JPH01113426A - Curable polyphenylene ether containing double bond and its preparation - Google Patents

Abstract

PURPOSE:To obtain the title polyphenylene ether giving a cured product having excellent chemical resistance and heat resistance, by metallizing a specified polyphenylene ether with an org. metal and carrying out its substitution reaction with an alkynyl halide. CONSTITUTION:The title polyphenylene ether having a substitution rate of alkynyl groups of formula IV represented by the equation V of 0.1-100mol% and being constituted substantially of formula III[wherein R1-4 is H or an alkynyl of formula IV; Q' is Q (substd. with an alkynyl of formula IV] is obtd. by metallizing a polyphenylene ether of formula I (wherein m is 1-6 representing the number of polyphenylene ether chains; n is the degree of polymn. of each chain; Q is H when m is 1 and a residue of a polyfunctional phenol compd. having 2-6 phenolic hydroxyl groups in the molecule and a nonpolymerizable substituent on an o- or p-position of the hydroxyl group when m is 2 or more) (A) with an org. metal (B), carrying out its substitution reaction with an alkynyl halide of formula II (wherein l is 1-4; L is Cl, Br or I; R5-7 are each H or CH3 and one or more of R5-7 is CH3 when l=1) (C).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a curable polyphenylene ether and a method for producing the same. The present invention relates to a curable polyphenylene ether that imparts properties and heat resistance, and a method for producing the same.

(Prior art) In recent years, there has been a remarkable trend towards miniaturization and higher density packaging methods in the field of electronic equipment for communications, consumer use, industrial use, etc. Heat-resistant,
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, polyphenylene ether is 2
When exposed to high temperatures over 00°C, it rapidly deforms,
This causes a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for circuit use. Furthermore, although polyphenylene ether has strong resistance to acids, alkalis, and hot water, it has extremely weak resistance to aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds, and dissolves in these solvents.

One method of improving the heat resistance and chemical resistance of polyphenylene ether has been proposed to introduce a crosslinking functional group into the chain of polyphenylene ether and use it as a curable polyphenylene ether. No satisfactory solution has been found. For example, U.S. Patent No. 34
No. 17053 discloses a method for 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.

On the other hand, US Pat. No. 4,634,742 discloses a method for introducing vinyl groups into the chains of polyphenylene ether through the following reaction. First, polyphenylene ether is reacted with bromine to bromate the 2- and 6-position methyl groups, or 1-chloromethoxy-4-chlorobutane and tin tetrachloride are used to perform a Friedel-Crach reaction to convert the phenyl groups into 3.5 Either method can be used to introduce a chloromethyl group into the position. 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 Witsch reaction using formaldehyde and sodium hydroxide. That is, this method requires three steps to introduce the vinyl group and also requires the use of a special reactant, which is extremely disadvantageous for industrial implementation. In addition, 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, so after crosslinking, it lacks flexibility and becomes an extremely brittle material. Not practical.

As a method of curing polyphenylene ether other than introducing a crosslinkable functional group, US Pat. 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 films or coatings on metals, glass, etc.

Furthermore, improvements in heat resistance and chemical resistance are also insufficient.

[Problem that the invention seeks to solve]

In view of the above circumstances, the present invention aims to provide a polyphenylene ether with significantly improved heat resistance and chemical resistance. In general, the present invention aims to provide a simple and economical method for producing this new polyphenylene ether.

[Means for solving problems]

The inventors of the present invention have conducted intensive studies to solve this problem.
An attempt was made to invent a polyphenylene ether with a novel structure and a method for producing the same in accordance with the object of the present invention.

That is, the first aspect of the present invention is - Monana [where m is the number of polyphenylene ether chains from 1 to 6,
n indicates the degree of polymerization of 6 chains, R1-R4 is hydrogen or the general formula (ρ is an integer of 1 to 4, R5-R7 represents hydrogen or a methyl group, and when J) = 1, at least one of R5-R7 One is a methyl group. ), Q' represents Q and/or Q substituted with the above alkenyl group (If), Q represents hydrogen when m is 1, and one molecule when m is 2 or more. It represents the residue of a polyfunctional phenol compound having 2 to 6 phenolic hydroxyl groups therein and polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. A curable polyphenylene ether consisting essentially of provide.

Substitution rate of alkenyl group = Roughly speaking, the second aspect of the present invention is based on the general formula [where m is the number of polyphenylene ether chains of 1 to 6,
n indicates the degree of polymerization of the polymer, Q represents hydrogen when m is 1, and when m is 2 or more, one molecule has 2 to 6 phenolic hydroxyl groups, and the ortho position of the phenolic hydroxyl group and The process of metallating a polyphenylene ether represented by a residue of a polyfunctional phenol compound having a polymerization-inactive substituent at the para position with an organic metal and the general formula (where Ω is an integer from 1 to 4). is chlorine, bromine or iodine, R5-R7 is hydrogen or a methyl group, and when 1.1l=1, at least one of R5-R7 is a methyl group). Provided is a method for producing the above-mentioned curable polyphenylene ether, which comprises a step of carrying out a substitution reaction.

It is represented by the polyphenylene ether used in the present invention. In the formula, m represents the number of polyphenylene ether chains of 1 to 6, and n represents the degree of polymerization of the polymer. In addition, Q represents hydrogen when m is 1, and when m is 2 or more, it has 2 to 6 phenolic hydroxyl groups in one molecule, and polymerizable inert substitution at the ortho and para positions of the phenolic hydroxyl group. Represents the residue of a polyfunctional phenol compound having a group.

Typical examples include compounds represented by the following four general formulas.

[In the formula, A1. A2 is the same or different 7 and has 1 to 4 carbon atoms
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 hydrocarbon residue. Represents residues and substituted derivatives thereof, aromatic hydrocarbon residues and substituted derivatives thereof, aralkyl groups and substituted derivatives thereof, Z represents oxygen, sulfur, sulfonyl group, carbonyl group, and 2 directly bonded to A2. two phenyl groups, A2 and X5
The bonding positions of A2 and Y and A2 and 7 all represent the ortho and para positions of the phenolic hydroxyl group, p represents an integer of 0 to 4, and q represents an integer of 2 to 6. ] Specific examples include the following.

The method for producing the polyphenylene ether of general formula (III) is not limited in carrying out the present invention,
For example, 2,6-cystylphenol is oxidatively polymerized alone, or 2,6-cystylphenol is polymerized in the presence of the above-mentioned polyfunctional phenol compound.
Oxidative polymerization may be carried out by the method known in No. 15, No. 40616, etc. There is also no particular restriction on its molecular weight, and it can be used from oligomers to polymers, but in particular, it should have a viscosity number ηsMc measured in a 0.5 g/dl chloroform solution at 30°C in the range of 0.2 to 1.0. It is preferable to use one.

The first method for producing the alkenyl group-substituted curable polyphenylene ether of the present invention comprises the steps of metalizing the above-mentioned polyphenylene ether (■) with an organometallic compound and then subjecting it to a substitution reaction with an alkenyl halide. Examples of organic metals include methyllithium, n-butyllithium, 5ec-butyllithium, tert-butyllithium, and phenyllithium and alkyl sodium. Moreover, the alkenyl halide used in the present invention is a compound represented by
5-R7 represents hydrogen or a methyl group, and when p=1, at least one of R5-R7 represents a methyl group. Specific examples include 4-bromo-1-butene, trans- and/or cis-1-bromo-2-butene, trans- and/or cis-1-chloro-2-butene, 1-
Chloro-2-methyl-2-propene, 5-bromo-1-
Pentene, 4-bromo-2-methyl-2-butene, 6-
Bromo-1-hexene, 5-bromo-2-methyl-2-
Examples include pentene.

The reaction is performed using tetrahydrofuran (hereinafter abbreviated as THF),
1. In addition to being carried out in ether solvents such as 4-dioxane and dimethoxyethane, cyclohexane, benzene, toluene, xylene, etc. can be carried out in the coexistence of N,N,N',N'-tetramethylethylenediamine (hereinafter abbreviated as TMEDA). It can also be carried out using a hydrocarbon solvent. In the actual reaction, it is preferable to use these solvents after pretreatment such as purification and dehydration, and even if they are mixed in an appropriate proportion, the first solvent other than the above, which does not inhibit the reaction, may be used.
A second solvent may also be present. It is particularly preferable that the reaction is carried out under an atmosphere of an inert gas such as nitrogen or argon.

There are no particular limitations on the temperature and time of the metalation reaction and the subsequent alkenylation reaction. For example, in the case of metallization, the reaction is carried out between 8°C and the boiling point of the system (for those that solidify, between the freezing point of the system and the boiling point of the system), particularly preferably 5°C.
C. to the boiling point of the system, and the time is preferably about 1 second to 50 hours, more preferably about 1 minute to 10 hours. Regarding the alkenylation reaction, the reaction is usually carried out between 8°C and the boiling point of the system (for those that solidify, between the freezing point of the system and the boiling point of the system), and the reaction time is approximately 1 second to 50 hours, generally preferred. is preferably about 1 minute to 10 hours.

According to this method, alkenyl groups can be substituted simultaneously at one or both positions of the methyl group at the 2.6-position of the polyphenylene ether chain and the 3- and 5-positions of the phenyl group. The phenyl group and alkyl group in the residue of the polyfunctional phenol compound roughly represented by Q can also be substituted.

Factors that control the substitution position of the alkenyl group include the temperature of the reaction system, reaction time, type of solvent, etc. Factors controlling the substitution rate include the temperature of the reaction system, the reaction time, the type of solvent, the amount of organic metal N and alkenyl halide used in the reaction, and the like. Although the substitution rate can be controlled by any factor, it is preferable to use a method of controlling the amount of organometallic and adding an equivalent amount or more of alkenyl halide, or a method of controlling the amount of alkenyl halide using an excess amount of organometal. Good to use. The amount of organometallic and alkenyl halide used here is preferably from o.ooi to 5 moles per mole of phenyl group.

The substitution rate of alkenyl groups in the present invention is defined as the ratio of the total number of alkenyl groups in the polymer to the total number of phenyl groups in the polymer, and is at most 400 mol%.

The substitution rate necessary to achieve the purpose of the present invention is 0.1 to 10
It is 0 mol%, particularly preferably 0.5 to 50 mol%. If the substitution rate is less than 0.1 mol%, it is not preferable because sufficient chemical resistance, which is the object of the present invention, cannot be obtained. Furthermore, if the substitution rate exceeds 100 mol%, the material becomes extremely brittle and difficult to handle before and after molding, which is also undesirable.

There is no particular restriction on the molecular weight of the alkenyl group-substituted curable polyphenylene ether of the present invention, and it can be used from oligomers to polymers. Particularly preferably, 30°C,
Viscosity number η measured in chloroform solution of 0.59/d+
sp/c ranges from 0.2 to 1.0.

The alkenyl group introduced into the alkenyl group-substituted curable polyphenylene ether of the present invention can be detected by nuclear magnetic resonance (hereinafter referred to as NMR).
It can be detected by methods such as infrared absorption (hereinafter abbreviated as IR) spectroscopy,
The substitution rate can be determined from the area ratio of the peaks in the 1-NMR spectrum.

Although the alkenyl group-substituted curable polyphenylene ether of the present invention can be cured by any method, heating is usually used.

The alkenyl group-substituted curable polyphenylene ether of the present invention can not only be used alone, but also be blended with fillers and additives in amounts that do not impair its original properties, in order to impart desired performance depending on the intended use. can do. The filler may be in the form of fibers or powder, and may include carbon fibers, glass fibers, boron fibers, ceramic fibers, asbestos fibers, carbon black, silica, talc, mica, glass peas, and the like. Further, as additives, antioxidants, heat stabilizers, flame retardants, antistatic agents, plasticizers, pigments, dyes, colorants, etc. can be blended. Furthermore, it is also possible to blend one or more types of crosslinkable 7-mer and other thermoplastic and thermosetting resins.

[Action of the invention]

The first feature of the alkenyl group-substituted curable polyphenylene ether of the present invention is that it improves heat resistance and chemical resistance through crosslinking, and specifically increases the glass transition temperature and decreases the linear expansion coefficient above the glass transition temperature. This is a significant decrease 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 by 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 having no 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 can be converted into curable polyphenylene ethers at low temperatures and in a short time through general reactions. . 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.

〔Example〕

EXAMPLES Hereinafter, in order to further clarify the present invention, the present invention will be explained using Examples, but the scope of the present invention is not limited to these Examples.

Examples 1 to 4 Bifunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane as the polyfunctional phenol compound) .

Hereinafter, it will be abbreviated as PPE-1. >2.09 THFioo
n-butyllithium (1,63 mol/
l, hexane solution)1. Od, 3.1ml, 4.1m
e.

and 6.1d were added, and the mixture was heated under reflux for 1 hour under a nitrogen atmosphere. After cooling to room temperature, 0.239, 0.68 g, 0.90 g, and 1.4 g of 4-bromo-1-butene were added, respectively, and the mixture was stirred at room temperature for 30 minutes.

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 rate of 3-butenyl group was determined by 'H-NMR, it was found to be 0.8%, 5%, and 11%, respectively.
%, 20%.

These polymers were dissolved in chloroform and poured onto a glass plate to form a film with a thickness of about 100 μm, which was then fixed on the glass plate and heat-treated in an air oven at 280° C. for 30 minutes. Solubility of this film in chloroform and thermomechanical analysis device (hereinafter abbreviated as TMA)
Glass transition temperature (Tg), linear expansion coefficient (α) measured at
are shown in Table 1.

Further, 20 layers of the above-mentioned cast film were formed, molded and heat-treated using a vacuum press at 280°C. Using the obtained sheet with a thickness of 2 m, the relative dielectric constant (εr
) The dielectric loss tangent (tan δ) was measured.

The results are also shown in Table-1.

Examples 5-7 PPE-12,09 was dissolved in THElood and n
10.2 m, 20.4 me, and 40.9 m of -butyllithium (1,63 mol/j!, hexane solution) were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. Zarani 4
-bromo-1-butene, 2.3 g, 4.5
g.

After adding 9.0 g 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 1H-NMR and were 27%, 49%, and 80%, respectively. Table 1 shows the physical properties measured according to Examples 1 to 4.

In addition, 1H- of Example 5 (3-butenyl group substitution rate 27%)
The NMR (CDCI! 3 solution) spectrum is shown in Figure 1.
The IR spectrum (diffuse reflection method) is shown in FIG.

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 2
Heat treatment was performed in an air oven at 80° C. for 30 minutes. Further, 20 sheets of cast film were laminated, molded and heat-treated by sandwiching them between a vacuum press at 280° C., and a sheet having a thickness of 2 m was obtained. 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 A reaction was carried out in the same manner as in Examples 5 to 7 using 12.0 g of PPE, 0.6 Id of n-butyllithium (1,63 mol/1), and 0.149 g of 4-bromo-1-butene.

The substitution rate of 3-butenyl group determined by 1H-NMR is O, O
It was S%. Table 1 shows the physical properties measured according to Examples 1 to 4.

Example 8 Poly(2,6-dimethylphenylene-1,4-ether) (hereinafter PPE-
(abbreviated as 2) 2.09 with 100% toluene and TH
A mixed solution of 1.3d was dissolved in ED, 5.1 parts of n-butyllithium (1.63 mol/fl, hexane solution) was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 6 hours. Next, 1.1 g of 4-bromo-1-butene was added and the mixture was roughly mixed at room temperature.
Stir for hours. When the polymer was precipitated with a large amount of methanol and 'H-NMR was measured after isolation, the substitution rate of 3-butenyl groups was 11%.

Table 2 shows the physical properties measured according to Examples 1 to 4.

Example 9 A reaction was carried out in exactly the same manner as in Example 8, using 0.76 g of 1-chloro-2-butene (cis/trans mixture) instead of 4-bromo-1-butene.

After isolation, the substitution rate of 2-butenyl group determined by '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 -22,0g, n-butyllithium (1,63
mole/, 1 ri 4.1, 4-bromo-2-methyl-2-
The reaction was carried out in the same manner as in Examples 1 to 4 using butene 1.0 (j). After isolation, the substitution rate of 3-methyl-2-butenyl group determined by 1H-NMR was 13%. The H-NMR spectrum (CDC, f) 3 solution) is shown in FIG. Further, the physical properties of this polymer measured according to Examples 1 to 4 are shown in Table 2.

Example 11 Poly(2
, 6-dimethylphenylene-1,4-ether) (hereinafter abbreviated as P'PE-3)2. og THElooml
n-butyllithium (1,63 mol/ρ,
After adding 1.02 g of a hexane solution at room temperature under a nitrogen atmosphere, the mixture was further heated under reflux for 30 minutes. After cooling to room temperature 4
- Add 2.57 bromo-2-methyl-2-butene to 3
Stirring was continued for 0 minutes and finally poured into a large amount of methanol. After isolation, 1H-NMR measurement revealed that 3-methyl-2
The substitution rate of -butenyl groups was 47%.

Table 2 shows the physical properties measured in the same manner as in Examples 1 to 4.

Example 12 PPE -32.0g, n-butyllithium (1,63
Mol/fl') 10.2d A reaction was carried out in the same manner as in Examples 5 to 7 using 1.5 g of 11-chloro-2-methyl-2-propene. 2- determined by 1H-NMR after isolation
The substitution rate of methyl-2-propenyl group was 21%.

Table 2 shows the physical properties measured in the same manner as in Examples 1 to 4.

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 sheets of these cast films were laminated and molded using a vacuum press to a thickness of 2 inches! It was set as an r1 sheet. Using this film and sheet, physical properties were measured in the same manner as in Examples 1 to 4. The results are shown in Table-2.

Examples 13 and 14 2.0 g of difunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using bis(3,5-dimethyl-4-hydroxyphenyl) sulfone as a polyfunctional phenol compound). Toluene 100In
i, T) Dissolved in a mixed solution of IEDA 2.5d, n
-butyl lithium (1,60 mol/j!, hexane solution>10.4 d) was added and reacted at 60°C for 1 hour in a nitrogen atmosphere. After cooling to room temperature, 0.5 g of 5-bromo-1-pentene and Add 1.0g and stir at room temperature for 30 minutes.
Subsequently, a large amount of methanol was used to precipitate the polymer.

When '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 Bifunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using 3,3°, 5,5°-tetramethyl phenyl-4,4′-diol as a polyfunctional phenol compound) >2.0 g was suspended in a mixed solution of 100 d of cyclohexane, TME DA2.5 rIJl, and
10.47 (mol/I, hexane solution) was added and reacted at 80° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, 2.7 g of 6-bromo-1-hexene was added, and the mixture was further stirred at room temperature for 30 minutes. After isolation, 'H-NMR was measured, and the substitution rate of 5-hexenyl group was 34%. Table 2 shows the physical properties measured according to Examples 1 to 4.

Example 16 2.0 g of trifunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using tris(3,5-dimethyl-4-hydroxyphenyl)methane as a polyfunctional phenol compound) in cyclohexane 10
Suspend in a mixed solution of 0 dSTME DAl and 3 rIII, add 5.27 n-butyllithium (1,60 mol/1, hexane solution), and heat at 60°C under nitrogen atmosphere.
The reaction was carried out for 1 hour. Subsequently, 1.4 g of 6-bromo-1-hexene was added, and the mixture was stirred roughly for 1 hour at 60°C.

After cooling, it was poured into a large amount of methanol to precipitate the polymer. After isolation, 'H-NMR was measured, and the substitution rate of 5-hexenyl group was 11%. Table 2 shows the physical properties measured according to Examples 1 to 4.

(The following is a blank space) (Effects of the Invention) According to the present invention, a crosslinkable alkenyl group can be introduced in one step through a 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.

Since the obtained alkenyl group-substituted polyphenylene ether 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. 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]

Figure 1 shows the 'H-NMR spectrum of Example 5 (CDCf
13 solution). FIG. 2 is the same IR spectrum (diffuse reflection method) of Example 5. Figure 3 shows the 'H-NMR spectrum (CDC) of Example 10.
, I13 solution). Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, m is the number of polyphenylene ether chains from 1 to 6,
n indicates the degree of polymerization of each chain, R_1 to R_4 represent hydrogen or a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (l is an integer from 1 to 4, R_5 to R_7 represent hydrogen or a methyl group , when l=1, at least one of R_5 to R_7 is a methyl group), and Q' represents Q and/or the above alkenyl group (I
Represents Q substituted with I), Q represents hydrogen when m is 1, and when m is 2 or more, it has 2 to 6 phenolic hydroxyl groups in one molecule, and the ortho position of the phenolic hydroxyl group and Represents the residue of a polyfunctional phenol compound having a polymerization-inactive substituent at the para position. A curable polyphenylene ether consisting essentially of: Substitution rate of alkenyl group = (total number of moles of alkenyl group/total number of moles of phenyl group) ×
100 (%) 2) The curable polyphenylene ether according to claim 1, wherein in the general formula (I), m is 1 or 2. 3) The substitution rate of alkenyl group is 0.5 mol% or more and 5
The curable polyphenylene ether according to claim 2, which has a content of 0 mol % or less. 4) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, m is the number of polyphenylene ether chains from 1 to 6,
n indicates the degree of polymerization of each chain, Q represents hydrogen when m is 1, and when m is 2 or more, one molecule has 2 to 6 phenolic hydroxyl groups, and the ortho position of the phenolic hydroxyl group and Represents the residue of a polyfunctional phenol compound having a polymerization-inactive substituent at the para position. ] Process and general formula for metalizing polyphenylene ether with organometallic formula ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) (In the formula, l represents an integer from 1 to 4, L represents chlorine or bromine or represents iodine, 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.) A method for producing a curable polyphenylene ether according to claim 1. 5) The method for producing a curable polyphenylene ether according to claim 4, wherein m is 1 or 2 in general formula (III).