KR101074500B1 - Method for preparing norbornene monomer comprising non-polar alkyl functional group - Google Patents

Abstract

The present invention is a step of mixing cyclopentadiene, dicyclopentadiene or a mixture thereof and dienophile in a molar ratio of 1: 1 to 1: 3, and reacting for 0.5 to 10 hours at a temperature of 170 ~ 240 ℃ It relates to a method for producing a norbornene monomer comprising a. According to the present invention, by adjusting the molar ratio of reaction temperature, reaction time and reaction starting materials which are variables of the reaction without addition of the catalyst, or improving the introduction method of the dienophile into the reactor, a norbornene monomer containing a nonpolar alkyl group may be prepared in high purity, It can be produced in high yield.

Diels-Alder reaction, nonpolar alkyl group, norbornene monomer

Description

The manufacturing method of the norbornene monomer containing a nonpolar alkyl group {METHOD FOR PREPARING NORBORNENE MONOMER COMPRISING NON-POLAR ALKYL FUNCTIONAL GROUP}

The present invention provides high purity and high purity of norbornene monomers containing non-polar alkyl groups by adjusting the reaction temperature, reaction time and molar ratio of reaction starting materials, which are variables of the reaction without addition of a catalyst, or by introducing a method of introducing a dienophile into a reactor. It relates to a process for producing in yield.

Norbornene-based additive polymers are excellent in optical properties, transparency, thermal stability, strength and secondary workability, so that they are protective films of polarizing plates, optical films such as retardation films, plastic substrate materials, transparent polymers such as POF, and PCBs or insulating materials. It is used as an insulating electronic material.

The development of the technology for producing norbornene monomers containing polar or non-polar functional groups is very important because it not only improves profitability by developing high value-added products, but also significantly affects the breakthrough performance of electrical and electronic products by developing related optical materials. have.

Empirically, cyclopentadiene, dicyclopentadiene, or a mixture thereof and 1-hexene, 1-octene, etc. may be mixed in a high-temperature, high-pressure reactor and reacted at a high temperature to prepare a norbornene monomer including alkyl as a nonpolar functional group. Butyl norbornene and hexyl norbornene can be prepared in high yield and high purity.

However, when the styrene monomer is mixed with cyclopentadiene, dicyclopentadiene or a mixture thereof and reacted at a temperature of 150 to 180 ° C., polystyrene having a very high viscosity is generated, which lowers the yield of phenyl norbornene. .

After synthesizing the phenyl norbornene monomer and distilling off the crude monomer by vacuum distillation to separate the pure phenyl norbornene monomer, the remaining polystyrene is very viscous. In order to treat this, it is very undesirable in terms of cost or distillation purification apparatus because it is necessary to completely dissolve and remove polystyrene with toluene after adding toluene.

Therefore, when manufacturing a phenyl norbornene monomer using styrene, the manufacturing technique which can raise the yield of a phenyl norbornene monomer while suppressing production | generation of polystyrene is calculated | required.

In order to prepare norbornene-based monomers in high yield and high purity, a long reaction time is required, but when the reaction temperature is increased to shorten the reaction time, the product becomes very impure due to the increase of side reactions.

As a solution to this problem, Nippon Zeon performed the synthesis of phenyl norbornene by using excess styrene as a solvent (EP-A2-0 345 674), but to produce the product in high yield and high purity. It is not possible to use this method.

To solve these problems, Finland's Optatech Corporation has gradually introduced cyclic dienes into the reaction with olefin compounds to keep the concentration of cyclic dienes low during the reaction in order to keep the concentration of cyclic dienes low. By preparing a phenyl norbornene monomer.

That is, a portion of the diene was first fed into the reactor together with the olefinic compound to produce a reaction mixture, and then the remainder of the diene was introduced into the reactor in one or more aliquots or as a continuous stream after the reaction had been to some extent (PCT / FI1997). / 00169).

However, this method also has a problem in that the yield of phenyl norbornene cannot be increased because styrene already introduced into the reactor is converted to polystyrene during a high temperature reaction.

The present invention is to solve the problems of the prior art, in the production of norbornene monomers containing a non-polar alkyl group, by adjusting the reaction temperature, reaction time, the molar ratio of the reaction starting material, which is a variable of the reaction without the addition of a catalyst, It is an object of the present invention to provide a method for producing a norbornene monomer containing a nonpolar alkyl group in high purity and high yield by improving a method of adding a dienophile into a reactor.

In order to achieve the above object, the present invention, cyclopentadiene, dicyclopentadiene or a mixture thereof and the compound represented by the following formula (1) is mixed in a molar ratio of 1: 1 to 1: 3, 170 ~ 240 ℃ It provides a method for producing a norbornene monomer comprising the step of reacting at a temperature of 0.5 to 10 hours.

<Formula 1>

CH ₂ = CH-R

In Formula 1, R is an aliphatic alkyl group or an aromatic alkyl group having 1 to 6 carbon atoms.

The present invention provides a high purity of a norbornene monomer containing a non-polar alkyl group by appropriately adjusting the reaction temperature, reaction time, the molar ratio of the reaction starting material, or the method of adding the compound represented by Chemical Formula 1 into the reactor. It can be produced in high yield.

The present invention mixes a diene compound cyclopentadiene, dicyclopentadiene or a mixture thereof and a dienophile compound in a molar ratio of 1: 1 to 1: 3, the temperature of 170 ~ 240 ℃ It relates to a method for producing a norbornene monomer comprising the step of reacting for 0.5 to 10 hours. That is, a dienes-Alder reaction between a diene compound and a dienophile compound having a double bond, such as α-olefin, to prepare a norbornene monomer containing alkyl as a nonpolar functional group It is a way.

In the method for producing the norbornene monomer, the dienophile compound used as the reaction starting material may be represented by the following formula (1).

CH ₂ = CH-R

In Formula 1, R is an aliphatic alkyl group or an aromatic alkyl group having 1 to 6 carbon atoms.

According to an embodiment of the present invention, in the method for preparing the norbornene monomer, the compound represented by Chemical Formula 1 is 1-hexene, 1-hexene, 1-octene, or styrene. desirable.

 According to another embodiment of the present invention, in the method for producing the norbornene monomer, it is preferable that the reaction is carried out under pressure conditions of 1 to 25 atmospheres.

According to another embodiment of the present invention, in the production method of the norbornene monomer, it is preferable to further add a polymerization inhibitor.

According to another embodiment of the present invention, it is preferable that the polymerization inhibitor is at least one compound selected from the group consisting of hydroquinone, benzoquinone, 4-tert-butylcatechol, resorcinol, and Igarnox.

According to another embodiment of the present invention, the weight ratio of the cyclopentadiene, dicyclopentadiene or the mixture thereof and the polymerization inhibitor added to the total weight of the compound represented by Formula 1 is 0.1 to 2.0 It is preferably in the% range.

According to another embodiment of the present invention, when the compound represented by Chemical Formula 1 is styrene, the cyclopentadiene, dicyclopentadiene or a mixture thereof is introduced into the reactor, and the cyclopentadiene and dish are introduced into the reactor. When clopentadiene or a mixture thereof is brought to a temperature of 170 ~ 180 ℃, it is preferable to introduce the styrene into the reactor at a flow rate of 1.0 to 5.0 cc / min.

According to another embodiment of the present invention, the styrene is preferably introduced through the sampling tube of the reactor.

According to another embodiment of the present invention, if the styrene is added to the reactor is completed, the temperature of the reactor is lowered to room temperature (25 ℃) to 60 ℃, it is preferable to stop the reaction.

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

In the present invention, the reaction temperature is maintained at approximately 170 ℃ or more it is characterized in that the cyclopentadiene which is one of the raw materials for the production of norbornene monomers can be used to replace the dicyclopentadiene which is a more stable form of the compound.

In general, it is unstable at room temperature and easily changed into dicyclopentadiene, making it very difficult to exist as pure cyclopentadiene. However, since dicyclopentadiene decomposes itself into two molecules of cyclopentadiene at 170 ° C. or higher, and participates in the reaction, in the present invention, either cyclopentadiene or dicyclopentadiene can be used as a raw material for the reaction. Therefore, there is an advantage that the purification process from dicyclopentadiene to cyclopentadiene is unnecessary and the process is simplified.

In addition, in the production method of the present invention, the reaction is preferably carried out under the condition that the reaction pressure is 1 to 25 atm, and the reaction time is 0.5 to 10 hours. The vaporization of the reactants at high temperatures results in high pressures during the reaction. Therefore, in the reaction state, it is difficult to maintain the reaction pressure below 1 atm, and it is inevitably brought to the above reaction pressure condition. However, it is possible to adjust the pressure so that it does not rise to a certain degree. If it exceeds 25 atm, it is difficult to manufacture a reactor that can withstand the pressure, and if the high pressure is not lowered during the reaction, there may be a problem of reaction control and stability. have.

The reaction time is adjusted to 0.5 to 10 hours, preferably 1 hour to 7 hours. This is because it affects the degree of reaction progression and the selectivity.

In the method for preparing a norbornene monomer according to the present invention, the molar ratio of the compound represented by the formula (1) with respect to cyclopentadiene, dicyclopentadiene or a mixture thereof in the reactants ranges from 1: 1 to 1: 3. It is preferable that it is, More preferably, it is good to adjust to the range of 1: 1-1: 2.5. This is because there is a change in the progress and selectivity of the reaction.

That is, when the ratio is less than 1: 1, the yield of the reaction is low, and when the ratio is 1: 3 or more, the amount of the substance represented by Formula 1 remains unreacted.

In addition, in the preparation method according to 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. Such polymerization inhibitors consist of hydroquinone, benzoquinone, 4-tert-butylcatechol, resorcinol, and Igarnox. It is preferably at least one compound selected from the group, but is not limited thereto.

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

In the preparation method according to the present invention, the weight ratio of the reactant cyclopentadiene, dicyclopentadiene or a mixture thereof and the total weight of the compound represented by Formula 1 is 0.1 to 2.0%. It is preferable. If the weight ratio is less than 0.1%, the polymerization of the reactant itself may not be effectively prevented, and the weight ratio of 1.0% may be sufficient to serve as a polymerization inhibitor. That is, even if the use of more than 2.0% by weight of the polymerization inhibitor does not affect the yield any more, when using a large amount of the problem occurs that the polymerization inhibitor must be removed after the synthesis is completed.

Meanwhile, in order to prepare a norbornene monomer including a nonpolar alkyl group, cyclopentadiene, dicyclopentadiene, or a mixture thereof and 1-hexene and 1-octene in the compound represented by Chemical Formula 1 are mixed in a high pressure reactor to form 220 By reacting for 2-7 hours at a high temperature of ~ 240 ℃ butyl norbornene and hexyl norbornene can be produced in high yield, high purity. However, when the styrene monomer of the compound represented by Chemical Formula 1 is mixed with cyclopentadiene, dicyclopentadiene or a mixture thereof and reacted at a temperature of 150 to 180 ° C., polystyrene having a very high viscosity is formed to form phenyl norbornene. There is a problem of lowering the yield.

After synthesizing the phenyl norbornene monomer and distilling and purifying the unpurified monomer under reduced pressure to separate the pure phenyl norbornene monomer, the remaining polystyrene is very viscous, so in order to treat this, toluene is added to toluene. Since it must be completely dissolved and then removed, it is not preferable in terms of cost or distillation unit management.

Therefore, in the present invention, when cyclopentadiene, dicyclopentadiene or a mixture thereof is introduced into the reactor and the cyclopentadiene, dicyclopentadiene or a mixture thereof introduced into the reactor reaches a temperature of 170 to 180 ° C, In addition, styrene is introduced into the reactor at a flow rate of 1.0 ~ 5.0cc / min to provide a method for producing a phenyl norbornene monomer to react.

In the above production method, when the cyclopentadiene, dicyclopentadiene or a mixture thereof already introduced into the high pressure reactor has a high temperature of 170 to 180 ° C, a styrene monomer is introduced into the high pressure reactor using a liquid transfer pump. It is preferable. In addition, styrene is preferably introduced into the reactor as slowly as possible at a flow rate in the range of 1.0 to 5.0 cc / min, and styrene monomer is preferably introduced into the reactor through the sampling tube rather than into the sample injection tube at the upper part of the reactor. Do. The reason for this is that when styrene is introduced into the sampling tube, the styrene monomer is vaporized as it enters the reactor, and the vaporized styrene monomer is immediately introduced into the reactor by uniformly mixing the vaporized styrene monomer. This is because reaction with vaporized cyclopentadiene, dicyclopentadiene or mixtures thereof forms phenyl norbornene, which is a desirable product, and the formation of polystyrene, which is an undesirable product, is significantly inhibited.

In addition, if the reaction time is kept long, the amount of polystyrene, which is an unnecessary product, is increased. Therefore, it is preferable to reduce the production of unnecessary polystyrene by stopping the reaction immediately when the styrene monomer is added to the reactor.

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

[Example]

Preparation of norbornene monomers comprising nonpolar alkyl groups was carried out using a 300 mL high pressure reactor as shown in FIG. 1, and the reaction time was defined as from the point at which the given reaction temperature was reached.

Gas chromatography (GC) analysis used a HP 6890 GC equipped with a flame ionization detector (FID) and an AT 1000 column.

Butyl Norborneen  Preparation of Monomers: Comparative example  1 and 2 and Example  1 to 2

DCPD (dicyclopentadien, Acros, purity 97%) and 1-hexene (Aldrich, 99%) were added to a 300 mL high-pressure reactor at the molar ratios described in the following Comparative Examples and Examples, and then the temperature was raised to 220-250 ° C., respectively, 300 rpm. The reaction was carried out for 1 to 2 hours while stirring. After the reaction, the mixture was cooled to room temperature, and the liquid obtained as yellow with little viscosity was distilled under vacuum and passed through an alumina column to obtain a butyl norbornene monomer. All reactions were deoxygenated and run under nitrogen atmosphere. The yield of the product produced by the Diels-Alder reaction was obtained from the weight of the product obtained by passing through a distillation purification and alumina column under reduced pressure, and the purity of the product was gas chromatography equipped with a flame ionization detector (FID) and an AT 1000 column. Was measured. The butyl norbornene monomer production conditions and the yield and purity are shown in Table 1 below.

As shown in Comparative Examples 1 and 2 and Examples 1 and 2, the butyl norbornene monomer of high yield and high purity may be prepared by appropriately adjusting the molar ratio of the starting materials, the reaction temperature, and the reaction time.

Hexyl Norborneen  Preparation of Monomers: Comparative example  3 to 4 and Example  3 to 5

DCPD (dicyclopentadien, Acros, purity 97%) and 1-octene (Aldrich, 98%) were added to a 300 mL high-pressure reactor at a predetermined molar ratio, and the temperature was raised to 200-250 ° C and stirred at 300 rpm for 4-7 hours. Reacted for a while. After the reaction, the mixture was cooled to room temperature, and the resulting liquid was distilled under vacuum to give a pale yellow color with little viscosity to obtain a hexyl norbornene monomer. All reactions were deoxygenated and run under nitrogen atmosphere. The yield of the product produced by the Diels-Alder reaction was determined from the weight of the product obtained by distillation purification under reduced pressure, and the purity of the product was measured by gas chromatography equipped with a flame ionization detector (FID) and an AT 1000 column. Hexyl norbornene monomer preparation conditions and yields and purity are shown in Table 2 below.

As shown in Comparative Examples 3 to 4 and Examples 3 to 5, hexyl norbornene monomers of high yield and high purity may be prepared by appropriately adjusting the molar ratio of the starting materials, the reaction temperature, and the reaction time.

Phenyl Norborneen  Preparation of Monomers: Example  6 to 13 and Comparative example  5, 6

In a 300 mL high-pressure reactor, DCPD (dicyclopentadien, Acros, purity 97%), styrene monomer (99%) and 4-tert-butylcatechol (4-tBC) as polymerization inhibitors were added at a predetermined molar ratio, and then the polymerization inhibitor was completely Melted and stirred for 10 minutes to mix the reactants well. Then, the temperature was raised to 180 ° C and reacted for 4 hours while stirring at 300 rpm (injection of styrene at room temperature).

Alternatively, put 4-tert-butylcatechol with DCPD and a polymerization inhibitor in a 300 mL high pressure reactor, raise the temperature to 150 ~ 180 ℃ and stir at 300rpm, and then the reactor temperature reaches 150 ~ 180 ℃. The styrene monomer was introduced into the sample injection tube or the sampling tube of the reactor at a flow rate of 1.0 to 3.0 cc / min using a liquid transfer pump and reacted for 4 hours (high temperature injection of styrene).

When the addition of the styrene monomer was completed, the reaction was immediately stopped by dropping the temperature to room temperature in order to suppress the production of unnecessary polystyrene. After the reaction was completed, the high viscosity yellow product liquid was vacuum distilled to obtain phenyl norbornene monomer. All reactions were deoxygenated and run under nitrogen atmosphere. The yield of the product produced by the Diels-Alder reaction was determined from the weight of the product obtained by distillation purification under reduced pressure, and the purity of the product was measured by gas chromatography equipped with a flame ionization detector (FID) and an AT 1000 column. The phenyl norbornene monomer preparation conditions and the yield and purity are shown in Table 3 below.

As shown in Example 6, when the phenyl norbornene monomer is prepared, when the styrene monomer is added at room temperature and then the temperature is raised to 180 ° C. for 4 hours, the yield of phenyl norbornene is generally high, but the polystyrene of the corresponding polystyrene is obtained. There is also a problem that a lot of quantity.

When styrene monomer is not added at room temperature, dicyclopentadiene and polymerization inhibitor are first introduced into the reactor at room temperature, and when the mixture thereof is reached at a high temperature of 180 ° C., styrene monomer is added and reacted to yield a phenyl norbornene monomer. Somewhat lower but the amount of polystyrene which is an unnecessary product is reduced (Examples 7 and 8).

In addition, if the reaction is stopped by lowering the reactor temperature to room temperature without continuing the reaction after the completion of the addition of the styrene monomer, the yield of the phenyl norbornene monomer is lowered, but the amount of polystyrene, which is an unnecessary product, is further reduced (Example 10 and 11).

Furthermore, when the styrene monomer is introduced into the reactor at a high temperature of reaction temperature, the styrene monomer is added when the styrene monomer is introduced through the sampling tube of the reactor instead of the sample injection tube (see FIG. 1) attached to the upper part of the reactor. As it vaporizes immediately and is uniformly mixed and reacted by the impeller of the reactor, the yield of the phenyl norbornene monomer can be further reduced while further reducing the production of polystyrene, an unnecessary product (Examples 12 and 13). However, lowering the reaction temperature below 160 ° C. is undesirable since it lowers the yield of the phenyl norbornene monomer to less than 20% (Comparative Examples 5 and 6).

Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the spirit of the present invention, it is obvious that such variations and modifications belong to the appended claims will be.

1 is a view schematically showing the structure of a 300 mL high pressure reactor used for preparing a norbornene monomer including a nonpolar alkyl group according to the present invention.

2 is a gas chromatogram of a butyl norbornene monomer prepared according to Example 2 and vacuum distilled.

3 is a gas chromatogram of hexyl norbornene monomers prepared according to Example 5 and vacuum distilled.

4 is a gas chromatogram of phenyl norbornene monomer prepared according to Example 8 and vacuum distilled.

Claims (11)

Cyclopentadiene, dicyclopentadiene or mixtures thereof, Styrene is mixed at a molar ratio of 1: 1 to 1: 3, and reacted at a temperature of 170 to 240 ° C. for 0.5 to 10 hours, When the cyclopentadiene, dicyclopentadiene or a mixture thereof is introduced into the reactor, and the cyclopentadiene, dicyclopentadiene or a mixture thereof introduced into the reactor reaches a temperature of 170 to 180 ° C, the styrene is Method for producing a norbornene monomer comprising a non-polar alkyl group, characterized in that the reaction is introduced into the reactor. delete delete The method of claim 1, wherein the styrene is introduced into the reactor at a flow rate of 1.0 ~ 5.0cc / min to react the norbornene monomer. The method of claim 1, wherein the reaction is stopped when the styrene is added into the reactor. The method of claim 1, wherein the styrene is introduced through the sample collection tube of the reactor. The method for producing a norbornene monomer according to claim 1, wherein the reaction is performed under a pressure condition of 1 to 25 atmospheres. The method for producing a norbornene monomer according to claim 1, wherein an additional polymerization inhibitor is added during the reaction. The method of claim 8, wherein the polymerization inhibitor is added to the cyclopentadiene, dicyclopentadiene or a mixture thereof and 0.1 to 2.0% based on the total weight of the styrene. The method according to claim 8, wherein the polymerization inhibitor is at least one selected from the group consisting of hydroquinone, benzoquinone, 4-tert-butylcatechol , resorcinol, and Igarnox (Igarnox). The method of claim 10, wherein the iganox is selected from the group consisting of Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1081, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1520, Irganox 1726, and Irganox 245 Manufacturing method.

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