WO2019176855A1 - ポリ（ビニルベンジル）エーテル化合物の製造方法 - Google Patents

ポリ（ビニルベンジル）エーテル化合物の製造方法 Download PDF

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WO2019176855A1
WO2019176855A1 PCT/JP2019/009689 JP2019009689W WO2019176855A1 WO 2019176855 A1 WO2019176855 A1 WO 2019176855A1 JP 2019009689 W JP2019009689 W JP 2019009689W WO 2019176855 A1 WO2019176855 A1 WO 2019176855A1
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ether compound
vinylbenzyl
poly
compound
solvent
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PCT/JP2019/009689
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French (fr)
Japanese (ja)
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賢志 村上
利治 門脇
敏之 大西
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第一工業製薬株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment

Definitions

  • the present invention relates to a method for producing a poly (vinylbenzyl) ether compound.
  • Poly (vinyl benzyl) ether compound is used as a material for electronic devices that handle high-frequency signals because of its excellent dielectric properties and hygroscopic heat resistance.
  • a poly (vinylbenzyl) ether compound for example, a polyphenylene ether compound and a halogenated methylstyrene (vinylbenzyl halide) are reacted in a toluene solution in the presence of an alkali metal hydroxide, followed by this reaction.
  • a method is disclosed in which a solution is neutralized with an acid, washed, and then reprecipitated with a large amount of methanol (Patent Document 1).
  • Patent Document 1 it is possible to remove the halogen-based compound and halide ions, but since the purification step by reprecipitation is included, the yield decreases and the process time becomes long, so the production cost Improvement in terms is desired.
  • halogen-based compound epichlorohydrin: boiling point: about 118 ° C.
  • vacuum distillation is used as described in the example of Patent Document 2, for example.
  • the boiling point of halogenated methylstyrene (chloromethylstyrene) used in the present invention is 229 to 240 ° C., it is difficult to remove it by distillation under reduced pressure.
  • the reaction solution obtained in the reaction step is treated with an alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst. This has a removal step of removing unreacted vinyl benzyl halide, and there is room for further improvement in yield and production cost.
  • JP 2009-96953 A Japanese Patent Application Laid-Open No. 10-036484 JP 2014-189781 A
  • the present invention has been made in view of the above problems, and is a method for producing a poly (vinylbenzyl) ether compound, which can reduce the production cost while reducing the residual amount of halogen-based compounds and halide ions.
  • An object of the present invention is to provide a simple manufacturing method.
  • the present inventor used a halogenated methylstyrene having a low content of a specific by-product, and performing a reaction step in a solvent having a predetermined formulation, thereby allowing reprecipitation and the like. It has been found that the remaining amount of halogen compounds and halide ions can be reduced without going through a purification step.
  • the method for producing a poly (vinylbenzyl) ether compound of the present invention is a method for producing a poly (vinylbenzyl) ether compound by reacting a compound having a phenolic hydroxyl group with halogenated methylstyrene, In a solvent containing an aromatic hydrocarbon and an aprotic polar solvent in the presence of an aqueous alkali metal hydroxide solution, a compound having a protic hydroxyl group and a halogenated methylstyrene represented by the following general formula (1): Including a dihalide compound represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine) in the halogenated methylstyrene, including a reaction step of reacting The amount is 1.5% by mass or less, and the content of the aprotic polar solvent in the solvent is 5% by mass or more.
  • X represents any atom selected from chlorine and bromine.
  • the compound having a phenolic hydroxyl group has a repeating unit represented by the formula (2) or (3) and has a phenolic hydroxyl group at its terminal, a terpene phenol resin, a dicyclopentadiene phenol resin, and It can be at least one selected from the group consisting of polyvinylphenol resins.
  • R 1 to R 16 are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and A is a linear, branched or cyclic group having 20 or less carbon atoms And m and n each represents an integer of 0 to 100, at least one of which is not 0.
  • R 17 to R 20 are independently selected hydrogen atoms or carbon atoms of 1 to 5 Wherein o is an average value of the number of repeating units and represents an integer of 1 to 100.
  • the concentration of the alkali metal hydroxide aqueous solution may be 1.0 to 50.0% by mass.
  • the aromatic hydrocarbon may be one or two selected from the group consisting of toluene and xylene.
  • the solvent may further contain one or a mixture of two or more selected from the group consisting of aliphatic alcohols having 3 to 6 carbon atoms.
  • the aprotic polar solvent may be one or a mixture of two or more selected from the group consisting of dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone and propylene carbonate.
  • the production cost can be reduced, and the poly (vinylbenzyl) ether compound has a high purity, a low halogen compound, and a halide ion concentration. Can be obtained.
  • 6 is a chart showing measurement results of gas chromatography of chloromethylstyrene used in Examples 4 and 7 to 13 of the present invention.
  • the method for producing a poly (vinylbenzyl) ether compound of the present invention is a method for producing a poly (vinylbenzyl) ether compound by reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene, which comprises a phenolic hydroxyl group.
  • the dihalide compound content is 1.5% by mass or less
  • the aprotic polar solvent in the reaction solvent is 5% by mass or more. And the.
  • a dihalogenated organic compound represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine)
  • X represents any atom selected from chlorine and bromine
  • X is chlorine, it may be a dichloro compound.
  • X represents any atom selected from chlorine and bromine.
  • halogenated methylstyrene When halogenated methylstyrene is produced by a known method, it is obtained as a mixture of (mono) halogenated methylstyrene represented by general formula (1) and a by-product, and details of the by-product are not clear, It is considered that isopropenyl halogenated benzene, a dihalide compound described later, di (methyl halide) styrene and the like are contained. In the present specification, the term “halogenated methylstyrene” is a concept including these by-products.
  • halogenated methylstyrene represented by the general formula (1) include, for example, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, Examples thereof include p-bromomethylstyrene, and a mixture of two or more selected from these can be used as it is.
  • the halogenated methylstyrene it is represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine).
  • the content of the dihalide compound is 1.5% by mass or less, preferably 1.2% by mass or less, and more preferably 1.0% by mass or less, based on the total amount of methyl halide styrene.
  • Specific examples of the dihalide compound include dichloromethylstyrene, chloro (chloromethyl) styrene, dibromomethylstyrene, bromo (bromomethyl) styrene, and the like.
  • the content of the dihalide compound is 1.5% by mass or less, a low halogen compound and a poly (vinylbenzyl) ether compound having a halide ion concentration are easily obtained.
  • the blending ratio of the halogenated methylstyrene used in the present invention is preferably 1.01-1.50 mol, preferably 1.05-1.30 mol, based on 1 mol of the hydroxyl group of the compound having a phenolic hydroxyl group. More preferably, it is a mole.
  • the amount is less than 1.01 mol, the reaction rate decreases and the number of remaining hydroxyl groups increases. Therefore, when used as a material for electronic materials, there is a tendency for performance to deteriorate. The time for removing unreacted methyl styrene styrene tends to be long.
  • a compound which has a phenolic hydroxyl group used by this invention has a repeating unit shown by the following general formula (2) or (3), and has a phenolic hydroxyl group at the terminal.
  • examples thereof include polyphenylene ether compounds, terpene phenol resins, dicyclopentadiene phenol resins, and polyvinyl phenol resins.
  • R 1 to R 16 are independently selected hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and A is linear, branched or A cyclic divalent hydrocarbon group, and m and n each represents an integer of 0 to 100, at least one of which is not 0.
  • a in the general formula (2) is, for example, methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1-methylethylidene). ), Cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene and the like, but are not limited thereto.
  • polyphenylene ether compound represented by the general formula (2) examples include 2,2-bis (4-hydroxy-3,5-methylphenyl) propane ⁇ 2,6-dimethylphenol polycondensate, 2,2- Bis (4-hydroxy-3,5-methylphenyl) propane ⁇ 2,3,6-trimethylphenol polycondensate, 4,4'-methylenebis (2,6-dimethylphenol) ⁇ 2,6-dimethylphenol polycondensation Products, 4,4′-methylenebis (2,6-dimethylphenol) ⁇ 2,3,6-trimethylphenol polycondensate, and the like, but are not limited thereto.
  • These polyphenylene ether compounds can be produced by known methods, and the production method is not particularly limited, and commercially available products can also be used.
  • the polyphenylene ether compound represented by the general formula (3) used in the present invention is a hydrogen atom or a carbon number of 1 to 5 in which R 17 to R 20 are independently selected in the general formula (3).
  • polyphenylene ether compound represented by the general formula (3) examples include 2,6-dimethylphenol polycondensate and 2,3,6-trimethylphenol polycondensate, but are not limited thereto. is not.
  • These polyphenylene ether compounds can be produced by known methods, and the production method is not particularly limited, and commercially available products can also be used.
  • the aqueous alkali metal hydroxide solution used in the present invention is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide and a mixture thereof.
  • the blending ratio of the aqueous alkali metal hydroxide solution is not particularly limited, but is preferably 1.2 to 4.0 mol with respect to 1 mol of the hydroxyl group of the compound having a phenolic hydroxyl group. When it is 1.2 mol or more, the reaction time tends to be short, and when it is 4.0 mol or less, an unreacted alkali compound hardly remains. Further, the concentration of the aqueous alkali metal hydroxide solution is not particularly limited, but is preferably 1.0 to 50.0% by mass from the viewpoint of allowing the reaction to proceed more rapidly.
  • aromatic hydrocarbon used as a solvent in the present invention examples include benzene, toluene, ethylbenzene, xylene, ethyltoluene and the like. Of these, toluene or xylene is preferred from the viewpoint of easy availability and easy removal by reduced pressure.
  • the content of the aromatic hydrocarbon is not particularly limited, but is preferably 50 to 95% by mass, more preferably 60 to 90% by mass in the total amount of the solvent.
  • the aprotic polar solvent used in the present invention is not particularly limited, and examples thereof include dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, propylene carbonate and the like. Among these, easy handling and From the viewpoint of ease of removal, dimethyl sulfoxide, dimethyl formaldehyde, and acetonitrile are preferably used.
  • the content of the aprotic polar solvent is 5% by mass or more and preferably 10% by mass or more in the total amount of the solvent.
  • a low halogen compound and a poly (vinylbenzyl) ether compound having a halide ion concentration can be easily obtained.
  • the solvent may contain an aliphatic alcohol together with the aromatic hydrocarbon and the aprotic polar solvent, and the aliphatic alcohol is an aliphatic alcohol having 3 to 6 carbon atoms. It may be one or a mixture of two or more selected from the group.
  • the aliphatic alcohol is preferably an aliphatic alcohol having 3 to 6 carbon atoms.
  • n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, 2-ethyl examples include butanol and n-hexanol.
  • aliphatic alcohols having 3 or 4 carbon atoms are particularly preferred from the viewpoint that they can be easily removed under reduced pressure.
  • the content is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less in the total amount of the solvent. Is more preferable.
  • the total amount of the solvent used during the reaction is preferably 100 to 300 parts by mass with respect to 100 parts by mass of the compound having a phenolic hydroxyl group. If it is smaller than the above range, the viscosity of the reaction system becomes high and unreacted raw materials are likely to remain, and if it is larger than the above range, the yield per volume of the reaction vessel of the poly (vinylbenzyl) ether compound tends to decrease. .
  • reaction conditions are not particularly limited, and the reaction may be performed according to a conventionally used method. That is, for example, a compound having a phenolic hydroxyl group, halogenated methylstyrene and a solvent can be mixed and stirred, and the reaction can be carried out while dropping an alkali metal hydroxide thereto.
  • the reaction temperature is usually about 60 to 100 ° C., and the reaction time is about 2 to 16 hours.
  • the reaction solution obtained in the above reaction step can be neutralized by a conventionally used method. That is, for example, an organic solvent such as toluene or isopropanol and water are added to the reaction solution, and then neutralized with an acid such as hydrochloric acid.
  • the amount of the organic solvent and water used is not particularly limited, but the mass ratio of water / organic solvent is preferably 40/60 to 5/95, and more preferably 30/70 to 10/90.
  • the neutralization solution obtained in the neutralization step can be further reduced in halide ion concentration by washing with a mixed solution of water and an aliphatic alcohol as necessary.
  • aliphatic alcohol used in the washing those usable for the reaction solvent described above can be used.
  • the amount of water used is preferably a water / aliphatic alcohol mass ratio of 99/1 to 20/80, more preferably 90/10 to 30/70.
  • the ratio of the aliphatic alcohol is smaller than the above range, it may take a long time to separate the organic layer and the aqueous layer, or an intermediate layer may be formed between the organic layer and the aqueous layer. Moreover, when larger than the said range, a product will become easy to melt
  • the amount of the mixed liquid composed of water and aliphatic alcohol used per washing is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the polyphenylene ether compound. If it is smaller than the above range, the washing tends to be insufficient, and if it is larger than the above range, the amount of the poly (vinylbenzyl) ether compound that is a product increases and the yield may be reduced.
  • liquid-liquid separation may be performed according to a conventional method, and the target product can be obtained by performing dehydration and filtration after washing.
  • ⁇ Measurement condition> Column: “DB-1” manufactured by Agilent Technologies, inner diameter 0.32 mm ⁇ length 30 m, film thickness 0.25 ⁇ m ⁇ Measurement temperature: Hold at 100 ° C. for 1 minute, then heat up at ⁇ 10 ° C./min and hold at ⁇ 280 ° C. for 3 minutes. ⁇ Inlet temperature: 300 ° C. -Detection port temperature: 300 ° C
  • Example 1 A polyphenylene ether compound represented by the general formula (2) (R 1 , R 3 , R 5 , R 7 in the general formula (2) is added to a 2 L four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel.
  • R 10 , R 12 , R 14 , R 16 are methyl groups
  • R 2 , R 4 , R 6 , R 8 , R 9 , R 11 , R 13 , R 15 are hydrogen
  • A is isopropylidene group
  • m + n An average of 12 and a number average molecular weight of 1580) of 158 g (0.1 mol), 221 g of toluene, and 94.8 g of dimethyl sulfoxide (hereinafter referred to as DMSO) were charged to obtain a homogeneous solution, followed by tetra-n-butylammonium bromide, 0.1%.
  • DMSO dimethyl sulfoxide
  • the solution was filtered, and 345 g of a 50% toluene solution of vinylbenzylated polyphenylene ether compound (yield based on polyphenylene ether compound). 95%, hereinafter referred to as product).
  • the vinyl benzylated polyphenylene ether compound has a residual chloromethylstyrene amount (in terms of solid content) of less than 0.1%, a hydrolyzable chlorine amount of 76 ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,680. Met.
  • Example 2 The same operation as in Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to a dichloro compound content of 0.1% and a di (chloromethyl) styrene content of 0.0%, 345 g of product (yield 95% based on polyphenylene ether compound) was obtained.
  • the amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 103 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 3 The same operation as in Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to a dichloro compound content of 0.3% and a di (chloromethyl) styrene content of 0.0%, 345 g of product (yield 95% based on polyphenylene ether compound) was obtained.
  • the amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 169 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 4 The same operation as in Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to a dichloro compound content of 0.8% and a di (chloromethyl) styrene content of 0.0%, 345 g of product (yield 95% based on polyphenylene ether compound) was obtained.
  • the amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 227 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 5 The same operation as in Example 1 was carried out except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 1.1% and a di (chloromethyl) styrene content of 0.0%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 409 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 6 The same operation as in Example 1 was carried out except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 1.5% and a di (chloromethyl) styrene content of 0.0%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 595 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 7 The same operation as in Example 4 was carried out except that the amount of solvent used in the reaction was changed to 189.5 g of toluene and 126.3 g of DMSO to obtain 345 g of product (yield 95% based on polyphenylene ether compound). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 210 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 8 The same operation as in Example 4 was carried out except that the solvent species and amount used in the reaction were changed to 221 g of toluene, 31.6 g of isopropanol, and 63.2 g of DMSO to obtain 345 g of product (yield 95% based on polyphenylene ether compound). It was. The amount of residual chloromethylstyrene in the obtained product was 0.2%, the amount of hydrolyzable chlorine was 310 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 9 The same operation as in Example 4 was carried out except that the solvent type and amount used in the reaction were changed to 221 g of toluene, 63.2 g of isopropanol, and 31.6 g of DMSO to obtain 345 g of product (yield 95% based on polyphenylene ether compound). It was. The amount of residual chloromethylstyrene in the obtained product was 0.3%, the amount of hydrolyzable chlorine was 350 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 10 The same operation as in Example 4 was carried out except that the solvent species used in the reaction was changed from 221 g of toluene to 221 g of xylene to obtain 345 g of product (yield 95% based on polyphenylene ether compound). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 220 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 11 The same operation as in Example 10 was carried out except that the solvent species used in the reaction was changed from 94.8 g of DMSO to 94.8 g of N, N-dimethylformamide (DMF), and 345 g of product (yield 95 based on polyphenylene ether compound). %).
  • the amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 235 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 12 The same operation as in Example 5 was performed except that the polyphenylene ether compound used in the reaction was changed to 140 g (0.1 mol) of phenol resin A (terpene phenol resin, phenol amount 1,400 g / mol), and 273 g of product ( Yield 90% based on terpene phenol resin). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, and the amount of hydrolyzable chlorine was 212 ppm.
  • phenol resin A terpene phenol resin, phenol amount 1,400 g / mol
  • product Yield 90% based on terpene phenol resin
  • Example 13 The same operation as in Example 5 was carried out except that the polyphenylene ether compound used in the reaction was changed to 33.7 g (0.1 mol) of phenol resin B (dicyclopentadiene phenol resin, phenol amount 337 g / mol). 81.8 g (yield 90% based on dicyclopentadiene phenol resin) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, and the amount of hydrolyzable chlorine was 234 ppm.
  • phenol resin B dicyclopentadiene phenol resin, phenol amount 337 g / mol
  • Example 1 The same operation as in Example 5 was carried out except that the solvent species and amount used in the reaction were changed to 221 g of toluene and 94.8 g of isopropanol to obtain 345 g of product (yield 95% based on polyphenylene ether compound).
  • the amount of residual chloromethylstyrene in the obtained product was 1.0%
  • the amount of hydrolyzable chlorine was 2290 ppm
  • the number average molecular weight was 2,180
  • the weight average molecular weight was 3,650.
  • Comparative Example 3 The same operation as in Comparative Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 0.0% and a di (chloromethyl) styrene content of 0.9%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was 0.9%, the amount of hydrolyzable chlorine was 1800 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Example 4 The same operation as in Example 1 was carried out except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 3.9% and a di (chloromethyl) styrene content of 0.0%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 2132 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
  • Table 1 shows the reactants, solvents, and presence / absence of purification in each of the above Examples and Comparative Examples together with the amount of residual chloromethylstyrene and the amount of hydrolyzable chlorine in the obtained product.
  • Example 1 to 13 the amount of residual chloromethylstyrene and hydrolyzable chlorine in the poly (vinylbenzyl) ether compound could be reduced without going through a purification step by reprecipitation.
  • the reaction solvent does not contain an aprotic polar solvent.
  • the compound obtained in Comparative Example 1 could be reduced to the same level as in Comparative Example 2 subjected to the purification step by reprecipitation.
  • Example 2 shows that from the comparison between Example 1 and Example 2, among the by-products contained in the halogenated methylstyrene, the influence on the hydrolyzable chlorine content of di (chloromethyl) styrene is not significant, and the dihalide compound is used. It can be seen that a certain dichloro compound affects the amount of hydrolyzable chlorine.
  • Comparative Example 3 is an example in which the content of the dihalide compound in the halogenated methylstyrene is not more than a predetermined value, but the reaction solvent does not contain an aprotic polar solvent, and the purity of the halogenated methylstyrene is simply increased. However, the effect of reducing the amount of hydrolyzable chlorine in the poly (vinylbenzyl) ether compound was not obtained.
  • Comparative Example 4 is an example in which an aprotic polar solvent is contained in the reaction solvent, but the dihalide compound content in the halogenated methylstyrene is a predetermined value or more, and the aprotic polar solvent is contained in the reaction solvent. Only by doing, the effect of reducing the amount of hydrolyzable chlorine was not obtained.
  • FIGS. 1 to 3 show the results of gas chromatography measurements performed on the chloromethylstyrene used in Example 1, Example 5, and Examples 4 and 7 to 13.
  • a poly (vinylbenzyl) ether compound suitable as a material for electronic equipment that handles high-frequency signals is provided with reduced production costs while reducing halogen compounds and halide ions in the compound. it can.

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