JPH058933B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a curable polyphenylene ether and a method for producing the same, and more specifically, it provides chemical resistance and heat resistance after curing by partially introducing alkenyl groups. This invention relates to curable polyphenylene ether and its manufacturing method. [Prior Art] In recent years, there has been a remarkable trend toward miniaturization and higher density packaging methods in the field of electronic equipment for communications, consumer use, industrial use, etc. Heat resistance, dimensional stability, and electrical properties are increasingly required. For example, as printed wiring boards, copper-clad laminates made of thermosetting resins such as phenol resins and epoxy resins have traditionally been used. Although these have a good balance of various performances, they have the disadvantage of poor electrical properties, particularly poor dielectric properties in the high frequency range. Polyphenylene ether has recently attracted attention as a new material to solve this problem, and attempts have been made to apply it to copper-clad laminates. Polyphenylene ether is an engineering plastic with excellent mechanical and electrical properties, and has relatively high heat resistance. However, when attempting to use it as a printed wiring board, extremely high solder heat resistance is required, so the inherent heat resistance of polyphenylene ether is by no means sufficient. That is, when polyphenylene ether is exposed to high temperatures of 200° C. or higher, it rapidly deforms, causing a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for circuit use. Although polyphenylene ether has strong resistance to acids, alkalis, and hot water, it has extremely low resistance to aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds, and dissolves in these solvents. As one method to improve the heat resistance and chemical resistance of polyphenylene ether, a method has been proposed to introduce a crosslinking functional group into the chain of polyphenylene ether and use it as a curable polyphenylene ether. However, no satisfactory solution has been found so far. For example, US Pat. No. 3,417,053 discloses a method of introducing an alkoxysilyl group into the chain of polyphenylene ether. Alkoxysilyl groups are easily hydrolyzed when they come into contact with water,
It becomes siloxane through silanol and crosslinks.
However, this alkoxysilylated polyphenylene ether crosslinks even when exposed to water vapor in the air at room temperature, making it extremely difficult to handle. Furthermore, since alcohol and water are produced during hydrolysis and crosslinking, voids are likely to occur in the molded product, making it impractical. Kurian uses polymers of 2-allyl-6-methylphenol or 2,6-diallylphenol as curable polyphenylene ethers.
It is disclosed in Journal of Polymer Science, Vol. 49, p. 267 (1961). However, these homopolymerizations only yield low molecular weight products, and if the resulting polymers are left in the air,
It hardens in a few weeks and becomes unusable. U.S. Patent No. 328139 and U.S. Patent No. 3422062,
2,6-dimethylphenol and 2-allyl-6-
Copolymers with methylphenol or 2,6-diallylphenol are disclosed. Although this copolymer has a high molecular weight, it is impossible to thermoform it because the melting temperature is higher than the curing temperature (U.S. Pat. No. 3,422,062, Examples 3 and 4). As a method for improving moldability, US Pat. No. 3,422,062 attempts to use a large amount of plasticizer, but this impairs the excellent dielectric properties (low dielectric constant, low dielectric loss tangent) of polyphenylene ether. Not only that, but it also leads to a decrease in heat resistance and chemical resistance. In addition, the tensile strength of this cured product is an extremely low value of 28 Kg/cm ² as shown in Example 7, and it is difficult to say that it can withstand practical use. Tsuchida et al. reported that 2-(substituted allyl) is a polyphenylene ether containing a double bond other than an allyl group.
-6-Methylphenol or 2,6-di(substituted allyl)phenol polymer
No. 120729, No. 58-27719, Makromol, Chem.
Magazine volume 182, page 2361 (1981) and magazine volume 183, 1889
(1982). According to new findings based on their systematic research, a comparative study of the oxidative polymerizability of 2,6-disubstituted phenols with double bonds in their side chains revealed that (1) the double bond conjugated with the phenol nucleus With monomers such as 2,6-divinylphenol, branching and cross-linking occurs during polymerization due to its conjugated structure, making it impossible to obtain linear polyphenylene ether; In monomers in which the bonds are located far from the phenol nucleus, polymerization does not occur due to their steric bulk. Therefore, 2,
It has been concluded that phenols in which one or both of the substituents at the 6-position are substituted allyl groups are the only monomers that provide polyphenylene ethers having reactive double bonds in their side chains. Examples of substituted allyl groups include butenyl groups, prenyl groups, cinnamyl groups, etc., and it is disclosed that double bonds can be used for grafting, halogen addition, epoxidation, and amination reactions by radical polymerization of vinyl monomers. has been done. However, nothing has been shown about the crosslinking properties, thermal properties, and physical properties of polyphenylene ether, and it is expensive because it uses phenols with special double bonds such as butenyl, prenyl, and cinnamyl groups. There is a drawback. A vinyl group-substituted polyphenylene ether is disclosed in US Pat. No. 4,634,742 as a polyphenylene ether whose double bond is conjugated with a phenol nucleus. This can be obtained by using a polymer of 2,6-dimethylphenol and replacing the methyl groups of the polymer with vinyl groups, or by introducing vinyl groups into the 3 and 5 positions of the phenyl group. be. In other words, since the vinyl group introduced in this way is directly bonded to the aromatic ring of polyphenylene ether without going through a flexible carbon chain or ether bond, the material lacks flexibility and is extremely brittle after crosslinking. This makes it impractical for practical use. Additionally, this polymer has low crosslinking reactivity and requires high temperatures of 300°C or higher for crosslinking. Furthermore, as a method for producing the polyphenylene ether, first, polyphenylene ether is reacted with bromine to bromate the methyl groups at the 2 and 6 positions, or 1-chloromethoxy-4-chlorobutane and tin tetrachloride are used. Either a Friedel-Crafts reaction may be carried out to introduce chloromethyl groups into the 3 and 4 positions of the phenyl group. Subsequently, the halomethyl group thus obtained is reacted with triphenylphosphine to form a phosphonium salt. Finally, it is converted into a vinyl group by carrying out a Witzig reaction using formaldehyde and sodium hydroxide. That is, this method requires three steps to introduce the vinyl group and requires the use of a special reactant, which is extremely disadvantageous for industrial use. As a method of curing polyphenylene ether other than introducing a crosslinkable functional group, U.S. Patent No.
No. 3,455,736 discloses a method of heat treating polyphenylene ether in the presence of oxygen. The polyphenylene ether used here is only an unsubstituted phenol polymer, and no examples are given for 2,6-dimethyl substituted polyphenylene ether, which is widely known today. Furthermore, since contact with oxygen is required, its use is limited to coatings on films, metals, glass, etc. Furthermore, improvements in heat resistance and chemical resistance are also insufficient. [Problems to be Solved by the Invention] In view of the above circumstances, the present invention aims to provide a polyphenylene ether with significantly improved thermoformability, heat resistance, and chemical resistance.
Furthermore, the present invention aims to provide a simple and economical method for producing this new polyphenylene ether. [Means for solving the problem] As a result of intensive studies to solve this problem, the present inventors have invented a polyphenylene ether with a new structure and a method for producing the same that meets the purpose of the present invention. Ivy. That is, the first aspect of the present invention is the general formula [In the formula, m is the number of polyphenylene ether chains of 1 to 3, n indicates the degree of polymerization of each chain, and R ₁ to R ₄ are hydrogen or the general formula (l is an integer of 1 to 4, R ₅ to R ₇ represent hydrogen or a methyl group, and when l = 1, at least one of R ₅ to _{R 7} is a methyl group.) , Q' represents Q and/or Q substituted with the above alkenyl group ( Represents the residue of a polyfunctional phenol compound that has a phenolic hydroxyl group and has polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. ], the substitution rate of alkenyl groups defined by the following formula is
0.1 mol% or more and 100 mol% or less, and 30℃,
Provided is a curable polyphenylene ether characterized by having a viscosity number ηsp/C of 0.2 or more and 1.0 or less as measured with a 0.5 g/dl chloroform solution. Substitution rate of alkenyl group = total number of moles of alkenyl group / total number of moles of phenyl group x 100 (%) Furthermore, the second aspect of the present invention is that the general formula [In the formula, m represents the number of polyphenylene ether chains of 1 to 3, n represents the degree of polymerization of each chain, Q represents hydrogen when m is 1, and represents one molecule when m is 2 or 3. 2 or 3 phenolic hydroxyl groups in the polyphenylene ether, and represents a residue of a polyfunctional phenol compound having polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl groups. Process of metallization with organic metal and general formula (In the formula, l represents an integer of 1 to 4, L represents chlorine, bromine, or iodine, R ₅ to R ₇ represent hydrogen or a methyl group, and when l = 1, R ₅ to
At least one of R ₇ is a methyl group. ) There is provided a method for producing the above-mentioned curable polyphenylene ether, which comprises a step of carrying out a substitution reaction with an alkenyl halide represented by: The polyphenylene ether used in the present invention has the general formula It is expressed as In the formula, m represents the number of polyphenylene ether chains of 1 to 3, and n represents the degree of polymerization of each chain. Q represents hydrogen when m is 1, and when m is 2 or 3, each molecule has 2 or 3 phenolic hydroxyl groups, and the ortho and para positions of the phenolic hydroxyl groups are polymerizable and inactive. Represents the residue of a polyfunctional phenol compound having a substituent. Typical examples include compounds represented by the following four general formulas. [In the formula, A ₁ and A ₂ are the same or different carbon numbers 1
-4 represents a linear alkyl group, X represents an aliphatic hydrocarbon residue and their substituted derivatives, an aralkyl group and their substituted derivatives, oxygen, sulfur, a sulfonyl group, a carbonyl group, etc., and Y represents an aliphatic represents hydrocarbon residues and their substituted derivatives, aromatic hydrocarbon residues and their substituted derivatives, aralkyl groups and their substituted derivatives, and Z
represents oxygen, sulfur, sulfonyl group, carbonyl group, two phenyl groups directly bonded to A ₂ , A ₂
The bonding positions of and X, A ₂ and Y, and A ₂ and Z all indicate the ortho and para positions of the phenolic hydroxyl group,
p represents an integer of 0 or 1, and q represents an integer of 2 or 3. ] As a specific example, (However, X is −CH ₂ −,

[Formula]-O-,- S-,

【formula】 [Action of the invention]

Prior art polyphenylene ethers containing double bonds include vinyl group-substituted polyphenylene ethers in which the double bond is directly bonded to the phenyl group (U.S. Pat. No. 4,534,742) and polyphenylene ethers containing vinyl groups between the double bond and the phenyl group. Polyphenylene ether in which one methylene chain is interposed in the polyphenylene ether (U.S. Pat. No. 3,281,393, U.S. Pat. No. 3,422,062, and JP-A-56-120729, etc.)
can be mentioned. The alkenyl group-substituted curable polyphenylene ether, which is the first aspect of the present invention, has a structure different from conventional polymers because two methylene chains are interposed between the double bond and the phenyl group. It can be thermoformed and has improved heat resistance and chemical resistance after curing. Specifically, these include an increase in the glass transition temperature, a significant decrease in the coefficient of linear expansion above the glass transition temperature, and insolubilization in aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds. These effects occur because the double bond portion of the alkenyl group undergoes a polymerization reaction upon heating to give a cured product of polyphenylene ether. Since this polymerization reaction is an addition type, there is no generation of water or the like as in a condensation reaction, and a cured product without voids can be obtained, and there is almost no shrinkage in volume. The present invention is also characterized in that the excellent dielectric properties inherent to polyphenylene ether are maintained with almost no deterioration due to the introduction of alkenyl groups and crosslinking. Next, the second feature of the present invention, the method for producing alkenyl group-substituted curable polyphenylene ethers, is that existing polyphenylene ethers are converted into curable polyphenylene ethers in a short time at low temperatures through a one-step reaction. The point is that it can be converted. One of the characteristics is that the substitution rate of alkenyl groups can be easily controlled over a wide range by changing the reaction conditions. [Examples] Hereinafter, the present invention will be explained using examples to further clarify the present invention, but the scope of the present invention is not limited to these examples. Examples 1 to 4 Oxidative polymerization of 2,6-dimethylphenol using bifunctional polyphenylene ether (2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane as the polyfunctional phenol compound) (hereinafter abbreviated as PPE-1) 2.0g
Dissolved in 100 ml of THF, 1.0 ml of n-butyllithium (1.63 mol/l, hexane solution), 3.1 ml,
4.1 ml and 6.1 ml were added, and the mixture was heated under reflux for 1 hour under a nitrogen atmosphere. After cooling to room temperature, 0.23 g, 0.68 g of 4-bromo-1-butene, and
0.90g and 1.4g were added and stirred for 30 minutes at room temperature. After pouring into a large amount of methanol to precipitate the polymer, filtration and washing with methanol were repeated three times to obtain a white powder product. When the substitution rates of 3-butenyl groups were determined by ¹ H-NMR, they were 0.8%, 5%, 11%, and 20%, respectively. Dissolve these polymers in chloroform,
After pouring it onto a glass plate to form a film with a thickness of about 100 μm, it was fixed on a glass plate and heat-treated in an air oven at 280°C for 30 minutes. Table 1 shows the solubility of this film in chloroform, the glass transition temperature (Tg) and linear expansion coefficient (α) measured with a thermomechanical analyzer (hereinafter abbreviated as TMA). In addition, 20 sheets of the above cast film are laminated, and 280
It was molded and heat treated by being placed in a vacuum press at ℃. Using the obtained sheet with a thickness of 2 mm, the relative dielectric constant (εr) and dielectric loss tangent (tan δ) were measured at 1 MHz. The results are also shown in Table-1. Examples 5 to 7 2.0g of PPE-1 was dissolved in 100ml of THF, and n
10.2 ml, 20.4 ml, and 40.9 ml of -butyllithium (1.63 mol/hexane solution) were added and stirred at room temperature under nitrogen atmosphere for 1 hour. Furthermore, 2.3 g, 4.5 g, and 9.0 g of 4-bromo-1-butene, respectively.
After adding and stirring for 30 minutes, the mixture was poured into a large amount of methanol to precipitate the polymer. After isolation, the substitution rates of 3-butenyl groups were determined by ¹ H-NMR and were 27%, 49%, and 80%, respectively. Table 1 shows the physical properties measured in accordance with Examples 1 to 4. Moreover, in Example 5 (3-butenyl group substitution rate 27%)
¹ H-NMR (CDCl ₃ solution) spectrum is shown in Figure 1.
The IR spectrum (diffuse reflection method) is shown in Figure 2. Comparative Examples 1 and 2 A chloroform solution of PPE-1 was poured onto a glass plate and dried to form a film with a thickness of about 100 μm. This is referred to as Comparative Example 1. Furthermore, this cast film was fixed on a glass plate and heat treated in an air oven at 280°C for 30 minutes. In addition, 20 sheets of cast film are laminated, and 280
Shaped and heat treated by sandwiching it between a vacuum press at ℃,
It was made into a sheet with a thickness of 2 mm. These are referred to as Comparative Example 2. The physical properties of Comparative Examples 1 and 2 are shown in Table-1. Comparative Example 3 PPE-1 2.0g, n-butyllithium (1.63
mol/) 0.6ml, 4-bromo-1-butene 0.14
The reaction was carried out in the same manner as in Examples 5 to 7 using g. The substitution rate of 3-butenyl group determined by ¹ H-NMR is
It was 0.05%. Table 1 shows the physical properties measured in accordance with Examples 1 to 4.

[Table] *2 ○: Completely dissolved △: Partially dissolved and colored by chloroform ×: Insoluble *3 Measured at a chuck distance of 15 mm and a heating rate of 10°C/min.
*4 Coefficient of linear expansion from room temperature to glass transition temperature (Tg) *5 Coefficient of linear expansion above Tg *6 Measured value at 1MHz *7 No clear Tg shown up to 300°C.
Example 8 Poly(2,6-dimethylphenylene-1,4-ether) (hereinafter referred to as
(abbreviated as PPE-2) 2.0g with 100ml of toluene
Dissolved in a mixed solution of 1.3 ml of TMEDA, n-butyllithium (1.63 mol/, hexane solution) 5.1
ml was added and reacted for 6 hours at room temperature under a nitrogen atmosphere. Subsequently, 1.1 g of 4-bromo-1-butene was added, and the mixture was further stirred at room temperature for 2 hours. When the polymer was precipitated with a large amount of methanol and ¹ H-NMR was measured after isolation, the substitution rate of 3-butenyl groups was 11%. Table 2 shows the physical properties measured in accordance with Examples 1 to 4. Example 9 1-chloro- instead of 4-bromo-1-butene
A reaction was carried out in exactly the same manner as in Example 8 using 0.76 g of 2-butene (cis/trans mixture). After isolation, the substitution rate of 2-butenyl group determined by ¹ H-NMR was 11%. The physical properties of this polymer measured according to Examples 1 to 4 are shown in Table 2. Example 10 PPE-2 2.0g, n-butyllithium (1.63
mol/) 4.1ml, 4-bromo-2-methyl-2
The reaction was carried out in the same manner as in Examples 1 to 4 using 1.0 g of -butene. 3- determined by ¹ H-NMR after isolation
The substitution rate of methyl-2-butenyl group was 13%. This ¹ H-NMR spectrum (CDCl ₃ solution) is shown in FIG. Further, the physical properties of this polymer measured in accordance with Examples 1 to 4 are shown in Table 2. Example 11 Poly(2,6-dimethylphenylene-1,4-ether) (hereinafter referred to as
PPE-3) was dissolved in 100 ml of THF, and 0.2 ml of n-butyllithium (1.63 mol/hexane solution) was added at room temperature under a nitrogen atmosphere, and the mixture was further heated under reflux for 30 minutes. After cooling to room temperature, 2.5 g of 4-bromo-2-methyl-2-butene was added, stirring was continued for 30 minutes, and finally the mixture was poured into a large amount of methanol. After isolation, ¹ H-NMR measurement revealed that the substitution rate of 3-methyl-2-butenyl groups was 47%. The physical properties measured in the same manner as Examples 1 to 4 are shown in the table below.
Shown in 2. Example 12 PPE-3 2.0g, n-butyllithium (1.63
mol/) 10.2ml, 1-chloro-2-methyl-2
- Reactions were carried out in the same manner as in Examples 5 to 7 using 1.5 g of propene. 2 determined by ¹ H-NMR after isolation
The substitution rate of -methyl-2-propenyl group was 21%. The physical properties measured in the same manner as Examples 1 to 4 are shown in the table below.
Shown in 2. Comparative Examples 4 and 5 PPE-2 and PPE-3 were dissolved in chloroform and poured onto a glass plate to obtain a film with a thickness of about 100 μm. In addition, 20 of these cast films were laminated and formed into a sheet with a thickness of 2 mm using a vacuum press. Examples 1 to 2 using this film and sheet
Physical properties were measured in the same manner as in 4. The results are shown in Table-2. Examples 13 and 14 Difunctional polyphenylene ether (bis(3,5-dimethyl-
using 4-hydroxyphenyl) sulfone, 2,
Oxidative polymerization of 6-dimethylphenol)
Dissolve 2.0g in a mixed solution of 100ml of toluene and 2.5ml of TMEDA, and dissolve n-butyllithium (1.60mol/
, hexane solution) was added thereto, and the mixture was reacted at 60° C. for 1 hour under a nitrogen atmosphere. After cooling to room temperature 5
0.5 g and 1.0 g of -bromo-1-pentene were added and stirred at room temperature for 30 minutes, followed by precipitation of the polymer with a large amount of methanol. When ¹ H-NMR was measured after isolation, the substitution rates of 4-pentenyl groups were 4% and 10%, respectively. Table 2 shows the physical properties measured in the same manner as in Examples 1 to 4. Example 15 Difunctional polyphenylene ether (using 3,3',5,5'-tetramethylbiphenyl-4,4'-diol as the polyfunctional phenol compound, 2,
Oxidative polymerization of 6-dimethylphenol)
2.0 g was suspended in a mixed solution of 100 ml of cyclohexane and 2.5 ml of TMEDA, 10.4 ml of n-butyllithium (1.60 mol/hexane solution) was added, and the mixture was reacted at 80° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, add 2.7g of 6-bromo-1-hexene.
was added, and the mixture was further stirred at room temperature for 30 minutes. ¹ H after isolation
-NMR measurement revealed that the substitution rate of 5-hexenyl groups was 34%. Table 2 shows the physical properties measured in accordance with Examples 1 to 4. Example 16 Trifunctional polyphenylene ether (using tris(3,5-dimethyl-4-hydroxyphenyl)methane as the polyfunctional phenol compound, 2.6
-oxidative polymerization of dimethylphenol) 2.0
g was suspended in a mixed solution of 100 ml of cyclohexane and 1.3 ml of TMEDA, 5.2 ml of n-butyllithium (1.60 mol/hexane solution) was added, and the mixture was reacted at 60° C. for 1 hour under a nitrogen atmosphere. Subsequently, 1.4 g of 6-bromo-1-hexene was added, and the mixture was further stirred at 60°C for 1 hour. After cooling, it was poured into a large amount of methanol to precipitate the polymer. After isolation, ^1H -NMR measurement revealed that the substitution rate of 5-hexenyl group was 11%.
It was hot. Table 2 shows the physical properties measured in accordance with Examples 1 to 4. The cast films having a thickness of about 100 μm obtained in Examples 5 and 10 were placed in a press at 280° C. and heat-treated for 30 minutes. These films were cut into 1 cm wide pieces and subjected to a tensile test. A similar test was conducted on the film before heat treatment.
The results are shown in Table-3. All of them show that they have practical strength.

【table】

[Table] *2 ○: Completely dissolved ×: Insoluble *3 Measured at a chuck distance of 15 mm and a heating rate of 10°C/min.
*4 Coefficient of linear expansion from room temperature to glass transition temperature (Tg) *5 Coefficient of linear expansion above Tg *6 Measured value at 1MHz *7 No clear Tg shown up to 300°C.

〔Effect of the invention〕

According to the present invention, a crosslinkable alkenyl group can be introduced in one step by polymer reaction of polyphenylene ether. The reaction can be applied over a wide range from low molecular weight substances to high molecular weight substances, and any amount of alkenyl groups can be introduced at low temperatures and in a short period of time. The obtained alkenyl group-substituted polyphenylene ether can be thermoformed (Examples 1 to 4),
Furthermore, since it becomes a curable polymer by heat or the like, it is imparted with properties such as heat resistance and chemical resistance, and can be used as a thermosetting heat-resistant resin. Furthermore, it is a thermosetting heat-resistant resin that has practical strength. Since the curing reaction of alkenyl groups is an addition reaction, by-products such as gas and water are not produced during curing, so there are advantages such as a uniform film and a void-free molded product. Furthermore, since it has excellent dielectric properties, it is suitable as a dielectric material.

[Brief explanation of the drawing]

FIG. 1 is the ¹ H-NMR spectrum of Example 5 (CDCl ₃ solution). Figure 2 also shows Example 5.
This is the IR spectrum (diffuse reflection method) of FIG. 3 is the ¹ H-NMR spectrum of Example 10 (CDCl ₃ solution).

Claims (1)

[Claims] 1. General formula [In the formula, m is the number of polyphenylene ether chains of 1 to 3, n indicates the degree of polymerization of each chain, and R ₁ to R ₄ are hydrogen or the general formula (l is an integer of 1 to 4, R ₅ to R ₇ represent hydrogen or a methyl group, and when l = 1, at least one of R ₅ to _{R 7} is a methyl group.) , Q' represents Q and/or Q substituted with the above alkenyl group ( Represents the residue of a polyfunctional phenol compound that has a phenolic hydroxyl group and has polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. A curable polyphenylene ether consisting essentially of ], which has a substitution rate of alkenyl group ( A curable polyphenylene ether having a viscosity number ηsp/C of 0.2 or more and 1.0 or less as measured in a chloroform solution of dl. Substitution ratio of alkenyl groups = total number of moles of alkenyl groups/total number of moles of phenyl groups x 100 (%) 2 In the general formula (), m is 1 or 2, the curable polyester according to claim 1 Phenylene ether. 3. The curable polyphenylene ether according to claim 2, wherein the substitution ratio of alkenyl groups is 0.5 mol% or more and 50 mol% or less. 4 General formula [In the formula, m is the number of polyphenylene ether chains of 1 to 3, n indicates the degree of polymerization of each chain, and R ₁ to R ₄ are hydrogen or the general formula (l is an integer of 1 to 4, R ₅ to R ₇ represent hydrogen or a methyl group, and when l = 1, at least one of R ₅ to _{R 7} is a methyl group.) , Q' represents Q and/or Q substituted with the above alkenyl group ( Represents the residue of a polyfunctional phenol compound that has a phenolic hydroxyl group and has polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. ], and the substitution rate of the alkenyl group ( A method for producing a curable polyphenylene ether having a viscosity number ηsp/C of 0.2 or more and 1.0 or less as measured in a chloroform solution of 0.5 g/dl at 30° C.,
general formula [In the formula, m represents the number of polyphenylene ether chains of 1 to 3, n represents the degree of polymerization of each chain, Q represents hydrogen when m is 1, and represents one molecule when m is 2 or 3. It represents the residue of a polyfunctional phenol compound having two or three phenolic hydroxyl groups therein, and polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl groups. ] Process and general formula for metalizing polyphenylene ether represented by organometallic [In the formula, l represents an integer of 1 to 4, L represents chlorine, bromine, or iodine, R ₅ to R ₇ represent hydrogen or a methyl group, and when l = 1, R ₅ to
At least one of R ₇ is a methyl group. ) A method for producing a curable polyphenylene ether, comprising the step of carrying out a substitution reaction with an alkenyl halide represented by: 5. The method for producing a curable polyphenylene ether according to claim 4, wherein in the general formula (), m is 1 or 2.