JP2019172913A - Modified polyphenylene ether containing specific phenol unit and method for producing the same - Google Patents

Abstract

To obtain a modified low molecular polyphenylene ether in which the production of initiator-derived by-products and low-molecular weight components is suppressed in a redistribution reaction.SOLUTION: The present invention provides a modified polyphenylene ether containing a specific phenol unit; the polyphenylene ether having, for example, a structure shown below.SELECTED DRAWING: None

Description

  The present invention relates to a novel modified polyphenylene ether containing a specific phenol unit, which can be suitably used as a material for electrical and electronic equipment, and a method for producing the same.

  As materials for electrical and electronic applications, materials having low dielectric properties for processing a large amount of data in an advanced information society at high speed are required. Among them, polyphenylene ether is known to have excellent dielectric properties such as dielectric constant and dielectric loss tangent, and excellent dielectric properties even in a high frequency band (high frequency region) from MHz band to GHz band. Is used as a high-frequency molding material as a substrate material for constituting a base material of a printed wiring board provided in an electronic device using a high frequency band.

On the other hand, when used as a molding material such as a substrate material, it is required not only to have excellent dielectric properties but also to have excellent heat resistance and moldability. In this regard, the conventional polyphenylene ether is thermoplastic and may not have sufficient heat resistance. For this reason, it has been proposed to use a polyphenylene ether obtained by adding a thermosetting resin such as an epoxy resin, or a polyphenylene ether obtained by modifying polyphenylene ether (Patent Document 1).
Patent Document 1 discloses a modification having a predetermined polyphenylene ether moiety in the molecular structure and at least one p-ethenylbenzyl group, m-ethenylbenzyl group, or the like at the molecular end. Polyphenylene ether compounds are described.
Moreover, as a resin composition containing what modified polyphenylene ether, the polyphenylene ether resin composition of patent document 2 is mentioned, for example. Patent Document 2 has a polyphenylene ether moiety in the molecular structure, a p-ethenylbenzyl group, an m-ethenylbenzyl group, and the like at the molecular end, and a number average molecular weight of 1000 to 7000. A polyphenylene ether resin composition containing polyphenylene ether and a cross-linkable curing agent is described.
Patent Document 3 describes a modified polymer having a polyphenylene ether moiety in the molecular structure and a methacryl group at the molecular end.

Another problem with polyphenylene ether is that it generally has a relatively high molecular weight and a high softening point, which tends to result in high viscosity and low fluidity. When such a polyphenylene ether is used to form a prepreg used for manufacturing a multilayer printed wiring board and the like, and a printed wiring board is manufactured using the formed prepreg, voids are produced at the time of manufacturing, for example, multilayer molding. There is a possibility that molding defects such as the occurrence of defects occur, and there is a problem of moldability that it is difficult to obtain a highly reliable printed wiring board.
Therefore, in order to suppress the occurrence of such a problem, it is conceivable to use a relatively low molecular weight polyphenylene ether. Such a relatively low molecular weight polyphenylene ether can be synthesized by polymerizing a monomer such as 2,6-xylenol in the presence of a low molecular weight phenol such as tetramethylbisphenol (polymerization method), or a high molecular weight polyphenylene ether. There is a method (redistribution method) for synthesizing polyphenylene ether having a reduced molecular weight by performing a redistribution reaction in the presence of a radical initiator and a low molecular weight phenol.

In general, it is known that in the case where a low molecular weight product is produced in the production of polyphenylene ether in a polymerization method, the selectivity of by-products increases and the yield decreases.
As a method for producing a relatively low molecular weight polyphenylene ether, a production method has been proposed in which the molecular weight of polyphenylene ether obtained by adding 2,4,6-trimethylphenol is changed according to the amount added (see, for example, Patent Document 4). In this specification, a mixed solvent of a polyphenylene ether good solvent (for example, benzene, toluene, xylene) and a polyphenylene ether poor solvent (for example, ketone, ether, alcohol) is used as a solvent. It has been proposed that polymers of various molecular weights can be obtained by changing the solvent ratio. However, it is stated that this method is inaccurate and is not suitable as a method for obtaining a polymer having a required molecular weight.
Similarly, a mixed solvent of an aromatic hydrocarbon (eg, benzene, toluene, xylene, etc.) as a good solvent for polyphenylene ether, and an aliphatic hydrocarbon (eg, n-hexane, isohexane, n-heptane, etc.) as a poor solvent for polyphenylene ether. The method implemented in is disclosed (for example, refer to Patent Document 5). However, in the specification and the comparative example, when the reaction proceeds in a state where the generated water and amines are uniformly present in the reaction system, the reaction vessel is used when the oligopolyphenylene ether produces particles in a heterogeneous state. It has been described that there is a defect that tends to adhere to, etc., and was not satisfactory.

On the other hand, in the case of the redistribution method, a low molecular weight product can be obtained relatively easily as compared with the above polymerization method, but it is difficult to control the amount of the low molecular weight product, and an extremely low molecular weight component or initiator is used. There are problems such as a large amount of by-products derived from it. Since these ultra-low molecular weight substances and by-products derived from the initiator may inhibit the reaction when performing the denaturation reaction, it is necessary to suppress the production amount as much as possible in the polymerization or redistribution reaction.

JP 2004-339328 A International Publication No. 2004/067634 Pamphlet Japanese Patent No. 5147497 U.S. Pat. No. 3,440,217 Japanese Patent Publication No. 50-6520

An object of the present invention is to provide a modified polyphenylene ether having both heat resistance and moldability in addition to dielectric properties.
Another object of the present invention is to produce such a modified polyphenylene ether with high purity without producing an initiator-derived byproduct or an extremely low molecular weight product.

As a result of intensive studies to solve the above problems, the present inventors have found that a novel modified polyphenylene ether having a specific structure in the molecule is excellent in heat resistance.
And, when a method for producing such polyphenylene ether without producing a large amount of initiator-derived by-products and extremely low molecular weight components was examined, a low molecular phenol compound having the same structure as the specific structure in the molecule was obtained. When the redistribution reaction is carried out, it has been found that the modified polyphenylene ether can be obtained with a low molecular weight without producing a large amount of initiator-derived by-products or ultra-low molecular weight substances. It came.

That is, the present invention is as follows.
[1]
The polyphenylene ether which has a structure in any one of following formula (1)-(6).
In formula (1)-(6),
n and m each represents a repeating unit and is an integer of 0 to 100, and cannot be 0 at the same time.
X is an arbitrary divalent linking group.
Y is each independently a hydrogen atom or a substituent containing a carbon-carbon double bond and / or an epoxy bond, and both Y are not hydrogen atoms.
R ¹ and R ² are each independently a hydrogen atom, a C1-C6 hydrocarbon group, or a substituent containing a hydrocarbon group represented by formula (7), and at least one of R ¹ is represented by the formula ( The hydrocarbon group represented by 7) is included.
R ³ is each independently a C 1-6 saturated or unsaturated hydrocarbon group, R ⁴ is each independently a hydrogen atom or a C 1-6 saturated or unsaturated hydrocarbon group, The saturated hydrocarbon group may have a substituent as long as the condition of C1-6 is satisfied.
In formula (7), each b is independently 0 or 1,
R ¹¹ is each independently a C 1-8 alkyl group,
R ¹² is each independently a C 1-8 alkylene group;
R ¹³ represents a hydrogen atom, a C 1-8 alkyl group or a phenyl group,
The alkyl group, alkylene group, and phenyl group may have a substituent as long as the condition of C1-8 is satisfied.
[2]
The polyphenylene ether polymer according to [1], wherein Y in the formula (1) is selected from the group consisting of groups represented by the following formulas (8) to (11).
In formulas (8) to (11),
R ^{5 to} R ⁷ are each a hydrogen atom or a C 1 to C 30 hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, or hydroxyalkyl group.
R ⁸ and R ⁹ is a hydrocarbon group of C1-C30.
R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group of C1-C30, aryl group, alkoxy group, aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, or an isopropenyl group, R ¹⁰ At least one of them is a vinyl group or an isopropenyl group, and s and t are integers of 0 to 5.
[3]
The polyphenylene ether according to [1] or [2], wherein the hydrocarbon group represented by the formula (7) is directly bonded to the benzene ring to which R ¹ is bonded in the formulas (1) to (6).
[4]
The polyphenylene ether according to any one of [1] to [3], wherein R ¹¹ and R ¹³ in formula (7) are methyl groups.
[5]
The polyphenylene ether according to any one of [1] to [4], wherein the hydrocarbon group represented by the formula (7) is a t-Bu group.
[6]
The hydrocarbon group represented by the formula (7) is bonded to the 2-position and / or the 6-position of the benzene ring to which R ¹ is bonded in the formulas (1) to (6), [1] to [ 5]. The polyphenylene ether according to any one of [5].
[7]
The polyphenylene ether according to any one of [1] to [7], wherein each Y is independently a vinyl group, an allyl group, a methacryl group, an acrylic group, an isopropenylbenzyl group, or a vinylbenzyl group.
[8]
Polyphenylene ether [9] according to any one of [1] to [8], wherein the number average molecular weight in terms of polystyrene is 500-30000.
A polyphenylene ether composition comprising 0.5 to 95% by mass of the polyphenylene ether according to any one of [1] to [8].
[10]
A step of reacting a polyphenylene ether represented by the following formula (12) with a phenol compound represented by any one of the following formulas (1 ′) to (6 ′);
A step of introducing a substituent containing a carbon-carbon double bond and / or an epoxy bond into at least a part of the terminal of the obtained polyphenylene ether;
A process for producing polyphenylene ether, comprising:
In formula (12),
R ³ is a C 1-6 alkyl group, R ⁴ is a hydrogen atom or a C 1-6 alkyl group, and the alkyl group may have a substituent as long as the condition of C 1-6 is satisfied. . p is an integer of 1-100.
In formula (1 ′)-formula (6 ′),
X is an arbitrary divalent linking group;
R ¹ and R ² are each independently a hydrogen atom, a C1-C6 hydrocarbon group, or a substituent containing a hydrocarbon group represented by formula (7), and at least one of R ¹ is represented by the formula ( The hydrocarbon group represented by 7) is included.
In formula (7), each b is independently 0 or 1,
R ¹¹ is each independently a C 1-8 alkyl group,
R ¹² is each independently a C 1-8 alkylene group;
R ¹³ represents a hydrogen atom, a C 1-8 alkyl group or a phenyl group,
The alkyl group, alkylene group, and phenyl group may have a substituent as long as the condition of C1-8 is satisfied.
[11]
A curing agent composition comprising the polyphenylene ether according to any one of [1] to [8] and a polyfunctional curing agent capable of reacting with the terminal phenol.

  The modified polyphenylene ether of the present invention has appropriate fluidity at the time of molding such as prepreg formation, and has sufficient curing reactivity at the time of curing, so that a cured product having high heat resistance can be obtained.

2 is a 1H-NMR measurement result of polyphenylene ether 1 before modification obtained in Production Example 1. FIG.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

The polyphenylene ether of this embodiment is a polyphenylene ether having a structure of any one of formulas (1) to (6).
In formula (1)-(6),
n and m each represent a repeating unit, and are integers of 0 to 100, which are not simultaneously 0, X is an arbitrary divalent linking group,
Y is each independently a hydrogen atom or a substituent containing a carbon-carbon double bond and / or an epoxy bond, but Y is not a hydrogen atom.
R ¹ and R ² are each independently a hydrogen atom, a C1-C6 hydrocarbon group, or a substituent containing a hydrocarbon group represented by formula (7), and at least one of R ¹ is represented by the formula ( The hydrocarbon group represented by 7) is included.
R ³ is each independently a C 1-6 saturated or unsaturated hydrocarbon group, and R ⁴ is each independently a hydrogen atom or a C 1-6 saturated or unsaturated hydrocarbon group, The saturated hydrocarbon group may have a substituent as long as the condition of C1-6 is satisfied.
In formula (7), each b is independently 0 or 1,
R ¹¹ is each independently a C 1-8 alkyl group,
R ¹² is each independently a C 1-8 alkylene group;
R ¹³ represents a hydrogen atom, a C 1-8 alkyl group or a phenyl group,
The alkyl group, alkylene group, and phenyl group may have a substituent as long as the condition of C1-8 is satisfied.

Examples of X include the following structures.

Further, another example of X includes atoms such as nitrogen, phosphorus, silicon, and groups containing these, and examples thereof include the following structures.

In the above formula, R ^{31 to} R ³⁵ may be the same or different and each represents a hydrogen atom or a C1 to C8 hydrocarbon group. k and l may be the same or different and are integers of 0 to 4.
Specific examples of R ^{31 to} R ³⁵ include a hydrogen atom, methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, and n-hexyl. 2-hexyl, 3-hexyl, cyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, n-octyl, 2-ethylhexyl.

Specific examples of Y include groups represented by the following formulas (8) to (11).

In formulas (8) to (11),
R ^{5 to} R ⁷ are each a hydrogen atom or a C 1 to C 30 hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, or hydroxyalkyl group.
R ⁸ and R ⁹ is a hydrocarbon group of C1-C30.
R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group of C1-C30, aryl group, alkoxy group, aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, or an isopropenyl group, R ¹⁰ At least one of them is a vinyl group or an isopropenyl group, and s and t are integers of 0 to 5.

Specific examples of the hydrocarbon group represented by R ^{5 to} R ⁷ and R ¹⁰ include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1 -Methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1- Methylpentyl, 2-methylpentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3- Tylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethyl Pentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methyl Cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3- Ethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2 -Methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1, 1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3- Dimethyl hexyl, 1,4-dimethyl hexyl, 1,5-dimethyl hexyl, 2,3-dimethyl hexyl, , 4-dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl 2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl- 3-methylpentyl, 1- (2-methylpropyl) butyl, 1- (2-methylpropyl) -2-methylbutyl, 1,1- (2-methylpropyl) Til, 1,1- (2-methylpropyl) ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl- 1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5- Dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl- 2-ethylene, nonyl, a Sononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl and the like can be mentioned. Preferably, for example, methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl 3-methylpentyl, 4-methylpentyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl 3-methylcyclohexyl, 4-methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably, for example, methyl, Ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, Cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5 -Ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably, for example, methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n -Pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5 -Methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethyl Tilhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like.
Specific examples of the hydrocarbon group for R ⁸ and R ⁹ include, for example, methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, and pentamethylene. 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3 -Propylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1 , 3-propylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butyl Len, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1, 1-dimethyl-1,4-butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3- Dimethyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1, 6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1, 5-pentylene, 1,1-dimethyl-1,5 -Pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl-1,5-pentylene 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1,5-pentylene, 3, , 4-dimethyl-1,5-pentylene, 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl-3,3-dimethyl-1,4-butylene, 1,2,3-trimethyl 1,4-butylene, 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-si Rohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2,3-dimethyl-1,3-cyclopentylene, 2,4-dimethyl 1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1methyl-1,7-heptylene, 1-ethyl-1,6- Xylene, 1-propyl-1,5-pentylene, 2-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 5-methyl-1,7- Heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hex Len, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl-1,6-hexylene, 4, 4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1,6-hexylene, 1,4- Dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6-hexylene, 2,5-dimethyl- 1,6-hexylene, 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5-pentylene, 4,4-ethyl Methyl-1,5-pentylene, 1- Ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4-methyl-1,5-pentylene, 2-ethyl-1-methyl-1, 5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1-methyl-1,5-pentylene, 2-ethyl-3-methyl-1,5-pentylene, 2-ethyl- 4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 3-ethyl-4-methyl-1,5- Pentylene, 4-ethyl-3-methyl-1,5-pentylene, 1- (2-methylpropyl) -1,4-butylene, 1- (2-methylpropyl) -2-methyl-1,4-butylene, 1,1- (2-methylpropyl) ethylene 1,1- (2-methylpropyl) ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3-propylene, 1,1-ethylmethyl-2 , 2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl-1,4-butylene, 2,3- Dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl-1,4-cyclohexylene, 3, 5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4-methyl-1,4-cyclohexyl-1 −Me Len, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexylethylene, 1-cyclohexyl-2 -Ethylene, nonylmethylene, 1-methyl-1,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4-phenylene, 1,3-phenylene, 1, Examples include 2-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene, and preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl, and the like. -1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl -1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, -2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4- Butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylylene, 1-methyl-1, 6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1, 5-pentylene, 2-ethyl 1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, octa Methylene, 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7- Heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6- Hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like, more preferably, for example, methylene, ethylene, trimethylene, 1,2-propylene, tetramethyl Len, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4- Butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylylene, octamethylene 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene , Nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene, etc., more preferably, for example, methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1, 1-dimethylethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, octamethylene, 1- Methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6- Methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1 6- hexylene, 5-ethyl-1,6-hexylene, nonyl methylene, decylmethylene, undecyl methylene, dodecyl methylene like.

  Specific examples of the substituent containing a carbon-carbon double bond of Y include a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 1-pentenyl group, a p-vinylphenyl group, and a p-isopropenylphenyl group. M-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-isopropenylbenzyl group, m-vinylbenzyl group, m-isopropenyl Benzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenylpropenyl group, p-vinylphenylbutenyl group, m-vinylphenylethenyl group, m-vinyl Phenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenyl Propenyl group, o- vinylphenyl butenyl group, methacryl group, acryl group, 2-ethyl acrylate group, 2-hydroxymethyl acrylate group, and the like.

The preferred molecular weight range of the polyphenylene ether in the present embodiment is not limited, and when used in the production of a printed circuit board, any molecular weight range may be used as long as it is a range that dissolves in the solvent used at that time, but good moldability. In order to obtain the number average molecular weight (Mn) in the polystyrene-equivalent molecular weight using GPC, the number average molecular weight (Mn) is preferably in the range of 500 to 30000, more preferably 700 to 15000, and still more preferably 700 to 10,000.
The molecular weight distribution is preferably 1.1 to 5 in terms of Mw (weight average molecular weight) / Mn, preferably Mw / Mn is more preferably 1.4 to 4, more preferably 1.5 to 3. Range.

  The modified polyphenylene ether of this embodiment has a high curing reactivity, and a cured product having high heat resistance can be obtained. The reason for this is not clear, but it is presumed that the solvent affinity and the like are increased by the specific structure contained in the center, that is, the structure derived from the phenol compound having a hydrocarbon group represented by the formula (7). The However, the mechanism does not depend on this.

  The production method of the modified polyphenylene ether of this embodiment is not limited, but for example, a known redistribution reaction method is performed using a phenol compound having a hydrocarbon group represented by the formula (7) to obtain a polyphenylene ether. Thereafter, the terminal can be modified (introducing Y). When a polyphenylene ether skeleton is produced by a redistribution reaction method using a phenol compound having a hydrocarbon group of formula (7), the polyphenylene ether skeleton can be produced without producing a large amount of initiator-derived by-products or low molecular weight components. Thus, the subsequent denaturation can be efficiently advanced.

Production of polyphenylene ether by redistribution reaction can be carried out in accordance with conditions defined in known reaction conditions. In this case, since the molecular weight of the obtained polymer is lower than that of the polyphenylene ether as a raw material, it is necessary to adjust the ratio of the raw polyphenylene ether and the low molecular phenol compound in accordance with the target molecular weight.
In the present embodiment, the reaction is a phenol compound containing a hydrocarbon group represented by the formula (7) and X (hereinafter sometimes referred to as “low molecular phenol”) in a reaction solvent under an inert gas atmosphere. Then, after the raw material polyphenylene ether is dissolved in a solvent at a predetermined ratio, the temperature is raised to a predetermined reaction temperature, and then the radical initiator diluted in the reaction solvent is fed into the reaction system. The reaction solvent used for the redistribution reaction preferably has a boiling point that can dissolve the raw materials, has low reactivity with the radical initiator, and can be heated to a temperature at which the radical initiator can be decomposed. Usually, the reaction can be carried out at a temperature below the boiling point under normal pressure, but it may be carried out under reflux conditions. Moreover, when the boiling point of the reaction solvent used is too low, it can also carry out in pressurized reactors, such as an autoclave.

Examples of the low molecular weight phenol include bisphenol compounds represented by the following formulas (1 ′)-(6 ′). In the following formula, X, R ¹ and R ² are the same as X, R ¹ and R ^{2 in} the formula (1), respectively.

Specific examples of the low molecular phenol used in the method for producing polyphenylene ether include, for example, 6-t-butyl-3-methylcatechol, 4,6-di-t-butylbenzene-1,2,3-triol, 2,5- Di-t-amylhydroquinone, 3,5-di-t-butyl-4-hydroxybenzyl alcohol, 1,4-dihydroxy-2-t-butylbenzene, 1,5-dihydroxy-2-t-butylbenzene, 1 , 6-Dihydroxy-2-t-butylbenzene, 1,4-dihydroxy-2, 5-di-t-butylbenzene, 1,4-dihydroxy-2,6-di-t-butylbenzene, 4,4- Methylenebis (2,6-di-t-butylphenol), 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,5-bis- (1,1,3 , 3-Tetramethyl-butyl) -benzene-1,4-diol, 2,2-ethylidenebis- (4,6-di-t-butylphenol), 2,2-methylenebis (6-t-butyl-4-) Ethylphenol), 2,2-butylidenebis (4,6-di-t-butylphenol), α2, α2- (2,3,5,6-tetramethylbis (6-t-butyl-2,4-xylenol) 2,6-di-t-butyl {[(3,5-di-t-butyl-4-hydroxybenzyl) sulfanyl] methyl} phenol, 6,6-di-t-butyl-4,4-bi- Orthocresol, 3-t-butyl-2-hydroxy-5-methylphenyl sulfide, 3,3,5,5-tetra-t-butyl (1,1-biphenyl) -4,4, -diol, triethylene glycol bis (3-t -Butyl-4-hydroxy-5-methylphenyl) propionate, 2,2- (1,3-phenylene) bis (3- (3,5-di-t-butyl-4-hydroxyphenylacrylonitrile, 2,6- Di-t-butyl-4-3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4 , 8,10-tetraoxaspiro [5,5] -undecane, 2,2′-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol], 4,4′-isopropylidenebis ( 2-tert-butylphenol), probucol, bis (3,5-di-t-butyl-4-methoxyphenyl) phosphine, and the like, preferably, for example, 6-t-butyl 3-methylcatechol, 4,6-di-t-butylbenzene-1,2,3-triol, 2,5-di-t-amylhydroquinone, 3,5-di-t-butyl-4-hydroxybenzyl alcohol, 1 , 4-Dihydroxy-2-t-butylbenzene, 1,5-dihydroxy-2-t-butylbenzene, 1,6-dihydroxy-2-t-butylbenzene, 1,4-dihydroxy-2, 5-di- t-butylbenzene, 1,4-dihydroxy-2,6-di-t-butylbenzene, 4,4-methylenebis (2,6-di-t-butylphenol), 4,4′-butylidenebis (6-tert- Butyl-m-cresol), 2,5-bis- (1,1,3,3-tetramethyl-butyl) -benzene-1,4-diol, 2,2-ethylidenebis- (4,6-di-) -Butylphenol), 2,2-methylenebis (6-tert-butyl-4-ethylphenol), 2,2-butylidenebis (4,6-di-tert-butylphenol), α2, α2- (2,3,5, 6-tetramethylbis (6-tert-butyl-2,4-xylenol), 6,6-di-tert-butyl-4,4-bi-orthocresol, 3,3,5,5-tetra-tert-butyl (1,1-biphenyl) -4,4-diol, triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 2,6-di-tert-butyl-4- 3, 9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5 , 5] -Unde Emissions, 2,2'-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol, 4,4'-isopropylidene-bis (2-tert-butylphenol), and probucol.
More preferably, for example, 6-t-butyl-3-methylcatechol, 2,5-di-t-amylhydroquinone, 3,5-di-t-butyl-4-hydroxybenzyl alcohol, 1,4-dihydroxy-2 -T-butylbenzene, 1,5-dihydroxy-2-t-butylbenzene, 1,6-dihydroxy-2-t-butylbenzene, 1,4-dihydroxy-2, 5-di-t-butylbenzene, 1 , 4-Dihydroxy-2,6-di-t-butylbenzene, 4,4-methylenebis (2,6-di-t-butylphenol), 4,4′-butylidenebis (6-tert-butyl-m-cresol) 2,5-bis- (1,1,3,3-tetramethyl-butyl) -benzene-1,4-diol, 2,2-ethylidenebis- (4,6-di-t-butylphenol) ), 2,2-methylenebis (6-t-butyl-4-ethylphenol), 2,2-butylidenebis (4,6-di-t-butylphenol), 6,6-di-t-butyl-4,4 -Bi-orthocresol, 3,3,5,5-tetra-t-butyl (1,1-biphenyl) -4,4, -diol and the like.

Moreover, as raw material polyphenylene ether, what has a structure of following formula (12) is mentioned, for example. In the following formulas (12), R ³ and R ⁴ are each the same as R ³ and R ⁴ of formula (1) ~ (6), p is an integer of 1 to 100.

  Examples of the reaction solvent include benzene, m-xylene, o-xylene, p-xylene, toluene, cumene, ethylbenzene, n-propylbenzene, anisole, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include acetophenone, diethyl ketone, methyl-n-butyl ketone, cyclopentanone, cyclohexanone, tetrahydrofuran, cyclohexane, octane, hexane, cyclopentane, ethyl acetate, butyl acetate, chloroform, and the like, preferably benzene, m-xylene, o -Xylene, p-xylene, toluene, ethylbenzene, n-propylbenzene, anisole, tetrahydrofuran, dioxane, ethylene glycol dimethyl Ether, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, methyl-n-butyl ketone, cyclopentanone, cyclohexanone, tetrahydrofuran, cyclohexane, octane, ethyl acetate, butyl acetate, chloroform, etc., more preferably benzene, m-xylene, o-xylene , P-xylene, toluene, ethylbenzene, n-propylbenzene, anisole, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, methyl-n-butyl ketone, cyclohexanone, tetrahydrofuran, ethyl acetate, butyl acetate, chloroform, etc. And mixed solvent systems thereof.

  The molecular weight of the starting polyphenylene ether used in the reaction is not limited, but for example, those having a range of Mn = 100000 to 5000, preferably Mn = 50000 to 5000, and more preferably Mn = 30000 to 5000 can be used.

  The concentration of polyphenylene ether during the reaction is not particularly limited as long as it dissolves and can be stirred. Specifically, for example, the range is 0.5 to 70 wt%, preferably 5 to 65 wt%, and more preferably 10 to 60 wt%.

Since the ratio of the low molecular weight phenol to the raw material polyphenylene ether is determined by the molecular weight of the target polyphenylene ether, it can be set to an arbitrary ratio according to the target molecular weight.
In the present embodiment, the charging ratio at the time of reaction can be represented by, for example, the ratio of the hydroxyl groups of the low molecular weight phenol and the raw material polyphenylene ether. The amount of hydroxyl groups per mole of low molecular weight phenol can be determined from the molecular structure, and the amount of hydroxyl groups per mole of raw polyphenylene ether can be calculated based on the number average molecular weight. Moreover, when the polymer of the one-end hydroxyl group and the polymer of the both-end hydroxyl group are mixed in the raw material polyphenylene ether by a polymerization method, the correction may be performed by measurement such as NMR. The preferred ratio of the low molecular phenol and the hydroxyl group of the raw polyphenylene ether during the reaction is, for example, the hydroxyl group of the low molecular phenol / the hydroxyl group of the raw phenol = 0.5 / 100 to 80/100, preferably the hydroxyl group of the low molecular phenol. / Hydroxyl hydroxyl group of raw material = 1/100 to 50/100, more preferably hydroxyl group of low molecular phenol / hydroxyl group of raw material phenol = 5/100 to 30/100.

  There is no limit to the method of charging the low molecular weight phenol and the raw material polyphenylene ether, and it is common to charge the reactor in advance before starting the reaction. However, depending on the purpose, it may be divided and added to the reaction system. It doesn't matter. Moreover, the low molecular phenol or raw material polyphenylene ether solution dissolved in advance may be continuously added to the reaction system even after the start of the reaction.

As the initiator used in the reaction together with the solvent, for example, any peroxide capable of generating radicals can be used.
Examples of peroxides that can be used in this embodiment include p-menthane hydroperoxide, benzoyl peroxide, dilauroyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, disuccinic acid peroxide, and diisobutyrate. Tyryl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, t -Butylperoxyisopropyl monocarbonate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxybe Zoate, t-butylperoxy-3-methylbenzoate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxy Acetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, benzoyl m-methylbenzoyl peroxide, m-toluyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 1,1 , 3,3-tetramethylbutyl hydroperoxyneodecanoate, 1,1,3,3-tetramethylbutylhydroperoxy-2-ethylhexanoate, cumene hydroperoxide, cumylperoxyneodecanoate, diisobutylbenzene Hydrope Oxide, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, t-butylcumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, 2,2-di (t- Butylperoxy) butane, 2,5-dimethyl-2,5-di (benzylperoxy) hexane, 2,5-dimethyl-2,5-di (2-ethylhydroxyperoxy) hexane, 1,1-di (t- Butylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, n-butyl 4,4-di (t-butylperoxy) valerate, di-t-hexyl peroxide, t-hexylperoxyisobutyl monocarbonate, t -Hexylperoxyneodacanoate, t-hexylperoxy-2-ethylhexanoe And t-hexyl peroxypivalate, t-hexyl peroxybenzoate, and the like, and mixtures thereof.
More preferably, for example, p-menthane hydroperoxide, benzoyl peroxide, dilauroyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, disuccinic peroxide, t-butylperoxyisopropyl monocarbonate, t-butyl Peroxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxybenzoate, t-butylperoxy-3-methylbenzoate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxy-3, 5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, benzoyl m-methylbenzoylperoxy M-toluyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxy-2-ethylhexanoate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, t- Butylcumyl peroxide, di-t-butyl peroxide, 2,2-di (t-butylperoxy) butane, 2,5-dimethyl-2,5-di (benzylperoxy) hexane, 2,5-dimethyl-2, 5-di (2-ethylhydroxyperoxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, n-butyl 4,4-di (t-butyl) Peroxy) valerate, di-t-hexyl peroxide, t-hexyl peroxyisobutyl monocarbonate, t-hexylpe Oxy neodecanoate, t-hexyl peroxy-2-ethylhexanoate, t-hexyl peroxypivalate, a t-hexyl peroxybenzoate.
Further, a metal catalyst such as cobalt naphthenate may coexist during the reaction.

The reaction temperature is not particularly limited as long as the raw material polyphenylene ether and the low molecular weight phenol are dissolved and can generate an initiator radical during the reaction. As a guideline, it is preferable to carry out the reaction within the range of ± 20 ° C. of the one-hour half-life temperature of the initiator used.
In addition, for the purpose of completing the reaction after adding the initiator, stirring may be continued under heating conditions to continue the reaction.

  The method of adding the initiator includes a method of adding all at once at the start of the reaction, a method of adding several times in the middle of the reaction, a method of adding continuously or intermittently from the start of the reaction, the target polymer, Any method may be used according to the purpose such as the nature of the initiator and the control of reaction conditions. In addition, if necessary, the low molecular phenol or a part of the low molecular phenol is reacted with the initiator in advance, and this is added to the reaction system in which the raw polyphenylene ether or the raw polyphenylene ether and the low molecular phenol are dissolved. A method may be adopted. Alternatively, a method may be employed in which a raw material polyphenylene ether or a part of the raw material polyphenylene ether is reacted with an initiator and then added to the reaction system in which the low molecular weight phenol or the raw material polyphenylene ether and the low molecular weight phenol are dissolved.

  Although the reaction time depends on the reaction temperature, substrate, and raw material concentration, the reaction can usually be carried out in about 0.5 to 6 hours.

There is no limitation on the method for treating the polyphenylene ether solution after the reaction (hereinafter sometimes referred to as “polymer solution”). For example, the polymer solution is added to a poor solvent such as alcohol and the polymer is precipitated by reprecipitation. And then dried after fractionation with a solvent. Examples of the poor solvent that can be used for reprecipitation include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, n-hexane etc. are mentioned, Preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol etc. are mentioned.
As another method, there is a method of distilling off the solvent under reduced pressure after the reaction. In this case, if necessary, a radical stabilizer such as a polymerization inhibitor may be added before the solvent is distilled off.

  In addition, the polymer solution can be washed before removing the polyphenylene ether for the purpose of removing the initiator-derived compound and reaction by-products. When washing the polymer solution, water or a water / alcohol mixed solvent system can be suitably used. Moreover, you may add alkalis, such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, to a washing | cleaning solvent as needed.

  The obtained polyphenylene ether can be identified by NMR, IR, GPC or the like. If necessary, if an unreacted polymer, a by-product insoluble in the solvent, or the like is generated after the reaction, the above operation may be performed after the operation such as filtration.

The modified polyphenylene ether of the present embodiment has low dielectric properties and excellent heat resistance, and therefore can be suitably used as a material for various electric / electronic devices. In particular, the modified polyphenylene ether of the present embodiment also has good fluidity and moldability, and therefore can be suitably used for the production of prepregs for electric / electronic parts (printed wiring board base materials, etc.).
The modified polyphenylene ether of this embodiment may be used alone as a thermoplastic resin, or may be used as a polyphenylene ether composition in combination with various known additives. In this case, the content of polyphenylene ether in the composition can be, for example, 0.5 to 95% by mass.

Furthermore, the modified polyphenylene ether of the present embodiment can be used as a curing agent composition in combination with a polyfunctional curing agent capable of reacting with the terminal phenol. Examples of such a polyfunctional curing agent include an epoxy compound. Although there is no limitation in content of polyphenylene ether in such a hardening | curing agent composition, it can be 10-60 mass%, for example. In addition, known additives such as Br flame retardants, silica, and thermoplastic elastomers may be added to the curing agent composition.
Since the modified polyphenylene ether of this embodiment has high curing reactivity, a cured product having high heat resistance can be obtained.

Various methods can be used for introducing Y into the polyphenylene ether end depending on the type of the functional group.
For example, when Y is a functional group having the structure of (8), the introduction can be generally carried out by formation of an ether bond by the Williamson synthesis method.
Specifically, the hydroxyl group at the end of the polyphenylene ether is converted to an alkali metal salt with a base or the like, and then reacted with the alkyl halide end (the end of the introduction group raw material). The reaction of a hydroxyl group with an alkali metal salt can be obtained, for example, by reacting an alkali metal, an alkali metal hydride, an alkali metal amide, an alkali metal hydroxide, or the like with a hydroxyl group at the end of polyphenylene ether. The reaction system is generally selected from a solvent that is inert to the reaction and can dissolve the polyphenylene ether. For example, when an alkali metal hydroxide is used during the synthesis of an alkali metal salt, A two-layer system of an organic phase in which polyphenylene ether is dissolved and an aqueous phase in which alkali metal hydroxide or the like is dissolved may be used. In the case of such a reaction system, if necessary, a salt such as a quaternary amine salt may be used as a phase transfer catalyst during the reaction.
After the reaction, in order to remove the by-product alkali salt or amine salt used in the reaction, it may be washed with water, an acidic or alkaline aqueous solution, and the polyphenylene ether solution may be washed with a poor solvent such as alcohols. The target product may be recovered by dropping into the solution and reprecipitation. Further, after washing the polyphenylene ether solution, the solvent may be distilled off under reduced pressure to recover the polyphenylene ether.

In addition, when Y is a functional group having a structure of (10) (t is 1 or more), an ester bond is formed by the following method after introducing a hydroxyalkyl group into the polyphenylene ether terminal in advance by the above method. It doesn't matter if you let them.
When Y is a functional group having the structure of (9), the introduction is a reaction for forming an ester bond between a hydroxyl group at the terminal of the polyphenylene ether and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid). . Various known methods can be used for forming the ester bond. For example, a. Reaction of a carboxylic acid halide with a hydroxyl group at the end of a polyphenylene ether, b. Formation of an ester bond by reaction with a carboxylic anhydride, c. Direct reaction with carboxylic acid, d. Examples thereof include a method using a transesterification reaction.
a. The reaction with carboxylic acid halides is one of the most common methods. As the carboxylic acid halide, chloride and bromide are generally used, but other halogens may be used. The reaction may be a direct reaction with a hydroxyl group or a reaction with an alkali metal salt of a hydroxyl group. In the direct reaction between a carboxylic acid halide and a hydroxyl group, an acid such as hydrogen halide is generated. Therefore, a weak base such as an amine may be allowed to coexist for the purpose of trapping the acid.
b. Reaction with carboxylic acid anhydrides of c. In the direct reaction with carboxylic acid, for example, a compound such as carbodiimides or dimethylaminopyridine may be allowed to coexist in order to activate the reaction site and promote the reaction.
d. In the case of the transesterification reaction, it is desirable to remove the produced alcohols as necessary. In order to accelerate the reaction, a known metal catalyst may coexist.
Removal of by-products after the reaction can be generated by the same method as that used in the ether reaction synthesis.

  Hereinafter, the present embodiment will be described in detail with reference to examples. However, the present embodiment is not limited to the following examples.

(Synthesis reaction of polyphenylene ether by redistribution reaction)
All reactions were basically carried out under an inert gas atmosphere. The solvent used for the reaction was a commercially available reagent. The raw materials and reagents used are as follows.
1. Solvent Toluene: Wako Pure Chemical reagent special grade was used as it was.
Methyl isobutyl ketone: Wako Pure Chemical reagent special grade was used as it was.
Methyl ethyl ketone: Wako Pure Chemical reagent special grade was used as it was.
Ethylene glycol dimethyl ether: Wako Pure Chemical reagent special grade was used as it was.
Methanol: Wako Pure Chemical reagent special grade product was used as it was.
Isopropanol: Wako Pure Chemical reagent special grade was used as it was.
Ethanol: A reagent special product manufactured by Wako Pure Chemicals was used as it was.

2. Initiator:
NIPER BMT: Nippon Oil & Fats Co., Ltd. product was used as it was.

3. Raw material polyphenylene ether S202A (polystyrene equivalent number average molecular weight 16000): Asahi Kasei Corporation product was used as it was.
S203 (polystyrene equivalent number average molecular weight 10,000) A: The product made by Asahi Kasei Corporation was used as it was.
Each of S202A and S203A has the following structure.

4). Low molecular weight phenol 4,4′-butylidenebis (6-tert-butyl-m-cresol): A product manufactured by ADEKA (AO-40) was used as it was.
4,4′-isopropylidenebis (2-tert-butylphenol): Aldrich reagent product was used as it was.
4,4-methylenebis (2,6-di-t-butylphenol): Aldrich reagent product was used as it was.
Tetramethylbisphenol A: Asahi Organic Materials Co., Ltd. product was used as it was.
Bisphenol A: Aldrich reagent product was used as it was.
5. Modified group raw material Methacrylic anhydride: Aldrich reagent product was used as it was.
Dimethylaminopyridine: Aldrich reagent product was used as it was.
Methacryloyl chloride: Aldrich reagent product was used as it was.
Triethylamine: Aldrich reagent product was used as it was.
Chloromethylstyrene (ratio of p-chloromethylstyrene and m-chloromethylstyrene is 50/50): A product manufactured by Tokyo Chemical Industry Co., Ltd. was used as it was.
Tetra-n-butylammonium bromide: Aldrich reagent product was used as it was.
Allyl bromide: Aldrich reagent product was used as it was.

(Identification and analysis of polyphenylene ether)
1. Number average molecular weight measurement The molecular weight was measured by GPC in a chloroform solvent. The molecular weight was determined by a polystyrene conversion method based on a calibration curve using standard polystyrene.
The low molecular weight contained in the polymer was calculated as the area of the low molecular region in the entire molecular weight distribution by converting the GPC measurement result into an integral molecular weight.
2. NMR measurement A sample was dissolved in deuterated chloroform to a concentration of 5% by mass, and NMR measurement was performed. The progress of the reaction (synthesis reaction of polyphenylene ethers 1 to 6) was confirmed by confirming that the hydroxyl peak of the low molecular phenol disappeared from the aromatic peak of the low molecular phenol unit and the proton peak of the hydroxyl group. .
There are peaks of by-products derived from the initiator around 8.0 ppm and 8.2 ppm of the product. By-products derived from the initiator were calculated from the peak areas of the by-products derived from the initiator at around 8.0 ppm and 8.2 ppm, assuming that the peak of the methyl group at the 2,6-position of the main chain was 1.
3. Solution Viscosity Measurement 200 ml of 20% by mass methyl ethyl ketone solution of each sample was placed in a beaker, and the viscosity was measured at 25 ° C. and a rotation speed of 30 rpm using a B type rotational viscometer.

(Production Example 1)
Synthesis of polyphenylene ether 1 A 500 ml three-neck flask was equipped with a Dim funnel and an isostatic dropping funnel with a three-way cock. After replacing the inside of the flask with nitrogen, 100 g of raw material polyphenylene ether S202A, 150 g of toluene and 50 g of methyl ethyl ketone were added, and 10.2 g of 4,4′-butylidenebis (6-tert-butyl-m-cresol) was added as a low molecular weight phenol. A thermometer was installed in the flask, and the flask was heated to 90 ° C. in an oil bath while stirring with a magnetic stirrer to dissolve the raw polyphenylene ether. As an initiator, 37.5 g of a 40 mass% metaxylene solution (manufactured by NOF: Nyper BMT) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluyl peroxide was diluted to 87.5 g of toluene, and the pressure was constant. The dropping funnel was charged. The reaction was started when the initiator solution started dropping into the flask. The initiator was added dropwise over 2 hours, and after the addition, stirring was continued at 80 ° C. for 4 hours. After the reaction, the polymer solution was dropped into methanol and reprecipitated, and then separated from the solution to recover polyphenylene ether 1. Thereafter, the polymer was dried at 100 ° C. for 3 hours under vacuum. The measurement result of 1H-NMR of the dried polymer is shown in FIG.
The reaction progress was monitored by 1H-NMR, and the peak of the hydroxyl group of 4,4′-butylidenebis (6-tert-butyl-m-cresol) near 4.5 ppm decreased with the progress of the reaction and eventually disappeared. I confirmed that Further, in the product, a peak corresponding to the methyl group of the polyphenylene ether unit was confirmed near 2.1 ppm, and a proton peak at the meta position of the polyphenylene ether unit was confirmed near 6.5 ppm. The peaks corresponding to the 4,4′-butylidenebis (6-tert-butyl-m-cresol) unit are the methine proton of the butylidene carbon near 4.1 ppm and the hydroxyl group of the phenol unit near 7.1 ppm and 6.5 ppm. In contrast, the shift of protons corresponding to the meta and ortho positions toward the high magnetic field was confirmed. Furthermore, it was confirmed that the proton of the ortho-butyl group at the ortho position slightly shifted with respect to the hydroxyl group near 1.3 ppm and was split. This confirmed that the raw material 4,4′-butylidenebis (6-tert-butyl-m-cresol) was incorporated into the polymer. From the above 1H-NMR results, the product was estimated to have the following structure.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1700.
The component of Mn <500 in the GPC measurement result was about 10% by mass. The peak area ratio of the initiator-derived byproduct to the methyl group of the main chain measured by 1H-NMR was 13.1 × 10 ⁻³ .
Moreover, the solution viscosity in a 20 mass% methyl ethyl ketone solvent was 126 cPois.

(Production Example 2)
Synthesis of polyphenylene ether 2 A 500 ml three-necked flask was equipped with a Dim funnel and an isobaric dropping funnel with a three-way cock. After substituting the inside of the flask with nitrogen, 100 g of raw material polyphenylene ether S203A and 200 g of toluene were added, and 9.8 g of 4,4′-isopropylidenebis (2-tert-butylphenol) was added as a low molecular weight phenol. A thermometer was installed in the flask, and the flask was heated to 90 ° C. in an oil bath while stirring with a magnetic stirrer to dissolve the raw polyphenylene ether. As an initiator, 37.5 g of a 40 mass% metaxylene solution (manufactured by NOF: Nyper BMT) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluyl peroxide was diluted to 87.5 g of toluene, and the pressure was constant. The dropping funnel was charged. The reaction was started when the initiator solution started dropping into the flask. The initiator was added dropwise over 2 hours, and after the addition, stirring was continued at 80 ° C. for 4 hours. After the reaction, the polymer solution was dropped into methanol and reprecipitated, and then separated from the solution to recover polyphenylene ether 2. Thereafter, this was dried at 100 ° C. under vacuum for 3 hours.

It was confirmed by 1H-NMR that the low molecular phenol hydroxyl peak had disappeared, and that the low molecular phenol was incorporated into the polymer from the shift of the low molecular phenol aromatic peak as in Production Example 1. . As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1900.
The component of Mn <500 in the GPC measurement result was 9.7% by mass. The peak area ratio of the initiator-derived byproduct to the methyl group of the main chain measured by 1H-NMR was 12.8 × 10 ⁻³ .
Moreover, the solution viscosity in a 20 mass% methyl ethyl ketone solvent was 151 cPois.

(Production Example 3)
Synthesis of polyphenylene ether 3 A 500 ml three-necked flask was equipped with a Dim funnel and an isobaric dropping funnel with a three-way cock. After replacing the inside of the flask with nitrogen, 100 g of raw material polyphenylene ether S202A and 200 g of mesitylene were added, and 9.8 g of 4,4-methylenebis (2,6-di-t-butylphenol) was added as a low molecular weight phenol. A thermometer was installed in the flask, and the flask was heated to 150 ° C. in an oil bath while stirring with a magnetic stirrer to dissolve the raw polyphenylene ether. As an initiator, 37.5 g of a 40 mass% metaxylene solution (manufactured by NOF: Nyper BMT) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluyl peroxide was diluted to 87.5 g of toluene, and the pressure was constant. The dropping funnel was charged. The reaction was started when the initiator solution started dropping into the flask. The initiator was added dropwise over 1 hour, and after the addition, stirring was continued at 150 ° C. for 1 hour. After the reaction, the polymer solution was dropped into methanol and reprecipitated, and then separated from the solution to recover Polyphenylene ether 3. Thereafter, it was dried at 100 ° C. under vacuum for 3 hours.

By 1H-NMR, the peak of the hydroxyl group of the low molecular weight phenol disappears, and the low molecular weight phenol is incorporated into the polymer from the shift of the aromatic peak of the low molecular weight phenol as in Production Example 1. confirmed. As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1700.
The component of Mn <500 in the GPC measurement result was 11.2% by mass. The peak area ratio of the initiator-derived byproduct to the methyl group of the main chain measured by 1H-NMR was 13.1 × 10 ⁻³ .
Moreover, the solution viscosity in a 20 mass% methyl ethyl ketone solvent was 138 cPois.

(Production Example 4)
Synthesis of polyphenylene ether 4 Polyphenylene ether 4 was produced in the same manner as in Production Example 3 except that 10.2 g of 4,4′-butylidenebis (6-tert-butyl-m-cresol) was used as the low molecular weight phenol. did.
By 1H-NMR, the peak of the hydroxyl group of the low molecular weight phenol disappears, and the low molecular weight phenol is incorporated into the polymer from the shift of the aromatic peak of the low molecular weight phenol as in Production Example 1. confirmed. As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1600.
The component of Mn <500 in the GPC measurement result was 11.5% by mass.
The peak area ratio of the initiator-derived byproduct to the methyl group of the main chain measured by 1H-NMR was 13.0 × 10 ⁻³ .
Moreover, the solution viscosity in a 20 mass% methyl ethyl ketone solvent was 132 cPois.

(Comparative Production Example 1)
Synthesis of polyphenylene ether 5 Polyphenylene ether 5 was produced in the same manner as in Production Example 1 except that tetramethylbisphenol A was used as the low molecular weight phenol.
By 1H-NMR, the peak of the hydroxyl group of the low molecular phenol disappeared, and it was confirmed that the low molecular phenol was incorporated into the polymer.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1700.
The component of Mn <500 in the GPC measurement result was 16.2% by mass.
The peak area ratio of the initiator-derived byproduct to the methyl group of the main chain measured by 1H-NMR was 16.4 × 10 ⁻³ .
Moreover, the solution viscosity in a 20 mass% methyl ethyl ketone solvent was 138 cPois.

(Comparative Production Example 2)
Synthesis of polyphenylene ether 6 Polyphenylene ether 6 was produced in the same manner as in Production Example 2 except that bisphenol A was used as the low molecular weight phenol.
By 1H-NMR, the peak of the hydroxyl group of the low molecular phenol disappeared, and it was confirmed that the low molecular phenol was incorporated into the polymer. As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1600.
The component of Mn <500 in the GPC measurement result was 17.4% by mass.
The peak area ratio of the initiator-derived by-product to the methyl group of the main chain measured by 1H-NMR was 16.8 × 10 ⁻³ .
Moreover, the solution viscosity in a 20 mass% methyl ethyl ketone solvent was 132 cPois.

Example 1
80 g of toluene and 40 g of polyphenylene ether 1 synthesized in Production Example 1 were mixed and heated to about 85 ° C. 0.55 g of dimethylaminopyridine was added. When all the solids seem to have dissolved, 4.9 g of methacrylic anhydride was gradually added. The resulting solution was maintained at 85 ° C. for 3 hours with continuous mixing. Next, the solution was cooled to room temperature to obtain a toluene solution of methacrylate-modified polyphenylene ether.
A part of the solution was collected and dried, and 1H-NMR measurement was performed. Since the peak derived from methacrylic anhydride was shifted, the peak derived from methacrylic acid was generated, and the peak derived from the hydroxyl group of polyphenylene ether had disappeared, it was determined that the reaction was proceeding, and the purification operation was started. 120 g of the above-mentioned methacrylate-modified polyphenylene ether solution was dropped into 360 g of methanol vigorously stirred with a magnetic stirrer in a 1 L beaker over 30 minutes. The resulting precipitate was filtered through a membrane filter under reduced pressure and dried to obtain 38 g of a polymer.
1H-NMR measurement was performed, and the disappearance of the polyphenylene ether-derived hydroxyl peak and the methacrylic olefin-derived proton peak were confirmed. Moreover, since the peak derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid almost disappeared by GC measurement, the peak derived from the methacrylic group of NMR was determined to be bonded to the polyphenylene ether terminal. From this result, it was confirmed that the obtained polymer was a modified polyphenylene ether having the following structure.

As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1600.

(Example 2)
Synthesis was performed in the same manner as in Example 1 except that 40 g of polyphenylene ether 2 synthesized in Production Example 2 was used and 5.1 g of methacrylic anhydride was used. At the time of purification, purification was performed in the same manner as in Example 1 except that 400 g of ethanol was used with respect to 120 g of the polymer solution.
1H-NMR measurement was performed, the peak derived from methacrylic anhydride was shifted, the peak derived from methacrylic acid was generated, and the peak derived from the hydroxyl group of polyphenylene ether disappeared. A proton peak derived from a methacrylic olefin was confirmed. Moreover, since the peak derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid almost disappeared by GC measurement, the peak derived from the methacrylic group of NMR was determined to be bonded to the polyphenylene ether terminal.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1820.

(Example 3)
It was synthesized and purified in the same manner as in Example 2 except that the polyphenylene ether 3 synthesized in Production Example 3 was used.
1H-NMR measurement was performed, and the peak derived from methacrylic anhydride was shifted, a peak derived from methacrylic acid was generated, the disappearance of the peak of the hydroxyl group derived from polyphenylene ether and the proton peak derived from the olefin of methacrylic group were confirmed. Moreover, since the peak derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid almost disappeared by GC measurement, the peak derived from the methacrylic group of NMR was determined to be bonded to the polyphenylene ether terminal.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1900.

(Example 4)
80 g of toluene and 40 g of polyphenylene ether 4 synthesized in Production Example 4 were mixed. When 4 g of triethylamine was added and all solids were considered dissolved, 3.9 g of methacryloyl chloride was gradually added at 0 ° C. The resulting solution was reacted at 25 ° C. for 12 hours while continuously mixing to obtain a toluene solution of methacrylate-modified polyphenylene ether. The toluene solution was washed with 120 g of water and purified in the same manner as in Example 2.
1H-NMR measurement was performed, and the disappearance of the polyphenylene ether-derived hydroxyl peak and the methacrylic olefin-derived proton peak were confirmed. Further, by GC measurement, a peak derived from methacryloyl chloride (that is, a peak of methacrylic acid)
Since almost disappeared, it was determined that the peak derived from the methacrylic group in NMR was bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1900.

(Example 5)
It was synthesized and purified in the same manner as in Example 4 except that polyphenylene ether 2 synthesized in Production Example 2 was used.
1H-NMR measurement was performed, and the disappearance of the polyphenylene ether-derived hydroxyl peak and the methacrylic olefin-derived proton peak were confirmed. Moreover, since the peak derived from methacryloyl chloride (that is, the peak of methacrylic acid) almost disappeared by GC measurement, the peak derived from the methacrylic group of NMR was determined to be bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1500.

(Example 6)
40 g of polyphenylene ether 1 synthesized in Production Example 1, chloromethylstyrene (p-chloromethylstyrene and m-chloromethylstyrene) was added to a 300 ml three-necked flask equipped with a temperature controller, a stirrer, cooling equipment and a dropping funnel. The ratio was 50/50, manufactured by Tokyo Chemical Industry Co., Ltd.) 4.4 g, tetra-n-butylammonium bromide 0.2 g, and toluene 80 g. The mixture was dissolved by stirring, and the liquid temperature was adjusted to 75 ° C. An aqueous sodium hydroxide solution (2.2 g of sodium hydroxide / 3 g of water) was added dropwise to the mixture over 20 minutes, and stirring was further continued at 75 ° C. for 4 hours. Next, after neutralizing the flask contents with a 10% hydrochloric acid aqueous solution, 120 g of the polymer solution was dropped into 360 g of methanol vigorously stirred in a 1 L beaker over 30 minutes. The resulting precipitate was filtered through a membrane filter under reduced pressure and dried to obtain 39 g of polymer.
1H-NMR measurement was performed, and the disappearance of the peak of the hydroxyl group derived from polyphenylene ether and the proton peak derived from the olefin of the styryl group were confirmed. Further, since the peak of chloromethylstyrenes almost disappeared by GC measurement, it was determined that the peak derived from the styryl group of NMR was bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1590.

(Example 7)
The compound was synthesized in the same manner as in Example 6 except that the polyphenylene ether 2 synthesized in Production Example 2 was used.
1H-NMR measurement was performed, and the disappearance of the peak of the hydroxyl group derived from polyphenylene ether and the proton peak derived from the olefin of the styryl group were confirmed. Further, since the peak of chloromethylstyrenes almost disappeared by GC measurement, it was determined that the peak derived from the styryl group of NMR was bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1900.

(Example 8)
The compound was synthesized in the same manner as in Example 6 except that the polyphenylene ether 3 synthesized in Production Example 3 was used.
1H-NMR measurement was performed, and the disappearance of the peak of the hydroxyl group derived from polyphenylene ether and the proton peak derived from the olefin of the styryl group were confirmed. Further, since the peak of chloromethylstyrenes almost disappeared by GC measurement, it was determined that the peak derived from the styryl group of NMR was bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1890.

Example 9
Synthesis was performed in the same manner as in Example 6 except that the polymer of polyphenylene ether 4 synthesized in Production Example 4 was used.
1H-NMR measurement was performed, and the disappearance of the peak of the hydroxyl group derived from polyphenylene ether and the proton peak derived from the olefin of the styryl group were confirmed. Further, since the peak of chloromethylstyrenes almost disappeared by GC measurement, it was determined that the peak derived from the styryl group of NMR was bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1880.

(Example 10)
The polymer was synthesized in the same manner as in Example 6 except that the polymer of polyphenylene ether 4 synthesized in Production Example 4 was used and allyl bromide was used instead of chloromethylstyrene.
1H-NMR measurement was performed, and the disappearance of the peak of the hydroxyl group derived from polyphenylene ether and the proton peak derived from the olefin of the allyl group were confirmed. Moreover, since the peak derived from allyl bromide almost disappeared by GC measurement, it was determined that the peak derived from the allyl group of NMR was bonded to the end of polyphenylene ether.
As a result of GPC measurement, the molecular weight in terms of polystyrene was Mn = 1500.

(Comparative Example 1)
The compound was synthesized in the same manner as in Example 1 except that the polyphenylene ether synthesized in Comparative Production Example 2 was used. In the middle of the reaction, all of the methacrylic anhydride was consumed, but the peak of the hydroxyl group derived from the raw material polymer did not decrease, and the reaction did not proceed.
As a result of 1H-NMR measurement, a reaction product of methacrylic acid and an initiator-derived byproduct was confirmed, and it was presumed that the reaction with the initiator-derived byproduct or a decomposition product thereof proceeded simultaneously with the main reaction. The rate of progress of the main reaction as seen from NMR was about 60%.

(Comparative Example 2)
The compound was synthesized in the same manner as in Example 4 except that the polyphenylene ether synthesized in Comparative Production Example 1 was used. Although all of methacryloic acid chloride was consumed during the reaction, the peak of the hydroxyl group derived from the raw material polymer did not decrease and the reaction did not proceed.
As a result of IR measurement, a peak of carbonyl derived from an acid anhydride was confirmed, and it was presumed that the reaction of methacryloyl chloride with an initiator-derived by-product or a decomposition product thereof proceeded simultaneously with the main reaction. The rate of progress of the main reaction as seen from NMR was about 60%.

(Comparative Example 3)
The compound was synthesized in the same manner as in Example 10 except that the polyphenylene ether synthesized in Comparative Production Example 2 was used. Allyl bromide was consumed from the middle of the reaction, but the peak of hydroxyl group derived from the raw material polymer did not decrease and the reaction did not proceed.
As a result of IR measurement, a peak of carbonyl derived from the ester was confirmed, and it was presumed that the reaction of allyl bromide with the initiator-derived by-product or its decomposition product proceeded simultaneously with the main reaction. The rate of progress of the main reaction as seen from NMR was about 60%.

  Since the modified polyphenylene ether of the present invention is excellent in fluidity, it can be used for various applications. In particular, the polyphenylene ether of the present invention can form prepregs with less voids and so on, so it can be used as a material for parts such as electrical and electronic equipment (specifically, it can process large amounts of data in an advanced information society at high speed). Therefore, it is useful as a material having a low dielectric property.

Claims (11)

The polyphenylene ether which has a structure in any one of following formula (1)-(6).
In formula (1)-(6),
n and m each represents a repeating unit and is an integer of 0 to 100, and cannot be 0 at the same time.
X is an arbitrary divalent linking group.
Y is each independently a hydrogen atom or a substituent containing a carbon-carbon double bond and / or an epoxy bond, and both Y are not hydrogen atoms.
R ¹ and R ² are each independently a hydrogen atom, a C1-C6 hydrocarbon group, or a substituent containing a hydrocarbon group represented by formula (7), and at least one of R ¹ is represented by the formula ( The hydrocarbon group represented by 7) is included.
R ³ is each independently a C 1-6 saturated or unsaturated hydrocarbon group, R ⁴ is each independently a hydrogen atom or a C 1-6 saturated or unsaturated hydrocarbon group, The saturated hydrocarbon group may have a substituent as long as the condition of C1-6 is satisfied.
In formula (7), each b is independently 0 or 1,
R ¹¹ is each independently a C 1-8 alkyl group,
R ¹² is each independently a C 1-8 alkylene group;
R ¹³ represents a hydrogen atom, a C 1-8 alkyl group or a phenyl group,
The alkyl group, alkylene group, and phenyl group may have a substituent as long as the condition of C1-8 is satisfied. The polyphenylene ether polymer according to claim 1, wherein Y in the formula (1) is selected from the group consisting of groups represented by the following formulas (8) to (11).
In formulas (8) to (11),
R ^{5 to} R ⁷ are each a hydrogen atom or a C 1 to C 30 hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, or hydroxyalkyl group.
R ⁸ and R ⁹ is a hydrocarbon group of C1-C30.
R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group of C1-C30, aryl group, alkoxy group, aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, or an isopropenyl group, R ¹⁰ At least one of them is a vinyl group or an isopropenyl group, and s and t are integers of 0 to 5. The polyphenylene ether according to claim 1 or 2, wherein the hydrocarbon group represented by the formula (7) is directly bonded to the benzene ring to which R ¹ is bonded in the formulas (1) to (6). The polyphenylene ether according to any one of claims 1 to 3, wherein R ¹¹ and R ¹³ in the formula (7) are methyl groups.   The polyphenylene ether according to any one of claims 1 to 4, wherein the hydrocarbon group represented by the formula (7) is a t-Bu group. The hydrocarbon group represented by the formula (7) is bonded to the 2-position and / or the 6-position of the benzene ring to which R ¹ is bonded in the formulas (1) to (6). The polyphenylene ether according to any one of the above.   The polyphenylene ether according to any one of claims 1 to 6, wherein each Y is independently a vinyl group, an allyl group, a methacryl group, an acrylic group, an isopropenylbenzyl group, or a vinylbenzyl group.   The polyphenylene ether according to any one of claims 1 to 7, wherein the number average molecular weight in terms of polystyrene is 500-30000.   A polyphenylene ether composition comprising 0.5 to 95% by mass of the polyphenylene ether according to any one of claims 1 to 8. A step of reacting a polyphenylene ether represented by the following formula (12) with a phenol compound represented by any one of the following formulas (1 ′) to (6 ′);
A step of introducing a substituent containing a carbon-carbon double bond and / or an epoxy bond into at least a part of the terminal of the obtained polyphenylene ether;
A process for producing polyphenylene ether, comprising:
In formula (12),
R ³ is a C 1-6 alkyl group, R ⁴ is a hydrogen atom or a C 1-6 alkyl group, and the alkyl group may have a substituent as long as the condition of C 1-6 is satisfied. . p is an integer of 1-100.
In formula (1 ′)-formula (6 ′),
X is an arbitrary divalent linking group;
R ¹ and R ² are each independently a hydrogen atom, a C1-C6 hydrocarbon group, or a substituent containing a hydrocarbon group represented by formula (7), and at least one of R ¹ is represented by the formula ( The hydrocarbon group represented by 7) is included.
In formula (7), each b is independently 0 or 1,
R ¹¹ is each independently a C 1-8 alkyl group,
R ¹² is each independently a C 1-8 alkylene group;
R ¹³ represents a hydrogen atom, a C 1-8 alkyl group or a phenyl group,
The alkyl group, alkylene group, and phenyl group may have a substituent as long as the condition of C1-8 is satisfied. A curing agent composition comprising the polyphenylene ether according to claim 1 and a polyfunctional curing agent capable of reacting with the terminal phenol.