JPH01113425A - Curable polyphenylene ether containing triple bond and method for producing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 provides good quality and heat resistance, and a method for producing the same.

[Prior Art] In recent years, there has been a remarkable trend toward smaller packaging methods and higher density mounting 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, copper-clad laminates made of thermosetting resins such as phenol resins and epoxy resins have been used as printed wiring boards. 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 of 00° C. or higher, it undergoes rapid deformation, resulting in a significant decrease in mechanical strength and peeling of the copper layer 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.

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, but this alkoxysilylated polyphenylene ether also crosslinks 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 requires the use of a special reactant, which is extremely disadvantageous for industrial use. 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.

Although an ethynyl group is known as a typical crosslinkable functional group along with a vinyl group, no example has been disclosed so far in which an ethynyl group, or generally an alkynyl group, is introduced into polyphenylene ether.

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.

[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 heat resistance and chemical resistance. In summary, it is an object of the present invention to provide a simple and economical method for producing a novel polyphenylene ether.

[Means for solving the problem] As a result of intensive studies, the present inventors have found that 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 the general formula (where m is the number of polyphenylene ether chains of 1 to 6,
n indicates the degree of polymerization of 8 chains, R1-R4 is hydrogen or the general formula % () (, l! indicates an integer from 1 to 4, R5 is a methyl group or ethyl group when N = 1, ρ = 2 to 4, represents hydrogen or an alkynyl group represented by a methyl group or an ethyl group, Qu represents Q and/or Q substituted with the above alkynyl group (II), Q represents m is 1; and when m is 2 or more, a polyfunctional phenol having 2 to 6 phenolic hydroxyl groups in one molecule and having polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. Represents a residue of a compound. ], the substitution rate of the alkynyl group (II> defined by the following formula is 0.1 mol%)
or more and 100 mol% or less is provided.

Substitution ratio of alkynyl group = Also, the second aspect of the present invention is -Momona (where m is the number of polyphenylene ether chains of 1 to 6,
n represents the degree of polymerization of 8 chains, Q represents hydrogen with m being 1, and when m is 2 or more, one molecule has 2 to 6 phenolic hydroxyl groups; Represents the residue of a polyfunctional phenol compound having a polymerization-inactive substituent at the para position. ] Process of metallating polyphenylene ether represented by the formula L(CH2), lICEC-R5(IV)
represents an integer of 1 to 4, L represents chlorine, bromine, or iodine, and R5 represents a methyl group or an ethyl group when ρ=1. Provided is a method for producing the above-mentioned curable polyphenylene ether, which comprises a step of carrying out a substitution reaction with an alkynyl halide represented by hydrogen or a methyl group or an ethyl group when Q=2 to 4.

Furthermore, the third aspect of the present invention is - Monka (where m is the number of polyphenylene ether chains of 1 to 6,
n indicates the degree of polymerization of 8 chains, R6-R9 is hydrogen or the general formula % ( (g indicates an integer of 1 to 4, R5 is a methyl group or ethyl group when ρ = 1, ρ = 2 to 4 represents hydrogen or an alkenyl group represented by a methyl group or an ethyl group), and Q' represents Q and/or the above alkenyl group (
Vl), 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 a residue of a polyfunctional phenol compound having a polymerization-inactive substituent at the para position. ] The above-mentioned curable polyphenylene ether is characterized by comprising the steps of adding a halogen to the double bond of the alkenyl group of the alkenyl group-substituted polyphenylene ether consisting essentially of A second manufacturing method is provided.

The first polyphenylene ether used in the present invention is represented by the following general formula.

In the formula, m represents the number of chains from 1 to 6, and n represents the degree of polymerization of 8 chains. In addition, Q represents hydrogen when m is 1, and when m is 2 or more, Q has 2 to 6 phenolic hydroxyl groups in one molecule, and the polymerization inertness is at the ortho and para positions of the phenolic hydroxyl group. Represents a residue of a polyfunctional phenol compound having a substituent.

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

(In the formula, A1 and A2 represent the same or different linear alkyl groups having 1 to 4 carbon atoms, and X represents aliphatic hydrocarbon residues and substituted derivatives thereof, aralkyl groups and substituted derivatives thereof, oxygen, sulfur , sulfonyl group, carbonyl group, etc., Y represents an aliphatic hydrocarbon residue and substituted derivatives thereof, an aromatic hydrocarbon residue and substituted derivatives thereof, an aralkyl group and substituted derivatives thereof,
Z represents oxygen, sulfur, sulfonyl group, carbonyl group, two phenyl groups directly bonded to A2, A and XSA
The bonding positions of and YSA2 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 polyphenylene ether of general formula (III) is
The method for carrying out the present invention is not limited, and for example, 2,6-dimethylphenol is oxidatively polymerized alone, or 2,6-dimethylphenol is polymerized in the coexistence of the above-mentioned polyfunctional phenol compound. Phenol was specially designated in 1984.
Oxidative polymerization may be carried out by the method known in No. 40615, 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 has a viscosity number η sp/c measured in a chloroform solution of 0.5 g/old at 30°C in the range of 0.2 to 1.0. It is preferable to use one in the following.

The first method for producing the alkynyl group-substituted curable polyphenylene ether of the present invention comprises a step of metalizing the above-mentioned polyphenylene ether (I[I) with an organometallic substance, and then subjecting it to a substitution reaction with an alkynyl halide. As organic metals, methyllithium, n-butyllithium, 5ec
Examples include -butyllithium, tert-butyllithium, and phenyllithium and alkyl sodium. Further, the alkynyl halide used in the present invention is a compound represented by the following formula: -Montana%%(), where g represents an integer of 1 to 4, L represents chlorine, bromine, or iodine, R
5 is a methyl group or an ethyl group when ρ=1, N=2-4
represents hydrogen, methyl group or ethyl group. Specific examples include 4-bromo-1-butyne, 4-bromo-2-butyne, 5-bromo-1-pentyne, 5-bromo-2-pentyne, 1-iodo-2-pentyne, 1-iodo- Examples include 3-hexyne, 6-bromo-1-hexyne, and the like.

The reaction is performed using tetrahydrofuran (hereinafter abbreviated as THF)
, 1,4-dioxane, dimethoxyethane (hereinafter referred to as DME)
), etc.), N, N
, N', N'-tetramethylethylenediamine (hereinafter referred to as T
It can also be carried out using a hydrocarbon solvent such as cyclohexane, benzene, toluene, xylene, etc. in the coexistence of MEDA (abbreviated as MEDA).

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 and second solvents other than those mentioned above will not inhibit the reaction. A solvent may also be present. The reaction is nitrogen,
It is particularly preferable to carry out the reaction under an inert gas atmosphere such as argon.

There are no particular limitations on the temperature and time of the metalation reaction and the subsequent alkynylation reaction. For example, in the case of metalization, the reaction is carried out between -78°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 between 5°C and the boiling point of the system. The time is preferably about 1 second to 50 hours, more preferably about 1 minute to 10 hours. Regarding the alkynylation reaction, the reaction is carried out between -78°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 time is approximately 1 second to 50 hours, generally preferred. is preferably about 1 minute to 10 hours.

According to this method, an alkynyl group can be simultaneously substituted at one or both of the methyl groups at the 2 and 6 positions of the polyphenylene ether chain and the 3 and 5 positions of the phenyl group. A phenyl group or an alkyl group in the residue of a polyfunctional phenol compound roughly represented by Q can also be substituted.

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

The second polyphenylene ether used in the present invention is represented by the following general formula.

In the formula, m is the number of polyphenylene ether chains from 1 to 6,
n indicates the degree of polymerization of 8 chains, R6-R9 is hydrogen or the general formula % formula % () (ρ indicates an integer of 1 to 4, R5 is a methyl group or an ethyl group when J2 = 1, g = 2 - 4 represents hydrogen or an alkenyl group represented by a methyl group or an ethyl group), Q' represents Q and/or Q substituted with the above alkenyl group (Vl), and Q represents when m is 1 A polyfunctional phenol compound that represents hydrogen, has 2 to 6 phenolic hydroxyl groups in one molecule when m is 2 or more, and has polymerization-inactive substituents at the ortho and para positions of the phenolic hydroxyl group. Represents a residue. Representative examples of alkenyl groups include 2-butenyl group, 3-butenyl group,
Examples include 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 3-hexenyl group, 5-hexenyl group, and the like. Typical examples of polyfunctional phenol compounds include the compounds represented by the aforementioned general formulas (W-a) to (■-d).

The method for producing the polyphenylene ether of general formula (v) is not limited in carrying out the present invention, and for example, the above-mentioned polyphenylene ether (I [I) is metalized with an organometallic material, and then substituted with an alkenyl halide. It can be obtained by a reaction method. There is also no particular restriction on its molecular weight, and it can be used from oligomers to polymers, but in particular, those with a viscosity number ηsp/c measured in chloroform of 0.59/dl at 30°C in the range of 0.2 to 1.0. It is preferable to use one.

The second method for producing the alkynyl group-substituted curable polyphenylene ether of the present invention is to add a halogen to the double bond of the allyl group of the above-mentioned polyphenylene ether (V), and then perform a dehydrohalogenation reaction with a metal amide. Consists of processes.

The halogen added to the double bond is either chlorine or bromine, and chloroform, dichloromethane, 1,2-
Halogen-substituted hydrocarbon compounds such as dichloroethane and 1,1,2,2-tetrachloroethane, and carbon disulfide are used as the solvent. Furthermore, the metal amide used here is a compound represented by -Momonen RR' NM, where R and R' are hydrogen, an aliphatic hydrocarbon group having 1 to 6 carbon atoms,
It represents a trimethylsilyl group, etc., and M represents lithium or sodium. Specific examples include lithium amide,
Examples include sodium amide, lithium diethylamide, lithium diisopropylamide, lithium dicyclohexylamide, lithium bis(trimethylsilyl)amide, and the like. As a solvent used for dehydrohalogenation,
Examples include ether solvents such as THF, 1,4-dioxane, and DME, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

There are no particular restrictions on the reaction temperature, time, or amount of halogen or metal amide used for the halogen addition reaction and the dehydrohalogenation reaction using a metal amide.

For example, the addition reaction of halogen is carried out between -78°C (or the freezing point of the system) and the boiling point of the system, particularly preferably between 178°C (or the freezing point of the system) and 30°C. of halogens are used. The reaction time is preferably 1 minute to 5 hours. In addition, the dehydrohalogenation reaction is
The reaction is carried out at a temperature of 8° C. (to the freezing point of the system) to the boiling point of the system, and 2 to 10 equivalents of the metal amide are used relative to the original alikenyl group. The reaction time is preferably 1 minute to 5 hours.

During these reactions, the substitution position and substitution rate of the original alkenyl group remain unchanged. Therefore, when this method is followed, the substitution position and substitution rate of the alkynyl group directly reflect the substitution position and substitution rate of the original alkynyl group. The substitution rate of the alkenyl group referred to herein is defined in exactly the same manner as the substitution rate of the alkynyl group defined above, and is calculated according to the following formula.

Substitution rate of alkynyl group=The substitution rate of alkynyl group in the present invention is defined as the ratio of the total number of alkynyl 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 alkynyl group-substituted curable polyphenylene ether of the present invention, and it can be used from oligomers to polymers. Particularly preferably 30°C
,0,5q/viscosity number η measured in old chloroform solution
sp/c ranges from 0.2 to 1.0.

The alkynyl group introduced into the alkynyl group-substituted curable polyphenylene ether of the present invention can be detected by nuclear magnetic resonance or NMR.
It can be detected by methods such as spectral method (abbreviated as IR), infrared absorption (abbreviated as IR hereinafter), etc.
The substitution rate can be determined from the area ratio of the peaks in the H-NMR spectrum.

The alkynyl group-substituted curable polyphenylene ether of the present invention can be cured by any method, but heating is usually used. Curing methods other than heating include electron beam,
A method using radiation, light, etc. can also be adopted.

The alkynyl 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, poron 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 monomers and other thermoplastic and thermosetting resins.

[Function of the Invention] The first feature of the alkynyl group-substituted curable polyphenylene ether of the present invention is improvement in heat resistance and chemical resistance due to crosslinking. A significant decrease in the coefficient of linear expansion and insolubility in aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds.

These effects occur because the triple bond portion of the alkynyl 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 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 alkynyl groups and crosslinking.

Next, the second feature of the present invention, the method for producing an alkynyl group-substituted curable polyphenylene ether, is that existing polyphenylene ether can be converted into a curable polyphenylene ether at a low temperature and in a short time by a general reaction. .

Furthermore, the manufacturing method shown in the third aspect of the present invention is characterized in that the conversion of an alkynyl group to an alkynyl group, which has not been disclosed in the past, is made possible by using a halogen and a metal amide.

[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 and 2 Bifunctional polyphenylene ether (polyfunctional [2,2-bis(3,5-dimethyl-4
2,6-dimethylphenol is oxidatively polymerized using -hydroxyphenyl)propane.

Hereinafter, it will be abbreviated as PPE-1. ) 2.0g to toluene 10
0ml, dissolved in a mixed solution of DingME[)A2,5d,
Add 4.2 and 10.4 moles of n-butyllithium (1,60 mol/ρ, hexane solution), and under nitrogen atmosphere,
The reaction was allowed to proceed at room temperature for 1 hour. Subsequently, the mixture was cooled to -70'C, 0.89 g and 2.2 g of 4-bromo-1-butyne were added, and the mixture was stirred for 10 minutes. The polymer was precipitated by pouring into a large amount of methanol, and the process of filtration and washing with methanol was repeated three times to obtain a white powdery product. 'H-
When the substitution rate of 3-butenyl group was determined by NMR,
They were 0.7% and 6%, respectively.

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 sandwiched between the glass plates and heat-treated in an air oven at 260° C. for 30 minutes. The solubility of this film in chloroform, the glass transition temperature (T(+)) and the linear expansion coefficient (
α) is shown in Table 1. In addition, the above cast film 20
The layers were laminated, molded using a vacuum press at 260° C., and heat treated. 1 using a sheet with a thickness of 2M made by
The relative dielectric constant (εr) and dielectric loss tangent (tan δ) were measured with M1-4z. The results are also shown in Table 1.

Examples 3 to 7 PPE-1 was alkenyl-ratioed with n-butyllithium and 4-bromo-1-butene, and the substitution rate was 11%, 19%, 27
%, 46%, and 82% of 3-butenyl group-substituted PPE-1 were obtained. 1.8 g of this polymer was dissolved in 60 ml of chloroform, and a dichloromethane solution of bromine (1,0
mol/1) respectively 2.4 mg, 3.9 d,
5.4at), 8.6m, 13.5d plus 30
Stir for a minute. Pour into a large amount of methanol to precipitate the polymer, repeat filtration and washing with methanol three times,
A white powdery product was obtained.

Next, the entire amount of this product was dissolved in THFlood, and -7
Cooled to 0"C. To this was diisopropylamine (0.56 g, 0.9311.29 g, 2.0 g, respectively)
3g.

3.20 g) and n-butyllithium (1,60 mol/,
l! , 3.4m, 5.8m, 7.9m, respectively.
A THF solution of lithium diisopropylamide prepared from 12.6 mg and 19.6d) was added, and the mixture was stirred for 5 hours under a nitrogen atmosphere. The reaction was stopped by adding a small amount of methanol, the temperature was raised to room temperature, and the mixture was poured into a large amount of methanol.

After isolation, the substitution rate of the 3-butynyl group was determined by 1H-NMR, and it was found to be consistent with the original substitution rate of the 3-butynyl group.

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

In addition, 1H- of Example 3 (3-butynyl group substitution rate 11%)
The NMR (CDC, I!3 solution) spectrum is shown in FIG. 1, and the IR spectrum (diffuse reflectance 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 sandwiched between two glass plates.
Heat treatment was performed in an air oven at 0° C. for 30 minutes.

Further, 20 sheets of cast film were laminated, molded and heat treated using a vacuum press at 260° C. to form a sheet with a thickness of 2M. These are referred to as Comparative Example 2. Comparative examples 1 and 2
The physical properties of are shown in Table 1.

Comparative Example 3 PPE-12,09, n-butyllithium (1,60 mol/j!) 1.0d14-bromo-1-butyne 0.2
The reaction was carried out in the same manner as in Examples 1 and 2 using No. 29.

'The substitution rate of 3-butynyl group determined by H-NMR is 0.0
It was 5%. Table 1 shows the physical properties measured according to Examples 1 and 2.

(The following is a blank space) Example 8 The viscosity number ηsp/C measured with a 30°C 10,5y/old chloroform solution is 0.59. Poly(2,6-dimethylphenylene-1,4-ether) (hereinafter referred to as PPE-
2.0 g was dissolved in 100 g of THF, 10.4 m of n-butyllithium (1.60 mol/ρ, hexane solution) was added, and the mixture was stirred for 2 hours at room temperature under a nitrogen atmosphere. followed by 4-bromo-1-butyne 2
．． 2 g was added, stirred roughly for 30 minutes, and poured into a large amount of methanol. The precipitated polymer was isolated and 'H-NMR
When measured, the substitution rate of 3-butynyl group was 5%. Table 2 shows the physical properties measured according to Examples 1 and 2.

Example 9 22.0 g of PPE-2 was dissolved in 100 ml of THE, and 5.2 g of n-butyllithium (1.60 mol/11, hexane solution) was added, and the mixture was heated under reflux for 1 hour under a nitrogen atmosphere. After cooling to room temperature, 1.13 g of 4-bromo-2-butyne was added and stirred at room temperature for 30 minutes. After isolation, 'H-NMR was measured, and the substitution rate of 2-butynyl group was 18%. Table 2 shows the physical properties measured according to Example 1.2.

Example 10 PPE-22.0g, n-butyllithium (1.60mol/ρ) 4.2m, 1-iodo-2-pentyne 1.3g
The reaction was carried out in the same manner as in Example 8 using.

The substitution rate of 2-pentynyl group determined by 1H-NMR is 11
%Met.

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

Example 11 Poly(2,6-dimethylphenylene-1,4-ether) (hereinafter PPE-3) with a viscosity number ηsp/c of 0.91 measured with 30'C10,5g/old chloroform solution
) 2.0g, n-butyllithium (1,8
0 mol/β) 4.2d, 1-iodo-2-pentyne 1.
The reaction was carried out in the same manner as in Example 9 using 3 g. 1H-N
The substitution rate of 2-pentynyl group determined by MR was 13%. Table 2 shows the physical properties measured in the same manner as in Examples 1 and 2.

Example 12 PEE-3 was alkenylated with n-butyllithium and 5-bromo-1-pentene to obtain 4-pentenyl group-substituted PPE-3 with a substitution rate of 41%. Bromine (7.9 m of 1 mol/l dichloromethane solution) was reacted with 1.9 g of this polymer in the same manner as in Examples 3 to 7. The entire amount of the obtained dibromo compound was dissolved in T)-IFlood and cooled to -70°C. Here, 3.3 g of dicyclohexylamine and n
-Butyllithium (1,60 mol/, 1! > 11.
A THF solution of lithium dicyclohexylamide prepared from 5m was added, and the mixture was stirred for 5 minutes under a nitrogen atmosphere. The reaction was stopped by adding a small amount of methanol, and after the temperature was raised to room temperature, the mixture was poured into a large amount of methanol. 1H-NM after isolation
When the substitution rate of the 4-pentynyl group was determined using R, it was found to match the substitution rate of the original 4-pentenyl group.

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

Furthermore, 20 sheets of these cast films were laminated and formed into a sheet with a thickness of 2 m using a vacuum press. Using this film and sheet, physical properties were measured in the same manner as in Examples 1 and 2. The results are shown in Table-2.

Examples 13 and 14 Trifunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using bis(3,5-dimethyl-4-hydroxyphenyl) sulfone as a polyfunctional phenol compound) to n- Alikenylation was performed with butyllithium and 6-bromo-1-hexene to obtain polymers with 5-hexenyl group substitution rates of 7% and 16%. Bromine (1 mol/1, 1 mol/1 each in dichloromethane solution) was prepared in the same manner as in Examples 3 to 7 using 2.0 g of each of these polymers.
．． 7 m, 3.6 d) was reacted. The entire amount of the obtained dibromo compound was dissolved in THEloom and cooled to -70°C. To this, o, zog, and 0.409 g of sodium amide were added, respectively, and the mixture was stirred for 30 minutes under a nitrogen atmosphere.

After adding a small amount of methanol to stop the reaction, the mixture was heated and poured into a large amount of methanol. When the precipitated polymer was isolated and the substitution rate of 5-hexenyl groups was determined by 1H-NMR, it was found to be consistent with the original substitution rate of 5-hexenyl groups. Table 2 shows the physical properties measured according to Examples 1 and 2.

Example 15 Trifunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using 3,3″, 5,5°-tetramethylbiphenyl-4,4′-diol as the polyfunctional phenol compound) )2.09 was suspended in a mixed solution of 100 d of cyclohexane and 2.5 ml of TMEDA, and n-butyllithium (1,60 mol/fI,
Hexane solution>10.4rn1 was added and reacted at 60° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature 1-
Add 2.5g of 10Mo3-pentyne and add 30g of
Stir for a minute. When 1H-NMR was measured after isolation, 3
-The substitution rate of the pentenyl group was 10%. Example 1.
Table 2 shows the physical properties measured according to 2.

Example 16 Trifunctional polyphenylene ether (2,6-dimethylphenol was oxidatively polymerized using tris(3,5-dimethyl-4-hydroxyphenyl)methane as a polyfunctional phenol compound) with n-butyllithium. was alkenylated with 4-bromo-1-butene to obtain a polymer with a 3-butenyl group substitution rate of 8%. 1.9g of this polymer
Bromine (1 mol/1, dichloromethane solution, 1.8 gg) was reacted using the same method as in 3 to 7. The entire amount of the obtained dibromo compound was dissolved in THFloor and cooled to -70°C. Here hediethylamine 0.31'J and n-
Add a THF solution of lithium diethylamide prepared from butyl lithium (1,60 mol/l) and 2.7 me;
Stirred for 5 minutes under nitrogen atmosphere. The reaction was stopped by adding a small amount of methanol, the temperature was raised to room temperature, and the mixture was poured into a large amount of methanol. After isolation, the substitution rate of 3-butynyl group was determined by 1H-NMR, and it was found to be consistent with the original substitution rate of 3-butynyl group.

Following Examples 1 and 2, the physical properties are shown in Table 2.

[Effects of the Invention] According to the present invention, a crosslinkable alkynyl group can be introduced in one step by polymer reaction of polyphenylene ether.

Alternatively, an alkynyl group introduced into polyphenylene ether can be quickly converted into alkynyl simply. These reactions can be applied to a wide range of materials, from low molecular weight materials to high molecular weight materials, and can introduce any amount of alkynyl groups at low temperatures and in a short period of time.

The resulting alkynyl group-substituted polyphenylene ether becomes a curable polymer when exposed to heat, light, etc., so it is endowed with properties such as heat resistance and chemical resistance, and can be used as thermosetting heat-resistant resins, photosensitive resins, resists, etc. Can be done. Since the curing reaction of alkynyl groups is an addition reaction, gas,
Since no by-products such as water are produced, there are also advantages such as a uniform film and 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 1H-NMR spectrum of Example 3 (CDCN
3 solutions). FIG. 2 is an IR spectrum (diffuse reflection method) of the same Example 3. 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 are hydrogen or general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (l indicates an integer from 1 to 4, R_5 is methyl when l = 1 or ethyl group, hydrogen or methyl group or ethyl group when l = 2 to 4), and Q'' represents Q and/or Q substituted with the above alkynyl group (II); , 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 a polymerizable inert substituent at the ortho and para positions of the phenolic hydroxyl group. represents the residue of a polyfunctional phenol compound having the following formula:
A curable polyphenylene ether characterized in that II) is 0.1 mol% or more and 100 mol% or less. Substitution rate of alkynyl group = (total number of moles of alkynyl 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 alkynyl 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, and R_5 represents a methyl group or ethyl group when l = 1, and hydrogen or a methyl group or ethyl group when l = 2 to 4). 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). 6) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (V) [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_6 to R_9 are hydrogen or general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (VI) (l indicates an integer from 1 to 4, R_5 is methyl when l = 1 or ethyl group, hydrogen or methyl group or ethyl group when l = 2 to 4), and Q' represents Q and/or Q substituted with the above alkenyl group (VI); , 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 a polymerizable inert substituent at the ortho and para positions of the phenolic hydroxyl group. represents the residue of a polyfunctional phenol compound having ] and a step of dehydrohalogenating the alkenyl group-substituted polyphenylene ether with a metal amide. A method for producing a curable polyphenylene ether according to item 1. 7) The method for producing a curable polyphenylene ether according to claim 6, wherein m is 1 or 2 in general formula (V).