JP2001181383A - Method of manufacturing polyvinylbenzyl ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing polyvinylbenzyl ether compounds of high purity in a high yield which have excellent dielectric properties. SOLUTION: In the method of manufacturing polyvinylbenzyl ether compounds which comprises a step of reacting (A) an aliphatic compound having a hydroxyl group or an aromatic compound having a hydroxyl group with (B) a vinylbenzyl halide in the presence of an alkali, the reaction is carried out while introducing an oxygen-containing gas into the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyvinyl benzyl ether compound. More particularly, the present invention relates to a method for producing a polyvinyl benzyl ether compound having excellent dielectric properties with high purity and high yield.

[0002]

2. Description of the Related Art With the development of electronic technology in recent years, materials for components used in computers, mobile communication devices, and the like are required to have excellent dielectric properties, and various materials have been developed in order to satisfy the requirements. Is being promoted. JP-A-9-
Japanese Patent No. 31006 discloses one of the few materials satisfying the current strict requirements for electric properties, in which an aromatic compound having a hydroxyl group and vinylbenzyl halide are present in a polar neutral solvent in the presence of an alkali or in the presence of a phase transfer catalyst. A method for producing a polyvinyl benzyl ether compound obtained by reacting in a water / organic solvent mixture is disclosed. However, when producing a polyvinyl benzyl ether compound, due to the high reactivity of the vinyl benzyl group,
The polymerization of the vinylbenzyl group proceeds, producing an undesired high molecular weight compound, making the purification operation of the product difficult, the molecular weight of the obtained polyvinylbenzylether compound being unstable, and adversely affecting the quality and properties. May have an effect. In order to prevent this undesired polymerization, it is necessary to use a polymerization inhibitor during the synthesis reaction, but usually, a phenolic polymerization inhibitor or phenothiazine used in a reaction system having a vinyl group produces a polyvinyl benzyl ether compound. Therefore, the effect may not be sufficiently exhibited in the presence of the necessary alkali.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a polyvinyl benzyl ether compound having excellent dielectric properties with high purity and high yield.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors were able to solve the above-mentioned conventional problems.

[0005] That is, the present invention provides a method in the presence of an alkali,
In the method for producing a polyvinyl benzyl ether compound, which comprises the step of reacting (A) an aliphatic compound having a hydroxyl group or an aromatic compound having a hydroxyl group with (B) vinylbenzyl halide, an oxygen-containing gas is reacted during the reaction. An object of the present invention is to provide a method for producing a polyvinyl benzyl ether compound, wherein a reaction is carried out while being introduced into a system.

In the present invention, the component (A) may be an aliphatic compound having two or more alcoholic hydroxyl groups in one molecule or an aromatic compound having two or more phenolic hydroxyl groups in one molecule. To provide a method for producing a polyvinyl benzyl ether compound.

In the present invention, the component (A) is preferably represented by the following general formula (I):

[0008]

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Wherein R ¹ is a methyl group or an ethyl group,
R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
n represents a number of 2 to 6).

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. The reaction between the component (A) and the component (B) can be carried out in a polar neutral solvent in the presence of an alkali, or in a water / organic solvent mixture in which a phase transfer catalyst is present. However, in this reaction, the vinyl benzyl halide as the raw material and the product, polyvinyl benzyl ether compound, are liable to cause a radical reaction in the vinyl benzyl group, and the ordinary synthesis reaction requires a polymerization inhibitor. Therefore, in the present invention, the polymerization of vinylbenzyl groups can be suppressed by introducing an oxygen-containing gas into the reaction system as a polymerization inhibitor. Further, the polymerization can be more effectively prevented than in the case where a conventional phenothiazine and phenol-based polymerization inhibitor are used, and a polyvinylbenzyl ether compound can be obtained with high purity and high yield.

The supply form of the oxygen-containing gas is not particularly limited, and oxygen may be used alone or air may be used. If necessary, it may be used by mixing with another gas, for example, nitrogen, argon or the like. As a supply method, for example, a method in which a cylinder or a compressor is connected to a reaction vessel to supply the same, and the like can be mentioned. Further, as long as the oxygen-containing gas comes into contact with the reaction system, the oxygen-containing gas may be directly blown into the solution or may be simply flowed into the reaction vessel, but it is more effective to blow directly into the solution. In order for oxygen to function as a polymerization inhibitor, it is preferable that 0.1 to 10% by volume of oxygen be present in the reaction system. The supply amount varies depending on the concentration of oxygen, the supply method, and the like, and thus cannot be specified unconditionally.
About 1 to 1% by volume / minute, preferably 0.005 to 0.5%
A volume% / minute is preferred. If the flow rate is too low, the effect as a polymerization inhibitor cannot be obtained, and the polymerization of vinylbenzyl groups tends to proceed. Conversely, if the flow rate is too high, the solvent and the raw materials tend to volatilize, which is not preferable. Further, other polymerization inhibitors, for example, known polymerization inhibitors such as phenothiazine and phenol-based polymerization inhibitors can be used in combination.

Component (A) In the present invention, the aliphatic compound having a hydroxyl group or the aromatic compound having a hydroxyl group used as the component (A) in the present invention may be arbitrarily selected according to the intended use, and commercially available ones are used. You can also. For example, examples of the aliphatic compound having a hydroxyl group include polyols such as ethylene glycol, trimethylolpropane, and pentaerythritol; alicyclic compounds such as 1,4-cyclohexanediol; And phenolic resins such as PP-700-300, PP-10
Phenol resins such as 00-180 and PP-1000-240 (manufactured by Nippon Petrochemical), and halogenated phenols such as tribromophenol and tetrabromobisphenol A. Above all, it is preferable to use a compound represented by the following general formula (I) as the component (A), since the effects of the present invention are more favorably exhibited.

[0013]

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(Wherein R ¹ is a methyl group or an ethyl group,
R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
n shows the number of 2-6).

Component (B) The vinylbenzyl halide used as the component (B) in the present invention includes p-vinylbenzyl chloride, m-vinylbenzyl chloride, a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride. , P-vinylbenzyl bromide, m-vinylbenzyl bromide, a mixture of p-vinylbenzyl bromide and m-vinylbenzyl bromide, and the like.
The production method of the present invention has a polymerization inhibiting effect when any vinylbenzyl halide is used. The mixing ratio of the component (B) is 0.5 to 1 equivalent of the hydroxyl group of the component (A).
About 1.5 equivalents is good. When the equivalent is 0.5 or less, the remaining hydroxyl groups increase, which adversely affects the dielectric properties, which is not preferable. Use of 1.5 equivalents or more is not preferable because it is necessary to remove the unreacted component (B).

As the alkali used in the present invention, alkoxides, hydrides and hydroxides of alkali metals or alkaline earth metals can be used, such as sodium methoxide, sodium ethoxide,
Examples thereof include sodium hydride, sodium hydroxide, sodium borohydride, potassium hydride, and potassium hydroxide. The alkali species may be selected depending on whether the reaction system is a non-aqueous system or a hydrated system. The mixing ratio of alkali is
The equivalent amount of the hydroxyl group of the component (A) is preferably about 1.1 to 3.0 equivalents. If it is less than 1.1 equivalents, the concentration of hydroxyl groups remaining in the resin will increase, which will have an undesirable effect on electrical properties. Use of more than 3.0 equivalents is not preferable because a large amount of a removing solvent such as washing water is used for removing residual alkali.

As the polar neutral solvent that can be used in the present invention, a solvent species that makes the reaction system uniform throughout may be selected according to the kind of the starting material and the reaction conditions. For example, dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane,
1,2-dimethoxypropane, tetramethylene sulfone, hexamethylphosphamide, methyl ethyl ketone,
Examples thereof include methyl isobutyl ketone, acetone, cyclohexanone, butyl alcohol, propyl alcohol, and mixtures thereof. The amount of polar neutral solvent used is
Since the effect differs depending on the solvent type or the reaction temperature, it cannot be unconditionally specified, but in general, for the component (A),
0.5 to 10 times the volume may be used. The reaction temperature and reaction time are 30-100 ° C and 0.5-2
It may be 0 hours.

As the phase transfer catalyst that can be used in the present invention, various onium salts, for example, tetra-n
Quaternary ammonium compounds such as -butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride, and tricaprylmethylammonium chloride; tetra-n-butylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, Quaternary phosphonium compounds such as tetraphenylphosphonium bromide; tertiary sulfonium compounds such as benzyltetramethylene sulfonium bromide; and mixtures thereof. The amount of the phase transfer catalyst to be used cannot be unequivocally specified because its effect varies depending on the type of the catalyst or the reaction temperature. However, generally, about 0.01 to 0.2 equivalent to 1 equivalent of the hydroxyl group of the component (A) is used. Just use it. The reaction temperature and reaction time were 3
The temperature may be 0 to 100 ° C. and 0.5 to 20 hours.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
Unless otherwise specified, parts in the examples mean parts by weight. The method of measurement performed in the examples is shown below. Gel permeation chromatography (GPC):
Shodex GPC System-21 (Column KF-80
2, KF-803, KF-805, manufactured by Showa Denko KK, column temperature 40 ° C, eluate tetrahydrofuran (T
HF), measured at an elution rate of 1 ml / min, and expressed as a standard polystyrene equivalent molecular weight. Dielectric properties: LCR meter 4285A manufactured by Yokogawa Hewlett-Packard Co., Ltd.
It was measured by the equilibrium bridge method using 4285B.

Example 1 5 equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel and an air pump
A phenolic resin PP-700-300 corresponding to the compound represented by the general formula (I) is placed in a liter four-necked flask.
(Mn = 1400, manufactured by NOF CORPORATION) 800 g
(2.5 equivalents), 1400 g of methyl isobutyl ketone, n
-600 g of butyl alcohol was charged, and the flow rate was 50 ml /
The mixture was stirred while blowing air in a minute, and the temperature was increased to 55 ° C. to form a uniform solution. After adding 26.5 g (0.082 mol) of tetra-n-butylammonium bromide,
An aqueous solution of sodium hydroxide (231.5 g of NaOH (purity 95%, 5.5 mol) /231.5 g of water) was added dropwise for 5 minutes, and the temperature after the addition was increased to 60 ° C. Next, vinylbenzyl chloride CMS-AM (m-
420 g (purity: 91%, 2.5 mol) of a / p-isomer: 50/50% by weight mixture (manufactured by Seimi Chemical Co., Ltd.) was added dropwise for 5 minutes, and stirring was continued at 60 ° C. for 5 hours. Air blowing was continued during the reaction. After cooling to room temperature, 1300 g of methyl isobutyl ketone was added for dilution, and then 2.2 L of 1.8N hydrochloric acid was added to neutralize the reaction mixture. 2.2 L of 0.9N hydrochloric acid was added to the organic layer. After washing twice, 4.0 liters of ion-exchanged water was added to the organic layer for washing. Here, a small amount of the organic layer was collected, and the molecular weight was measured by GPC.

Next, the organic layer was poured into 7.0 liters of methanol to precipitate a polyvinyl benzyl ether compound.
The precipitate was further washed twice with 2.0 liters of methanol. After collecting the solid by filtration, 5
As a result of drying at 0 ° C., a polyvinyl benzyl ether compound was obtained in a yield of 90%. The molecular weight of this polyvinyl benzyl ether compound was analyzed by GPC, and as a result, the weight-average molecular weight (Mw) was 3,500, and a high-molecular-weight substance that was considered to have a vinyl benzyl group polymerized was not contained. FIG. 1 shows a GPC chart of the polyvinyl benzyl ether compound obtained from the above organic layer.

Further, the obtained polyvinyl benzyl ether compound is dissolved in THF, and this is coated on a glass plate.
The operation of drying and recoating was repeated, and after laminating to a thickness of 1 mm, a cured product obtained by curing at 120 ° C. for 2 hours, 150 ° C. for 2 hours, and 180 ° C. for 4 hours was cut into a size of 5 × 5 cm. The dielectric constant and dielectric loss tangent at 1 MHz of the test piece were measured. Table 1 shows the results.

Example 2 1 equipped with a temperature controller, a stirrer, a cooling condenser, a dropping funnel and an air pump
Phenoxy resin YP-5 in a 4-liter four-neck flask
0S (Mn = 16000, MWD = 3.94, manufactured by Toto Kasei, structural formula is shown below)

[0024]

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85.2 g (0.3 equivalent) and 483 g of methyl ethyl ketone were charged, stirred while blowing air at a flow rate of 50 ml / min, and heated to 70 ° C. to form a uniform solution. After adding 0.6 g of phenothiazine and 3.2 g (9.84 mmol) of tetra-n-butylammonium bromide, an aqueous sodium hydroxide solution (NaOH 27.8) was added.
g (purity: 95%, 0.66 mol) / water: 27.8 g) was added dropwise for 5 minutes, and the temperature after the addition was increased to 75 ° C. Next, vinylbenzyl chloride CMS-AM
(M- / p-isomer: 50/50% by weight mixture, manufactured by Seimi Chemical Co., Ltd.) 50.4 g (purity 91%, 0.3 mo)
l) was added dropwise for 5 minutes, and stirring was continued at 70 ° C for 5 hours. Air blowing was continued during the reaction. After cooling to room temperature, 180 g of methyl isobutyl ketone was added for dilution, then 300 ml of 1.8 N hydrochloric acid was added to neutralize the reaction mixture, and the organic layer was washed twice with 300 ml of 0.9 N hydrochloric acid. The organic layer was washed by adding 300 ml of ion-exchanged water. Next, the organic layer was poured into 700 ml of methanol to precipitate a polyvinyl benzyl ether compound, and this precipitate was further washed twice with 300 ml of methanol. The solid content was collected and dried to obtain a polyvinyl benzyl ether compound in a yield of 95%. FIG. 2 shows a GPC chart of the obtained polyvinyl benzyl ether compound. The molecular weight of this polyvinyl benzyl ether compound was analyzed by GPC and found to be Mn = 28700, MWD
= 3.64, and no abnormal reaction product was observed.

Further, the obtained polyvinyl benzyl ether compound was cured in the same manner as in Example 1, and the dielectric constant and the dielectric loss tangent at 1 MHz of the produced test piece were measured. Table 1 shows the results.

[0027]

[Table 1]

Comparative Example 1 A polyvinyl benzyl ether compound was produced in the same manner as in Example 1 except that 5.0 g of phenothiazine was used as a polymerization inhibitor without introducing air into the reaction solution used in Example 1. did. The washing step was also performed in the same manner as in Example 1. However, when ion-exchanged water was added to the organic layer for washing, an insoluble emulsion appeared between the organic layer and the aqueous layer, making it difficult to separate the liquid. This insoluble matter is collected and G
As a result of analysis by PC, a very high molecular weight compound having Mw = 1500,000 or more, which is considered to have a vinylbenzyl group polymerized, was confirmed. FIG. 3 shows a GPC chart of the obtained impurity-containing polyvinyl benzyl ether compound.

Further, after removing the aqueous layer and the emulsion-like insoluble matter, a small amount of the organic layer was collected, and the molecular weight was measured by GPC. FIG. 4 shows a GPC chart of the polyvinyl benzyl ether compound obtained here.

The organic layer was poured into 7.0 liters of methanol for precipitation, and this precipitate was washed twice with 2.0 liters of methanol. After filtering and collecting the solids,
As a result of drying at 50 ° C. in a vacuum oven, a polyvinyl benzyl ether compound was obtained in a yield of 70%. The molecular weight of this polyvinyl benzyl ether compound was analyzed by GPC, and as a result, Mw was 8000, and a slight amount of a high molecular weight compound was still contained.

Comparative Example 2 A polyvinyl benzyl ether compound was produced in the same manner as in Example 2 except that no air was introduced into the reaction solution used in Example 2. However, a polyvinyl benzyl ether compound could not be produced due to gelation during the reaction.

From Examples 1 and 2, Comparative Examples 1 and 2, and FIGS. 1 to 4, when only the polymerization inhibitor of the prior art was used, the high molecular weight polymer whose vinylbenzyl group was considered to have polymerized from the GPC results was obtained. Was confirmed to have occurred. However, when an oxygen-containing gas is introduced into the reaction solution as a polymerization inhibitor in the present invention, since no high molecular weight product is generated, the method for producing a polyvinyl benzyl ether compound of the present invention is based on vinyl benzyl during the reaction. It is effective in suppressing the polymerization of groups. Because of the polymerization inhibiting effect, a polyvinyl benzyl ether compound having a high purity can be produced, so that the washing and purifying operation of the product is reduced and the yield can be improved.

[0033]

According to the present invention, there is provided a method for producing a polyvinyl benzyl ether compound which can obtain a polyvinyl benzyl ether compound having excellent dielectric properties in high purity and high yield.

[Brief description of the drawings]

FIG. 1 is a diagram showing a GPC chart of a polyvinyl benzyl ether compound obtained in Example 1.

FIG. 2 is a diagram showing a GPC chart of a polyvinyl benzyl ether compound obtained in Example 2.

FIG. 3 is a GPC chart of a polyvinyl benzyl ether compound containing impurities obtained in Comparative Example 1.

FIG. 4 is a diagram showing a GPC chart of a polyvinyl benzyl ether compound after removing impurities obtained in Comparative Example 1.

Claims (3)

[Claims] 1. A method for producing a polyvinyl benzyl ether compound, comprising the step of reacting (A) an aliphatic compound having a hydroxyl group or an aromatic compound having a hydroxyl group with (B) vinylbenzyl halide in the presence of an alkali. A method for producing a polyvinyl benzyl ether compound, wherein the reaction is carried out while introducing an oxygen-containing gas into the reaction system during the reaction. 2. The composition according to claim 1, wherein the component (A) is an aliphatic compound having two or more alcoholic hydroxyl groups in one molecule or an aromatic compound having two or more phenolic hydroxyl groups in one molecule. The method for producing the polyvinyl benzyl ether compound according to the above. The component (A) is represented by the following general formula (I): (Wherein, R ¹ is a methyl group or an ethyl group, R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 2 to 6). A method for producing an ether compound.