperature below 50 ° C.

Example 2

The reaction was carried out in the same manner as in Example 1 except that the reactor internal temperature was 210 ° C., and the feed rate was 5.8 g / min (space velocity 1.5 h ⁻¹ ).

Example 3

As the reactor, an autoclave 1 L high pressure reactor was used. First, the molar ratio of dicyclopentadiene and methyl acrylate in the high pressure reactor is 0.5: 1.3. 194.8 g of dicyclopentadiene with 96% purity, 314.9 g of methyl acrlyate with 99.5% purity, and 2,6-di-tert-butyl-4-methylphenol (2,6) as polymerization inhibitor 1.9 g of -di-tert-butyl-4-methylphenol) was added and substituted five times with nitrogen, and then the internal temperature was increased to 210 ° C. using an electric heater. After 1 hour from the time of reaching 210 ℃, using a LC pump (Hitachi Co., Ltd.), the mixture of the same composition as that put in the reactor at a rate of 2.84 g / min (space velocity 3 ^-1 ) Using the masterflex's peristaltic pump (peristaltic pump), the same amount was discharged. In order to prevent the risk of high temperature during discharge, the water was passed through a water bath to maintain the discharge temperature below 50 ° C.

Example 4

As a reactor, a tubular reactor made of 1/4 "tubes was used. First, the molar ratio of dicyclopentadiene and butyl acrylate in a 1 L flask was 0.5: 1.3. 153.1 g of dicyclopentadiene with 96% purity, 368.4 g of butyl acrlyate with 99.5% purity and 2,6-di-tert-butyl-4-methylphenol (2,6- After diluting 1.5 g of di-tert-butyl-4-methylphenol), a uniform state was made by stirring. The prepared solution is introduced into the reactor at a flow rate of 2.4 g / min (space velocity 0.5 h ^-1 ) using a Hitachi LC pump, and the pressure is maintained at 10 bar using a back pressure regulator. After confirming that the flow rate is uniformly discharged, the reaction temperature was maintained at 210 ° C. through an electric heater.

Comparative Example 1

As the reactor, an autoclave 1 L high pressure reactor was used. First, 83.5 g of dicyclopentadiene (96% pure) and 200.9 g of butyl acrlyate (99.5% pure) were polymerized in a high pressure reactor so that the molar ratio of dicyclopentadiene and methyl acrylate was 0.5: 1.3. 0.8g of 2,6-ditert-butyl-4-methylphenol (2,6-ditert-butyl-4-methylphenol) was added as an inhibitor, and substituted five times with nitrogen, followed by an electric heater. And the temperature was raised to 210 ° C to react.

Experimental Example 1

The products obtained through Examples 1 to 3 were quantitatively analyzed by gas chromatography every hour, and the yield and EXO ratio were calculated by the following equations, and the results are shown in Table 1 below. .

※ Yield = (DCPD usage + BA usage) × GC factor × BENB area × GC sample weight × 100 / (BENB theoretical amount × STD area)

-BENB theory = DCPD consumption × 2 × BENB M.W. / DCPD M.W.

-GC factor = area ratio at the same amount of BENB and internal standard on GC

BA = butyl acrylate

DCPD = dicyclopentadiene

BENB = norbornene produced by the reaction of DCPD with BA

-STD = internal standard used for GC measurement

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

Table 1

Elapsed time after continuous feeding (hr)	Example 1		Example 2		Example 3
	yield(%)	Exo Ratio (%)	yield(%)	Exo Ratio (%)	yield(%)	Exo Ratio (%)
One	90.72	49.24	93.77	45.70	91.50	46.74
2	90.64	49.12	92.96	45.47	91.78	45.44
3	90.30	49.11	94.11	45.07	92.18	45.50
4	90.30	49.11	93.51	45.05	91.77	45.49

Experimental Example 2

In Example 4, the reaction temperature was kept constant, and samples were obtained at intervals of 30 min from 1 hr after quantitative analysis using gas chromatography, and the results were obtained in Table 2 as follows.

TABLE 2

Elapsed time after continuous feeding (hr)	Example 4
	yield(%)	Exo Ratio (%)
1.5	93.77	51.90
2	94.45	52.10
2.5	93.68	52.27

Experimental Example 3

After experimenting with the batch reaction of Comparative Example 1, samples were obtained at 30 min intervals and quantitatively analyzed by gas chromatography, and the results are obtained in Table 3 as follows.

TABLE 3

Elapsed time after loading (hr)	Comparative Example 1
	yield(%)	Exo Ratio (%)
0.5	81.6	38.9
1.0	83.0	45.0
1.5	78.8	48.7

[Description of the code]

11: LC pump 12: CSTR reactor

13: Electric heater 14: Water bath

15: Peristaltic Pump 21: LC Pump

22: electric heater 23: tubular reactor

24: water bath

25: Back pressure regulator

26: Thermocouple

Claims (13)

1. Cyclopentadiene, dicyclopentadiene or mixtures thereof; And a reaction liquid containing a compound represented by the following Chemical Formula 1; continuously added to a continuous reactor to carry out the reaction,

   Norbornene in which the molar ratio of the cyclopentadiene and the compound represented by Formula 1 is 1: 1 to 1:10, or the molar ratio of the dicyclopentadiene and the compound represented by Formula 1 is 1: 2 to 1:20. Preparation of derivatives;

   [Formula 1]

   CH ₂ = CH- (CH ₂ ) _n -C (= O) OR

   In Chemical Formula 1,

   n is an integer of 0-10, R is a C1-C20 alkyl group.
2. The method according to claim 1,

   The continuous reactor is any one continuous reactor selected from a continuous stirred tank reactor, a tubular reactor, and a semi-batch reactor. Manufacturing method.
3. The method according to claim 1,

   The space velocity of the reaction solution introduced into the reactor

   Method for producing a norbornene derivative, characterized in that 0.05 ~ 5h ^-1 .
4. The method according to claim 1,

   The temperature of the reaction

   Method for producing a norbornene derivative, characterized in that 170 to 300 ℃.
5. The method according to claim 1,

   The pressure of the reaction

   Method for producing a norbornene derivative, characterized in that 1 to 20 bar.
6. The method according to claim 1,

   The reaction solution

   a) converting dicyclopentadiene to cyclopentadiene; And

   b) Diels-Alder Reaction with the cyclopentadiene compound represented by the following formula (1); a method for producing a norbornene derivative, comprising the production of norbornene derivatives.
7. The method according to claim 1,

   The reaction solution

   2,6-di-tert-butyl-4-methylphenol ((2,6-di-tert-butyl-4-methylphenol), 2,2-di (4-tert-octylphenyl) -1-picrylhydride Lazyl (2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl), aniline, cyclohexane, phenol, 4-ethoxyphenol, nitrobenzene, hydroquinone, benzoquinone, copper dichloride, and iganox A method for producing a norbornene derivative, further comprising at least one polymerization inhibitor selected from the group consisting of:
8. The method according to claim 7,

   The polymerization inhibitor is a method for producing a norbornene derivative, characterized in that it comprises 0.01 to 1 part by weight based on 100 parts by weight of the total of cyclopentadiene, dicyclopentadiene or a mixture thereof and the compound represented by the formula (1).
9. The method according to claim 1,

   Yield of the norbornene derivative is a method for producing a norbornene derivative, characterized in that 80 to 95%.
10. The method according to claim 1,

    The exo ratio of the norbornene derivative is a method for producing a norbornene derivative, characterized in that 20 to 70.
11. The method according to claim 1,

    The yield of the norbornene derivative is 85 to 95%, the exo ratio of the norbornene derivative is a method for producing a norbornene derivative, characterized in that 40 to 70.
12. The method according to claim 11,

    The exo ratio of the norbornene derivative is a method for producing a norbornene derivative, characterized in that 45 to 70.
13. The method according to claim 12,

    The exo ratio of the norbornene derivative is a method for producing a norbornene derivative, characterized in that 50 to 70.

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