KR101114662B1 - Method for producing polycyclic aromatic vinyl compound - Google Patents

Abstract

Provided are a method for producing a high purity polycyclic aromatic vinyl compound which is difficult to obtain in conventional separation and purification methods such as distillation.

Addition agents such as halogen, hydrogen halide and water to the vinyl group of a polycyclic aromatic vinyl compound such as divinyl naphthalene, divinyl biphenyl or acenaphthylene to form a corresponding polycyclic aromatic vinyl compound derivative, and then recrystallization, adsorption or The polycyclic aromatic vinyl compound derivative is purified by duct separation, and then the addition agent added to the polycyclic aromatic vinyl compound derivative is desorbed to obtain a high purity polyaromatic vinyl compound.

Polyaromatic, Vinyl Compound, High Purity, Tablet, Halogen, Additive

Description

Method for producing polycyclic aromatic vinyl compound {METHOD FOR PRODUCING POLYCYCLIC AROMATIC VINYL COMPOUND}

The present invention relates to a method for producing a polycyclic aromatic vinyl compound useful in electronic materials, optical materials and the like with high purity.

Polycyclic aromatic vinyl compounds are capable of imparting properties such as high heat resistance, low dielectric constant, low dielectric loss, high refractive index, flame retardancy, and low moisture absorption to various polymers, and are expected to be used in a wide range of fields. For example, Japanese Patent Application Laid-Open No. 08-048725 has been applied as a raw material for a resin having high refractive index and high heat resistance. In addition, Japanese Laid-Open Patent Publication No. 2002-018293 discloses that divinylbiphenyl is useful as a raw material of a high heat resistance cation exchange resin. In Japanese Patent Laid-Open No. 2001-294623, acenaphthylene is used as a material for imparting flame retardancy.

The polycyclic aromatic vinyl compound can be produced by coupling, cyclization of a monocyclic aromatic vinyl compound, or dehydrogenation of an ethyl polycyclic aromatic compound, but all of these methods also contain impurities other than the intended polycyclic aromatic vinyl compound, and thus high purity is desired. have. In particular, when a polycyclic aromatic vinyl compound is used as a polymer raw material, it is necessary to make high purity so as not to include impurities having no vinyl group as much as possible, since the performance of strength, heat resistance, dielectric properties, etc. of the produced polymer is lowered.

However, since polycyclic aromatic vinyl compounds have a high boiling point and are easy to polymerize, it is practically impossible to apply distillation used to prepare high purity products in monocyclic vinyl compounds. For example, Japanese Patent Laid-Open No. 11-140001 discloses nitroso such as N-nitroso-N, N'-di-pentyl-p-phenylenediamine when the vinyl compound is distilled at 65 to 150 ° C. The polymerization of the vinyl compound is prevented by adding the compound as a polymerization inhibitor. However, since polycyclic aromatic vinyl compounds are generally high boiling point, distillation is required in ultra-high vacuuming, and the polymerization inhibitor used here is volatilized and polymerization occurs during distillation.

Although Japanese Unexamined Patent Publication No. 10-139696 describes the high purity of divinyl biphenyl by adsorption, a high yield of divinyl biphenyl close to 100% requires a large number of stages and is not industrial. . In addition, about divinyl biphenyl, even if it cooled to -30 degreeC, crystal did not precipitate, and the purity improvement by cooling crystal precipitation was practically impossible.

A method for purifying hexen is disclosed on page 71 of "The Basics of Organic Chemistry" (co-authored by R.S.MONSON and J.C.SHELTON, issued by Tokyo Kagakudoujin). In this method, the unsaturated bonding portion of hexene containing impurities near its boiling point is easily added to bromine to be dibrohexane, and the difference in boiling point between dibrohexane and impurities is increased to facilitate distillation purification. Bromine, which is an adduct from hexane, is easily debrominated to be hexene. However, this method is difficult to apply to the separation of polyaromatic compounds that are difficult to distill.

An object of the present invention is to provide a method for producing a high-purity polycyclic aromatic vinyl compound by purifying a polycyclic aromatic vinyl compound that cannot be purified by conventional methods such as distillation, recrystallization, and adsorption.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, as a result, it isolate | separates with a non-vinyl-group containing compound by adding a halogen etc. to a vinyl group of a polycyclic aromatic vinyl compound, and once protecting it, and changing the characteristic largely, It has been found that high purity polyaromatic vinyl compounds can be prepared by desorbing the adduct after purification, and the present invention has been completed.

The present invention is to separate and prepare a polycyclic aromatic vinyl compound from a polycyclic aromatic vinyl compound-containing oil, (1) an addition step of adding hydrogen halide, halogen or water as an additive to a vinyl group of the polycyclic aromatic vinyl compound; (2) a purification step of purifying the polycyclic aromatic vinyl compound derivative produced in the addition step by at least one purification method selected from recrystallization, adsorption and adduct separation, and (3) an additive from the purified polycyclic aromatic vinyl compound derivative. It is a method for producing a polycyclic aromatic vinyl compound, characterized in that the desorption process of the deadditives.

The polycyclic aromatic vinyl compound may be at least one selected from monovinyl biphenyl, divinylbiphenyl, monovinyl naphthalene, divinylnaphthalene and acenaphthylene. Can be mentioned. Moreover, in the case of divinyl biphenyl, 3,3'- divinyl biphenyl is mentioned, It is preferable that the purification method in a refinement | purification process is recrystallization.

As a polycyclic aromatic vinyl compound containing oil used as a raw material in this invention, there exists a crude polycyclic aromatic vinyl compound, for example. The crude polycyclic aromatic vinyl compound can be prepared by coupling, cyclizing or dehydrogenating an ethyl polycyclic aromatic compound of the monocyclic aromatic vinyl compound. This crude polycyclic aromatic vinyl compound is advantageous to remove components having low boiling point and easy separation such as moisture and solids in advance.

For example, divinyl biphenyl and divinyl naphthalene are obtained by dehydrogenating diethylbiphenyl and diethylnaphthalene. In addition to addition of monoethylvinylbiphenyl and monoethylvinylnaphthalene, various isomers are produced or not. In many cases, the reaction raw material remains. The method of the present invention is effective for separation of divinyl compounds and monovinyl compounds or separation of isomers having different positions of substitution of vinyl groups. In addition, dehydrogenation of acenaphthene yields acenaphthylene, which also contains impurities such as unreacted acenaphthene. Therefore, the polycyclic aromatic vinyl compound-containing oil which is a raw material in the present invention contains the above impurity, and the content of the vinyl compound for the purpose of high purity is 5 wt% or more, preferably 10 wt% or more, more preferably. It is about 20 to 90wt%.

In the addition step, the substance added to the vinyl group of the polycyclic aromatic vinyl compound (hereinafter, referred to as an additive) may be stable in the added state and can be detached later. Hydrogen halide, halogen and One kind selected from water is used as the additive. Meanwhile, halogen in the present invention is usually represented by X ₂ , and hydrogen halide is usually represented by HX. X represents F, Cl, Br or I, but is preferably Cl, Br or I.

As the hydrogen halide to be used as the additive, hydrogen bromide, hydrogen chloride and hydrogen iodide are preferable. As addition temperature, 0 degreeC-200 degreeC is preferable. By addition of hydrogen halide, H and X atoms are added to each carbon of the vinyl group, and olefinic double bonds disappear.

As the halogen used as the additive, liquid bromine and chlorine gas are preferable. Fluorine is not preferred because it is too reactive and iodine is too weak. The addition reaction of liquid bromine and chlorine gas proceeds without catalyst. As addition temperature, -20 degreeC-100 degreeC is preferable. By addition of halogen, two X atoms in total are added to each carbon of the vinyl group, and the olefinic double bond disappears.

When water is used as the additive, the addition is preferably performed in the presence of an acid catalyst. As the acid catalyst, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and solid acid catalysts such as zeolite are preferable. The addition temperature is preferably 0 ° C. to 200 ° C. for the photoacid and 50 ° C. to 300 ° C. for the solid acid catalyst. By addition of water, H atom and OH group are added to each carbon of the vinyl group, and the olefinic double bond disappears.

Solvents may be used in all addition reactions. Examples of the solvent used include alcohols such as methanol, ethanol and propanol, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, paraffins such as hexane, heptane, cyclohexane and methylcyclohexane, methyl acetate, ethyl acetate and acetic acid. Oxygen esters, such as acetate esters, such as a propyl, dioxane, tetrahydrofuran, and dimethyl carbonate, etc. are mentioned, It is not limited to these.

After completion of the addition step, a purification step is performed to separate the target polycyclic aromatic vinyl compound and other components.

Since the polycyclic aromatic vinyl compound derivative obtained in the addition step does not have an olefinic double bond, high purity is applied by applying a general purification method. The purification method used in the present invention requires any one of recrystallization, adsorption and adduct separation, but other separation methods other than these may be used in combination. As another separation method, operations such as washing, drying and extraction can be considered. On the other hand, recrystallization herein refers to a series of operations in which a liquid substance or a slurry-like substance in which solids are precipitated is cooled to precipitate a sufficient amount of crystals, solid-liquid separation, rinsing, and recrystallization to obtain high purity crystals. The addition of the additive to the vinyl group results in the loss of polymerizability and the dissociation of the vinyl compound and the non-vinyl compound. In addition, when the monovinyl compound and the divinyl compound are separated, the same effect as described above occurs with a difference in degree. Since the purity of the polycyclic aromatic vinyl compound derivative in this process becomes the purity of the polycyclic aromatic vinyl compound of the intended final product, it is necessary to increase the purity of the polycyclic aromatic vinyl compound derivative to the purity required by the final product.

Next, a de-adding agent step of desorbing the additive from the high-purity polycyclic aromatic vinyl compound derivative obtained in the purification step is carried out to obtain a high-purity polycyclic aromatic vinyl compound as a target. In this process, the deintercalation reaction of the added additive is caused briefly.

The desorption reaction of the high-purity polycyclic aromatic vinyl compound derivative to which hydrogen halide is added dehydrohalogenates using a basic reagent to regenerate the vinyl group. As a basic reagent, what melt | dissolved alkali hydroxide in water or alcohol can be used, Especially, it is preferable to use potassium hydroxide melt | dissolved in ethanol. The vinyl group is also regenerated by dehydration after replacing the added halogen atom with a hydroxyl group.

In the desorption reaction of a high purity polycyclic aromatic vinyl compound derivative added with halogen, dehalogenation is carried out using a metal reagent or the like to regenerate the vinyl group. Examples of the dehalogenating agent include, but are not limited to, metal zinc. In the case of using metal zinc, the desorption temperature is preferably 30 ° C to 150 ° C.

In the desorption reaction of a high purity polycyclic aromatic vinyl compound derivative added with water, dehydration is carried out using an acid catalyst to regenerate the vinyl group. As the acid catalyst, mineral acids such as sulfuric acid and phosphoric acid, solid acids such as alumina and zeolite can be used.

Solvents may be used in the desorption of all additives. Examples of the solvent used include alcohols such as methanol, ethanol and propanol, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, paraffins such as hexane, heptane, cyclohexane and methylcyclohexane, methyl acetate, ethyl acetate and acetic acid. Oxygen esters, such as acetate esters, such as a propyl, dioxane, tetrahydrofuran, and a dimethyl carbonate, etc. are mentioned, It is not limited to these.

In addition, when the operation temperature of a desorption reaction is 10 degreeC or more, it is preferable to add superposition | polymerization inhibitors, such as tertiary-butylcatechol.

After completion of the desorption reaction, a suitable high purity polycyclic aromatic vinyl compound can be obtained by appropriate post-treatment as necessary.

Embodiment

Hereinafter, although the Example of this invention is described, this invention is not limited to an Example.

Example 1

Table 1 shows the composition of the raw divinyl biphenyl as a raw material. 625 g of raw divinylbiphenyl was dissolved in 625 g of toluene and cooled to 5 ° C while stirring. After cooling, 500 g of bromine was slowly dropped while maintaining the reaction temperature at 5 to 20 ° C. Crystals began to precipitate when approximately half of the bromine was dropped. The bromine was dropped and then filtered to recover white crystals. Furthermore, recrystallization was performed twice using toluene as a solvent to obtain 114.5 g of 3,3'-di (1,2-dibromethyl) biphenyl.

114.5 g of recrystallized purified 3,3'-di (1,2-dibromethyl) biphenyl and 0.3 g of tert-butylcatechol were added to a mixed solvent of 458 g of toluene and 19.8 g of pure water, with stirring. Heated to 80 ° C. While maintaining the reaction temperature at 80 ~ 90 ℃ was added little by little until the zinc powder is not dissolved. After completion of the zinc addition, the mixture was washed three times with 1000 ml of water, and then toluene was distilled off using a rotary evaporator to obtain 50.1 g of 3,3'-divinylbiphenyl having a purity of 99.0%.

ingredient ratio(%) Biphenyl 2.2 Methylbiphenyl 1.8 Dimethylbiphenyl 0.6 Ethyl biphenyl 0.9 Vinyl biphenyl 4.9 Methylethylbiphenyl 1.0 Methylvinylbiphenyl 11.2 Diethylbiphenyl 13.1 Ethyl vinyl biphenyl 19.3 Divinylbiphenyl
(My 3,3'-divinylbiphenyl) 43.8
(22.3) Phenylbiphenyl 1.0 Sum 100.0

[Example 2]

625 g of the same raw divinylbiphenyl as in Example 1 was dissolved in 156 g of toluene and 156 g of n-heptane and cooled to 5 ° C while stirring. After cooling, 500 g of bromine was slowly dropped while maintaining the reaction temperature at 5 to 20 ° C. Crystals began to precipitate when approximately half of the bromine was dropped. The bromine was dropped and then filtered to recover white crystals. Furthermore, recrystallization was performed twice using toluene as a solvent to obtain 126.0 g of 3,3'-di (1,2-dibromethyl) biphenyl.

126.0 g of purified 3,3'-di (1,2-dibromethyl) biphenyl and 0.3 g of tert-butylcatechol are added to a mixed solvent of 458 g of dioxane and 45.8 g of pure water, and stirred to 80 ° C. Heated. While maintaining the reaction temperature at 80 ~ 90 ℃ was added little by little until the zinc powder is not dissolved. After completion of the zinc addition, the mixture was washed three times with 1000 ml of water, and then dioxane was distilled off using a rotary evaporator to obtain 55.0 g of 3,3'-divinylbiphenyl having a purity of 99.0%.

Comparative Example 1

After adding 0.5 g of tert-butylcatechol to 500 g of the same raw divinyl biphenyl as in Example 1, distillation under reduced pressure was carried out at 5 torr. However, distillation was impossible because a polymer was produced in the column of the distillation column and the column was blocked.

Comparative Example 2

To 100 g of the same raw divinyl biphenyl as in Example 1, 0.5 times the amount of the solvent shown in Table 2 was added and cooled to -30 ° C. As a result, crystal precipitation did not occur in either case. Raw vinyl biphenyls, on the other hand, are liquid at room temperature.

menstruum Properties after cooling Solvent free High viscosity toluene High viscosity n-hexane 2-layer separation Methanol 2-layer separation Isopropanol 2-layer separation

Example 3

The composition of the raw acenaphthylene used as a raw material is shown in Table 3. 500 g of raw acenaphthylene was dissolved in 500 g of toluene and cooled to 5 ° C while stirring. After cooling, 474 g of bromine was slowly dropped while maintaining the reaction temperature at 5 to 10 ° C. Crystals began to precipitate when approximately half of the bromine was dropped. The bromine was dropped and then filtered to recover the crystals. Furthermore, recrystallization was performed twice using toluene as a solvent to obtain 321 g of 1,2-dibromacenaphthylene.

321 g of purified 1,2-dibromacenaphthylene and 0.2 g of tert-butylcatechol were added to a mixed solvent of 321 g of tetrahydrofuran and 15.8 g of pure water and heated to 80 ° C while stirring. While maintaining the reaction temperature at 80 ~ 90 ℃ was added little by little until the zinc powder is not dissolved. After completion of the zinc addition, the mixture was washed three times with 1000 ml of water, and then tetrahydrofuran was distilled off by a rotary evaporator to obtain 185 g of acenaphthylene having a purity of 99.9%.

ingredient ratio(%) naphthalene 0.79 1-methylnaphthalene 1.40 Acenaphthene 2.80 Acenaphthylene 94.83 Unknown 0.18 Sum 100.00

According to the method for producing a polycyclic aromatic vinyl compound of the present invention, it becomes possible to obtain a high-purity polycyclic aromatic vinyl compound that has been difficult with conventional methods such as recrystallization and distillation. Conventional low-purity polycyclic aromatic vinyl compounds have been difficult to resinize themselves, but the high-purity polycyclic aromatic vinyl compounds obtained in the present invention have no impurities that inhibit the resination, and have high heat resistance, low dielectric constant and low properties for various polymer polymers. Properties such as dielectric loss, high refractive index, flame retardant, and low moisture absorption can be provided, which can be widely used in the field of electronic materials and optical materials utilizing these characteristics.

Claims (7)

(1) an addition step of adding hydrogen halide, halogen, or water as an additive to the vinyl group of the polycyclic aromatic vinyl compound, in addition to producing the polycyclic aromatic vinyl compound from the oil containing the polycyclic aromatic vinyl compound, (2) A polycyclic aromatic polyvinyl aromatic derivative comprising: a purification step of refining the polycyclic aromatic vinyl compound derivative produced in the step by recrystallization; and (3) a polyaddition step of removing an additive from the purified polycyclic aromatic vinyl compound derivative. Method for producing aromatic vinyl compound. The method according to claim 1, wherein the polyaromatic vinyl compound is at least one selected from monovinylbiphenyl, divinylbiphenyl, monovinylnaphthalene, divinylnaphthalene, and acenaphthylene. The method according to claim 1, wherein the polycyclic aromatic vinyl compound is at least one of monovinylbiphenyl and divinylbiphenyl. The method according to claim 1, wherein the polycyclic aromatic vinyl compound is at least one of monovinyl naphthalene and divinyl naphthalene. The method according to claim 1, wherein the polyaromatic vinyl compound is acenaphthylene. The method according to claim 1, wherein the polyaromatic vinyl compound is 3,3'-divinylbiphenyl. The method according to claim 1, wherein the polyaromatic vinyl compound is 3,3'-divinylbiphenyl and the purification method in the purification step is recrystallization.