KR100831631B1 - Method of preparation norbornene derivatives - Google Patents

Abstract

The present invention relates to a method for preparing a norbornene derivative, and more particularly, dicyclopentadiene is converted to cyclopentadiene, and the cyclopentadiene is subjected to a Diels-Alder Cycloaddition reaction with an alkene compound. The present invention relates to a method for preparing a norbornene derivative, wherein a high purity norbornene derivative can be easily produced in high yield by cooling the reaction mixture in a tubular reactor and then cooling without using a solvent.

Norbornene, Dicyclopentadiene, Diels-Alder Cyclization Reaction

Description

Method for preparing norbornene derivatives {METHOD OF PREPARATION NORBORNENE DERIVATIVES}

1 is a schematic diagram showing a reaction apparatus used to prepare norbornene derivatives according to the present invention.

* Description of Major Symbols in Drawings *

10: reservoir 20: pump

30: heating bath 40: reactor

50: cooling tank 60: low temperature circulator

70: pressure regulator

The present invention relates to a process for preparing norbornene derivatives which can produce high purity norbornene derivatives in high yield.

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.

Among them, norbornene polymer is a polymer that is variously applied to the above fields. Thus, dicyclopentadiene or cyclopentadiene is reacted with an olefin as a monomer to introduce a double bond, and polymerized to prepare a norbornene polymer.

Since the synthesis of norbornene was first described in 1941 by LMJoshel and LWButz ( J. Am. Chem ., 63, 3350), U.S. Patent No. 2,340,908 has disclosed a pressure of about 200 ° C. under a pressure of 50 to about 100 bar. The reaction of dicyclopentadiene and ethylene at the temperature is initiated, with the final yield of norbornene being 45%.

In order to prepare the norbornene polymer, it is essential to use dicyclopentadiene in high purity, 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. Furthermore, in the case of the dicyclopentadiene, it is difficult to produce pure norbornene since distillation purification is difficult.

Thus, various studies have been conducted to prepare pure norbornene, and US Patent No. 3,007,977 discloses the synthesis of norbornene from a mixture of cyclopentadiene in addition to dicyclopentadiene as a raw material. It is mentioned that the control of reaction conditions is advantageous when used.

US Patent No. 3,763,253 discloses the following method for the production of norbornene. The molar ratio of olefin / dicyclopentadiene was introduced into the reactor at 3: 1 in the experiment and the reactants and products were kept in the gas phase, conditions under which norbornene formation is preferred, a temperature of 300 ° C., a pressure of 150 psi and 16 minutes The norbornene is collected by maintaining the residence time, with a yield of 75%.

EP 345 6674 prepared phenylnorbornene using styrene as a solvent, but the yield was very low at 43%.

German Patent No. 2 161 215 discloses a process for preparing 5-vinylnorbornene-2, wherein cyclopentadiene is a mixture of butadiene and di-tert-butyl-paracresol. After 60 minutes, 20% of cyclopentadiene was reacted to prepare 5-vinylnorbornene-2, but the yield was only 71.6%, and the impurities contained a large amount of purity.

US Pat. No. 6,294,706 discloses dicyclopentadiene at 160 ° C. by dropwise addition to olefins, resulting in 83% norbornene, 6% unreacted dicyclopentadiene, 10% unreacted styrene, Mercury impurities 1% were obtained. However, this method has a disadvantage in that a lot of unreacted raw materials remain when the temperature is low, and the amount of impurities rapidly increases when the temperature is raised above 240 ° C.

U.S. Patent 6,479,719 partially dimerizes dicyclopentadiene to cyclopentadiene by preheating at 140 to 240 ° C. and at an absolute pressure of 20 to 300 bar and this and ethylene to dicyclopentadiene and cyclopentadiene. Under stable reaction conditions between ethylene and ethylene, the molar ratio of ethylene / dicyclopentadiene is 1 to 20, the temperature is 200 to 320 ° C, and the reaction is carried out under an absolute pressure of 20 to 300 bar and under a residence time of 1 to 10 minutes. Obtained Bonen.

However, in common with these methods, a very high number of distillation steps are required to obtain pure norbornene by separating olefin and impurities, which are unreacted raw materials, after the completion of the reaction, and the actual yield is low due to the norbornene lost in the process. You lose. Moreover, the use of bulky high pressure reactors makes it difficult to operate and increases the price.

In addition, the production of norbornene derivatives having various substituents to meet various needs has not yet been established.

An object of the present invention for solving the above problems is to provide a method for producing a high purity norbornene derivative in a high yield.

The present invention to achieve the above object

a) converting dicyclopentadiene to cyclopentadiene; And

b) a method of preparing a norbornene derivative prepared by Diels-Alder Cycloaddition of the cyclopentadiene and an alkene compound.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a method for producing a norbornene derivative represented by the following formula (1).

R in Formula 1 is halogen;

An alkyl group selected from a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched haloalkyl group having 1 to 6 carbon atoms;

Acetate group selected from the group consisting of -C (= 0) OR ¹ , -OC (= 0) R ¹ , -R ² OC (= 0) R ¹ and -R ² OC (= 0) OR ¹ , Where R ¹ And R ² are independently the same as or different from each other, and are selected from a linear or branched alkyl group having 1 to 6 carbon atoms;

-R ³ -CN, wherein R ³ is selected from a linear or branched alkyl group having 1 to 6 carbon atoms; And

—Si (OR ⁴ ) (OR ⁵ ) (OR ⁶ ), wherein R ⁴ , R ⁵ and R ⁶ are the same as or different from each other, and are selected from the group consisting of a linear or branched alkyl group having 1 to 6 carbon atoms; .

In this case, the halogen group is selected from the group consisting of I, Cl, F and Br.

Diels-Alder cycloaddition is a reaction in which alkenes and conjugated dienes react with each other to form ring compounds.

In the present invention, after converting the dicyclopentadiene (DCPD) of the formula (1) to the cyclopentadiene of the formula (2) in Scheme 1, the norbornene derivative is prepared by reacting with the alkene compound of the formula (3).

(In Reaction Scheme 1, R is as described in Formula 1).

step a: conversion step

In step a, dicyclopentadiene (DCPD) represented by Formula 2 is converted to cyclopentadiene, as shown in Scheme 2:

The dicyclopentadiene represented by Formula 2 is a solid at room temperature, and is parallel to the cyclopentadiene represented by Formula 3. The conversion reaction of dicyclopentadiene to cyclopentadiene (or monomerization reaction) is an endothermic reaction, and is performed by applying an appropriate temperature and pressure. This endothermic reaction is achieved by controlling the total exotherm as much as possible, at which time the conversion depends on the temperature and pressure of the reaction.

Preferably, the conversion step is carried out at a temperature of 160 to 280 ° C and a pressure of 20 to 60 atm. However, when out of the above range, the conversion rate is lowered to obtain a high yield of norbornene, as well as unreacted dicyclopentadiene and side reactions of the dicyclopentadiene with cyclopentadiene or alkene compounds, thereby decreasing purity. .

step b: conversion step

In step b), a norbornene derivative is prepared by reacting cyclopentadiene of formula 3 converted in step a) with an alkene compound of formula 4, as shown in Scheme 3:

(In Reaction Scheme 3, R is as described in Formula 1).

The Diels-Alder cyclization reaction of Scheme 3 is carried out after the dicyclopentadiene is converted to cyclopentadiene, the same reactor under the same conditions as step a) at a temperature of 160 to 280 ℃ and a pressure of 20 to 60 atm Is performed continuously within.

The reaction rate of the cyclization reaction depends on the substituent of R, the reaction rate increases as the electron withdrawing group is present, and the detailed substituents are as shown in Chemical Formula 1.

At this time, the content of the alkene compound is determined in consideration of the conversion rate of the first injected dicyclopentadiene, preferably used in a molar ratio of 1:60 to 1:20 (alkene compound: dicyclopentadiene). If the molar ratio is less than the above range, the desired degree of norbornene yield cannot be achieved, and if it exceeds the above range, the cyclization reaction of unreacted cyclopentadiene, or the ring of dicyclopentadiene and cyclopentadiene Side reactions, such as oxidative reactions, proceed and produce by-products, which is undesirable.

In particular, it is preferable to perform cooling quickly to prevent the conversion of cyclopentadiene to dicyclopentadiene after completion of the reaction. This is due to the conversion of the cyclopentadiene to dicyclopentadiene corresponds to an exothermic reaction and suppresses side reactions due to the dicyclopentadiene through cooling.

As such, by converting dicyclopentadiene to cyclopentadiene and cyclization of the cyclopentadiene and alkene compounds, high purity norbornene can be produced in high yield. Furthermore, the reactions can be carried out without using a solvent to obtain norbornene with a simple purification process.

1 is a schematic diagram showing a reaction apparatus used to prepare norbornene derivatives according to the present invention.

Referring to FIG. 1, a reaction apparatus according to the present invention includes a feeding tank 10 in which an alkene compound and dicyclopentadiene are stored as starting materials; A pump 20 connected to one side of the reservoir 10 for controlling the injection and pressure of each of the starting materials at a constant molar ratio: heating to react the alkene compound and dicyclopentadiene of the reservoir 10. And a reactor 40 equipped with a pressurization device and a Diels-Alder reaction in the heating bath 30. A cooler 50 connected to the reactor 40 and equipped with a low temperature circulator 60 for cooling the produced norbornene derivatives; And a pressure regulator 70 for adjusting the pressure in the reactor.

Looking at the manufacturing process of the norbornene derivatives using the above reaction device are as follows.

First, the alkene compound and / or dicyclopentadiene of the storage tank 10 are injected at a constant molar ratio, and then transferred into the reactor 40 using the pump 20.

The reactor 40 is heated to a temperature of 160 to 280 ° C by the heating tank 30, and maintained in a pressure of 20 to 60 atm by the pressure regulator 70, thereby dicyclopentadiene in the reactor 40 Is converted to cyclopentadiene, and the converted cyclopentadiene and alkene compound are subjected to a Diels-Alder reaction to prepare a norbornene derivative according to the present invention.

The reactor 40 may be used in various forms, but a tube type reactor having a relatively large area-to-volume ratio is preferable, and more preferably, having a diameter as small as possible is thermal efficiency, but uniform temperature. Distribution, and for immediate cooling after the reaction. At this time, the size of the reactor 40 may vary depending on the content of the alkene compound and dicyclopentadiene used.

Subsequently, the norbornene derivative prepared in the reactor 40 passes through the cooling tank 50 equipped with the low temperature circulator 60 and quenches the reaction to terminate the reaction, thereby recovering the norbornene derivative of high purity.

Next, the cooled norbornene derivative is purified by conventional purification methods. In particular, the production process of norbornene derivatives according to the present invention is made by reacting only the reactants without using a separate solvent, it is possible to produce a high purity norbornene derivatives by a simple method without a separate complex purification device.

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

< Example  1> Butyl Norbornene  Manufacture 1

As shown in Scheme 4, butyl norbornene was prepared by reacting with dicyclopentadiene using 1-hexene (1-hexene) as an alkene compound.

Specifically, a mixed solution obtained by using a molar ratio of 1-hexene and dicyclopentadiene in a 1:60 molar ratio is injected into a 1/16 inch tubular reactor (1 ml volume) at a flow rate of 0.2 ml / min, and then the temperature of the reactor is increased. Butyl norbornene was prepared by heating to 280 ° C. and pressurizing the internal pressure to 50 atm. The resulting reaction was then passed through a heat exchanger cooled to 5.5 ° C. to produce butyl norbornene (yield 97%).

At this time, a small amount of the final reactant was collected and passed through gas chromatography (GC) to determine the conversion rate of dicyclopentadiene (DCPD), which was measured as 99.4% in Example 1.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.36 to 5.88 (m, 2H), 2.74 to 0.84 (m, 16H)

< Example  2> allyl acetate Norbornene  Manufacture 1

As shown in Scheme 5, allyl acetate norbornene was prepared by reacting with dicyclopentadiene using allyl acetate as an alkene compound.

Specifically, a mixed solution obtained by using a molar ratio of allyl acetate and dicyclopentadiene in a molar ratio of 1:30 is injected into a 1/16 inch tubular reactor (1 ml of volume) at a flow rate of 0.2 l / min, and then the temperature of the reactor is 260. It heated to ℃, and pressurized to an internal pressure of 50 atm to prepare allyl acetate norbornene (yield 97.5%).

At this time, dicyclopentadiene (DCPD) was measured as 99.9% conversion.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.17 to 5.91 (m, 2H), 4.15 to 3.63 (m, 2H), 2.91 to 2.88 (m, 2H), 2.38 (m, 1H), 2.05 (s , 3H), 1.83 (m, 1H), 1.60-1.25 (m, 2H), 0.57 (m, 1H)

< Example  3> allyl acetate Norbornene  Manufacture 2

As shown in Scheme 5, allyl acetate norbornene was prepared by reacting with dicyclopentadiene using allyl acetate as an alkene compound.

Specifically, the mixed solution obtained by using a molar ratio of allyl acetate and dicyclopentadiene in a molar ratio of 1:30 was injected into a 1/16 inch tubular reactor (volume 2 ml) at a flow rate of 0.2 ml / min, and then the temperature of the reactor was increased. Allyl acetate norbornene was prepared by heating to 210 ° C. and pressurizing to an internal pressure of 60 atm (yield 94.9%).

At this time, dicyclopentadiene (DCPD) was measured as 99.9% conversion.

< Example  4> allyl acetate Norbornene  Manufacture 3

As shown in Scheme 5, allyl acetate norbornene was prepared by reacting with dicyclopentadiene using allyl acetate as an alkene compound.

Specifically, a mixed solution obtained by using a molar ratio of allyl acetate and dicyclopentadiene in a molar ratio of 1:30 is injected into a 1/4 inch tubular reactor (5.2 ml by volume) at a flow rate of 0.52 ml / min, and then the temperature of the reactor is increased. Allyl acetate norbornene was produced by heating to 260 ° C. and pressurizing to an internal pressure of 60 atm (yield 98.3%).

At this time, dicyclopentadiene (DCPD) was measured as 99.9% conversion.

< Example  5> Acetonitrile Norbornene  Produce

As shown in Scheme 7, acetonitrile norbornene was prepared by reacting with dicyclopentadiene using butene nitrile as an alkene compound.

A mixed solution obtained with a butene nitrile and dicyclopentadiene in a molar ratio of 1:30 was introduced into a 1/4 inch tubular reactor (5.2 ml by volume) at a flow rate of 0.52 ml / min, and then brought to an internal pressure of 40 atm at room temperature. Pressurization afforded acetonitrile norbornene (yield 85.3%).

At this time, dicyclopentadiene (DCPD) was measured as 99.2% conversion.

< Example  6> Triethoxy Silane Norbornene  Produce

As shown in Scheme 7 below, triethoxy silane norbornene was prepared by reaction with dicyclopentadiene using an allyl triethoxy silane as an alkene compound.

Specifically, a mixed solution obtained by using an allyl triethoxy silane and dicyclopentadiene in a molar ratio of 1:30 is injected into a 1/4 inch tubular reactor (5.2 ml by volume) at a flow rate of 0.52 ml / min, and then the reactor. The temperature of was heated to 230 ℃, the internal pressure was pressed to 60 atm to prepare a triethoxy silane norbornene (yield 80%).

At this time, dicyclopentadiene (DCPD) was measured as 99.5% conversion.

< Example  7> Methyl acetate Norbornene  Produce

As shown in Scheme 8, methyl acetate norbornene was prepared by reacting with dicyclopentadiene using methyl butenoate as an alkene compound.

Specifically, a mixed solution obtained by using a methyl butenoate and dicyclopentadiene in a molar ratio of 1:60 is injected into a 1/4 inch tubular reactor (5.2 ml by volume) at a flow rate of 0.52 ml / min, and then The temperature was heated to 220 ° C and the internal pressure was pressed to 60 atm to prepare methyl acetate norbornene (yield 87%).

At this time, dicyclopentadiene (DCPD) was measured as 99.4% conversion.

< Example  8> Chloro  profile Norbornene  Produce

As shown in Scheme 9, chloropropyl norbornene was prepared by reacting with dicyclopentadiene using chloropentene as an alkene compound.

Specifically, the mixed solution obtained by using a chloropentene and dicyclopentadiene in a molar ratio of 1:30 was injected into a 1/4 inch tubular reactor (5.2 ml by volume) at a flow rate of 0.52 ml / min, and then the temperature of the reactor was increased. Chloropropyl norbornene was prepared by heating to 170 ° C. and internal pressure to 50 atm (yield 73%).

At this time, the dicyclopentadiene (DCPD) conversion was measured to 99.7%.

< Comparative example  1> Butyl Norbornene  Manufacture 2

1-hexene and dicyclopentadiene were injected and mixed in a molar ratio of 1: 4 into a commonly used batch type reactor, and then the inside of the reactor was 240 At the same time as heating to ℃ and the internal pressure was 22 atm to perform the Diels-Alder reaction for 3 hours, and then purified to prepare butyl norbornene.

At this time, the yield of butyl norbornene was 77%, dicyclopentadiene (DCPD) was measured as 98% conversion.

< Comparative example  2> allyl acetate Norbornene  Manufacture 4

Inject and mix allyl acetate and dicyclopentadiene in a molar ratio of 1: 2.5 in a commonly used batch type reactor, and then heat the reactor to 250 ° C. and at an internal pressure of 30 atm for 3 hours. After performing the Diels-Alder reaction, the product was purified twice to prepare butyl norbornene.

The yield of allyl acetate norbornene obtained at this time was 80%, dicyclopentadiene (DCPD) was measured as 98.2% conversion.

< Comparative example  3> Butyl Norbornene  Manufacture 3

The same procedure as in Comparative Example 1 was carried out except that the molar ratio of 1-hexene and dicyclopentadiene was 1:60. At this time, the yield of butyl norbornene was 72%, dicyclopentadiene (DCPD) was measured as 98% conversion.

< Comparative example  4> Butyl Norbornene  Manufacture 4

The same procedure as in Example 1 was carried out except that the molar ratio of 1-hexene and dicyclopentadiene was 1: 2.5. At this time, the yield of butyl norbornene was 75%, dicyclopentadiene (DCPD) was measured as 98% conversion.

< Comparative example  5> allyl acetate Norbornene  Manufacture 5

The same procedure as in Example 2 was carried out except that allyl acetate and dicyclopentadiene were used in a molar ratio of 1: 2.5. The yield of allyl acetate norbornene obtained at this time was 75.1%, dicyclopentadiene (DCPD) was measured as 99.1% conversion.

< Comparative example  6> allyl acetate Norbornene  Manufacture 6

The same procedure was followed as in Comparative Example 2, except that allyl acetate and dicyclopentadiene were used in a molar ratio of 1:30. The yield of allyl acetate norbornene obtained at this time was 72.4%, dicyclopentadiene (DCPD) was measured as 98.9% conversion.

Norbornene derivatives as obtained in Examples 1 to 6 and the yield thereof, and the conversion of dicyclopentadiene are shown in Table 1 below.

R Molar ratio Reaction temperature pressure yield Conversion rate Example 1 -C ₄ H ₉ 1:60 280 ℃ 50 atm 97% 99.4% Example 2 -OC (= O) -CH ₃ 1:30 260 ℃ 50 atm 97.5% 99.9% Example 3 -OC (= O) -CH ₃ 1:30 260 ℃ 60 atm 94.9% 99.9% Example 4 -OC (= O) -CH ₃ 1:30 260 ℃ 60 atm 98.3% 99.9% Example 5 -CH ₂ -CN 1:30 250 ℃ 40 atm 85.3% 99.2% Example 6 Si (OEt) ₃ 1:30 230 ℃ 60 atm 80% 99.5% Example 7 -C (= O) -O-CH ₃ 1:60 220 ℃ 60 atm 87% 99.4% Example 8 -CH ₂ -CH (CH ₃ ) -Cl 1:30 170 ℃ 50 atm 73% 99.7% Comparative Example 1 ^* -C ₄ H ₉ 1: 4 240 ℃ 22 atm 77.0% 98.0% Comparative Example 2 ^** -OC (= O) -CH ₃ 1: 2.5 250 ℃ 30 atm 80.0% 98.2% Comparative Example 3 ^*** -C ₄ H ₉ 1:60 240 ℃ 22 atm 72.0% 98.0% Comparative Example 4 -C ₄ H ₉ 1: 2.5 280 ℃ 50 atm 75.0% 98.0% Comparative Example 5 -OC (= O) -CH ₃ 1: 2.5 260 ℃ 50 atm 75.1% 99.1% Comparative Example 6 ^**** -OC (= O) -CH ₃ 1:30 250 ℃ 30 atm 72.4% 98.9% *, **, ***, ****: using batch type reactor

Referring to Table 1, it can be seen that the yield and conversion of the norbornene derivatives of the examples according to the present invention are higher than those of the comparative example.

In Example 1 and Comparative Examples 1, 3 and 4, butyl norbornene is prepared, and the conversion rate is at least 98.0. However, the butyl norbornene of Comparative Examples 1, 3 and 4 using a general batch type reactor was used. It can be seen that the yield is significantly different from 97% of Example 1, such as 77.0%, 72.0% and 75.0%, respectively. In particular, in Comparative Examples 1 and 2, as a large amount of unsaturated polymers such as dimers and trimers of cyclopentadiene were generated, not only the yield of norbornene derivatives was lowered, but also several purification steps were required.

As described above, the alkene compound and the dicyclopentadiene may be used to prepare norbornene derivatives substituted with various functional groups, and the reaction temperature and pressure may be adjusted to maximize the conversion of dicyclopentadiene. Could.

Thus, the method for preparing a norbornene derivative according to the present invention can maximize the conversion rate of dicyclopentadiene (DCPD) and the selectivity of norbornene and can simplify the purification process due to less impurities, thereby effectively increasing the yield.

Claims (6)

Represented by Scheme 1 below, a) converting dicyclopentadiene of formula 2 to cyclopentadiene of formula 3; And b) preparing a norbornene derivative of Formula 1 by Diels-Alder Reaction with the cyclopentadiene of Formula 3 and the alkene compound of Formula 4, wherein the alkene compound and dicyclopentadiene Used in a molar ratio of 1:20 to 1:60, Step a) and b) is a method for producing a norbornene derivative is carried out continuously in the same tube type reactor (tube type):  Scheme 1

In Scheme 1, R is halogen; An alkyl group selected from a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched haloalkyl group having 1 to 6 carbon atoms; Acetate group selected from the group consisting of -C (= 0) OR ¹ , -OC (= 0) R ¹ , -R ² OC (= 0) R ¹ and -R ² OC (= 0) OR ¹ Wherein R ¹ and R ² are the same as or different from each other, and are selected from a linear or branched alkyl group having 1 to 6 carbon atoms; -R ³ -CN, wherein R ³ is selected from a linear or branched alkyl group having 1 to 6 carbon atoms; And —Si (OR ⁴ ) (OR ⁵ ) (OR ⁶ ), wherein R ⁴ , R ⁵ and R ⁶ are the same or different from each other and are selected from a linear or branched alkyl group having 1 to 6 carbon atoms; It is selected. The method of claim 1, wherein the steps a) and b) are performed at a temperature of 160 to 280 ° C. The method of claim 1, wherein steps a) and b) are performed under a pressure of 20 to 60 atm. delete delete delete

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