JP5370273B2 - Star-shaped polyphenylene ether and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide star PPE which is excellent in compatibility with linear polyphenylene ether (PPE), has heat resistance and other characteristics equal to those of PPE, and also can effectively improve the fluidity of PPE. <P>SOLUTION: The star polyphenylene ether has a benzene ring as a nucleus and three or more polyphenylene ether chains extended from carbon atoms on the benzene ring. The polyphenylene ether chains are preferably coupled to carbon atoms of the first, third and fifth positions on the benzene ring. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

The present invention relates to a star-shaped polyphenylene ether and a method for producing the same. Specifically, the present invention relates to a star-shaped polyphenylene ether useful for improving the fluidity of linear polyphenylene ether and a method for producing the star-shaped polyphenylene ether.
The present invention also relates to a polyphenylene ether mixture containing the star-shaped polyphenylene ether and a fluidity improver for polyphenylene ether containing the star-shaped polyphenylene ether.

  Polyphenylene ether (PPE), for example poly (2,6-dimethyl-1,4-phenylene ether) obtained by catalytic oxidative polymerization of 2,6-dimethylphenol, has a high glass transition temperature and is also resistant to acid. Engineering plastics that have a good balance of properties such as mechanical properties, alkali resistance, mechanical properties, electrical insulation properties, low hygroscopicity, and dimensional stability.

  Conventional general PPE has a linear structure in which a plurality of phenylene ether structural units extend linearly. Hereinafter, such a conventional general PPE may be referred to as “linear PPE”. In the present specification, when simply described as “polyphenylene ether” or “PPE”, a plurality of phenylene “Linear polyphenylene ether” having a linear structure in which ether structural units extend linearly.

  However, PPE has low thermal stability under air (oxidation deterioration starts at 250 ° C.), and various problems such as discoloration and oxidation deterioration occur during melt molding. That is, since the glass transition temperature of the resin is 210 ° C., the melt molding temperature needs to be 250 ° C. or more, but oxidation deterioration occurs at such a temperature.

  For this reason, conventionally, various techniques have been devised for lowering the molding processing temperature of PPE. For example, blends with polystyrene resins (for example, US Pat. No. 3,383,435), addition of glidants such as saturated polyalicyclic resins and terpene phenols (for example, JP-A-2001-152006) JP-A-10-81818, JP-B-57-13484, JP-A-58-129050, JP-A-58-129051, JP-A-59-126460, JP-A-47-3136. And Japanese Patent Laid-Open No. 9-59508). However, polystyrene, terpene phenol, and other glidants lower the heat deflection temperature of PPE and increase the flammability of the resin, typically measured by the UL94 standard protocol.

  Thus, a method of adding a polyester dendritic oligomer (weight average molecular weight 1000 to 5000) was developed (for example, Japanese Patent Publication No. 59-41663, Japanese Patent Publication No. 61-502195, Japanese Patent Laid-Open No. 63-10655).

  However, polystyrene is compatible with PPE, but other polymers (polyamide, polyolefin, polyurethane) are hardly compatible with PPE. In the conventional method, compatibilization is achieved by chemical reaction under special conditions such as high temperature extrusion. However, since these polymers are essentially incompatible with PPE, they are thus incompatible with PPE. In the composite resin composition in which the polymer is blended, the mechanical strength of the obtained molded product is lowered.

  For the purpose of improving compatibility and maintaining various properties such as heat resistance, a blending technique with ultra-low molecular weight PPE has been developed (Japanese Patent Publication No. 2003-53234). However, in order to lower the melt viscosity, it is necessary to add very low molecular weight PPE. As a result, the mechanical properties of the resulting molded article are impaired.

US Pat. No. 3,383,435 JP 2001-152006 A JP-A-10-81818 Japanese Patent Publication No.57-13484 JP 58-129050 A JP 58-129051 A JP 59-126460 A JP-A-47-3136 JP-A-9-59508 Japanese Patent Publication No.59-41663 JP-T 61-502195 JP-A 63-10655 Special table 2003-53234 gazette

  In order to improve the processability of linear PPE, the heat resistance of the linear PPE itself in the air is better than the blend of different polymers, or it is very compatible with the linear PPE and has the same heat resistance as PPE. It is desired to develop a high fluidizing agent having a high viscosity.

  The present invention provides a star-shaped PPE that has excellent compatibility with linear PPE, has heat resistance equivalent to that of linear PPE, and other characteristics, and is effective in improving the fluidity of linear PPE. Let it be an issue.

  The present inventors have intensively studied to solve the above-mentioned problems, and when a PPE star polymer is synthesized and blended with linear PPE, the viscosity of the solution is greatly reduced. As a result, the present invention was completed.

  That is, the gist of the present invention is as follows.

[1] A star-shaped polyphenylene ether having a benzene ring as a nucleus and having three or more polyphenylene ether chains extending from carbon atoms on the benzene ring.

[2] The star-shaped polyphenylene ether according to [1], wherein the polyphenylene ether chain has an oxymethylene group and is bonded to a carbon atom on the benzene ring via an oxymethylene group.

[3] A star-shaped polyphenylene ether according to [1] or [2], wherein the polyphenylene ether chain per one chain has a weight average molecular weight of 1,000 or more.

[4] A star-shaped polyphenylene ether according to any one of [1] to [3], wherein the weight average molecular weight is 7,000 to 20,000.

[5] A star-shaped polyphenylene ether according to any one of [1] to [4], wherein the polyphenylene ether chain is bonded to the 1st, 3rd and 5th carbon atoms on the benzene ring. .

[6] The star-shaped polyphenylene according to any one of [1] to [5], wherein bromomethylbenzene substituted with three or more bromomethyl groups is reacted with polyphenylene ether in the presence of a catalyst. A method for producing ether.

[7] A method for producing a star-shaped polyphenylene ether according to [6], wherein the bromomethylbenzene is 1,3,5-trisbromomethylbenzene.

[8] A polyphenylene ether mixture comprising the star-shaped polyphenylene ether according to any one of [1] to [5] and polyphenylene ether.

[9] A fluidity improver for polyphenylene ether comprising the star-shaped polyphenylene ether according to any one of [1] to [5].

  The star PPE of the present invention has excellent mechanical and thermal property balance equivalent to that of linear PPE in terms of mechanical properties, thermal properties, insulation properties, dimensional stability, and the like. On the other hand, it has excellent fluidity due to its unique shape in which the PPE chain has a star shape extending radially from the benzene nucleus.

  Therefore, the PPE mixture obtained by mixing the star-shaped PPE of the present invention with the linear PPE can ensure sufficient fluidity without being alloyed with other resins such as styrene-based resins, and is an option for molding processing. Spread. Furthermore, since it is extremely excellent in heat resistance, it is very useful in a wide range of fields such as electric / electronic parts, machine / mechanical parts, vehicle parts and building materials that require higher heat resistance.

2 is a ¹ H-NMR spectrum of the linear PPE obtained in Comparative Example 1. 2 is a ¹ H-NMR spectrum of a triple-stranded star PPE obtained in Example 1. In the 7.2-7.8 ppm region of the NMR spectrum of the linear PPE obtained in Comparative Example 1, the three-substitution model obtained in Reference Example 2, and the three-chain star PPE obtained in Example 1. It is an enlarged view. 2 is a graph showing a thermal decomposition curve of the three-chain star PPE obtained in Example 1 under air. 6 is a graph showing a Huggins plot (chloroform solvent, 30 ° C.) of the linear PPE obtained in Comparative Examples 1, 3, 4, and 5 and the three-stranded star PPE obtained in Example 3. FIG. 4 is a graph showing a Huggins plot and a Mead-Fuoss plot (chloroform solvent, 30 ° C.) of the triple-stranded star PPE obtained in Example 3. FIG. It is a graph which shows the Mark-Howink-Sakurada plot (chloroform solvent, 30 degreeC) of the linear PPE obtained in Comparative Examples 1-5 and the triple chain star-shaped PPE obtained in Examples 1-4. The linear PPE obtained in Comparative Example 6 (Mw = 188,000) and (A) the linear PPE obtained in Comparative Example 4 (Mw = 9,000) or (B) obtained in Example 2. The relationship between the weight ratio (weight%) of linear PPE (Mw = 188,000) in a mixture and intrinsic viscosity (solution viscosity) in a mixture with a three-chain star PPE (Mw = 10,000) is shown. It is a graph.

  Hereinafter, embodiments of the present invention will be described in detail.

[Star-shaped PPE]
The star PPE of the present invention is characterized by having three or more PPE chains having a benzene ring as a nucleus and extending from a carbon atom on the benzene ring.

When the number of PPE chains is 2 or less, there is no great difference in flowability from linear PPE, and 3 or more PPE chains are required.
The PPE chain of the star-shaped PPE of the present invention can be arbitrarily formed in the range of 3 to 6, but it is preferably 3 to 4 and particularly preferably 3 for ease of synthesis. It is preferable that a PPE chain is bonded to the 1-position, 3-position, and 5-position of the above (hereinafter, a star PPE in which three PPE chains are introduced may be referred to as a “three-chain star PPE”). .

  If the molecular weight of the PPE chain of the star PPE of the present invention is excessively small, mechanical properties as PPE tend to be reduced. If it is excessively large, it is difficult to synthesize the star PPE with high purity. In addition, since the weight average molecular weight of the linear PPE currently in circulation is 30,000, synthesizing a star PPE having a molecular weight higher than this tends to lower the meaning of lowering the viscosity. Therefore, the weight average molecular weight of the PPE chain of the star-shaped PPE is preferably 1,000 to 10,000, particularly 3,000 to 10,000. The weight average molecular weight per PPE chain is substantially equal to the weight average molecular weight of the linear PPE used for the production of the star PPE.

  In addition, the molecular weight of the star PPE itself of the present invention is 3,000 to 30,000, more preferably 7,000 to 30,000, particularly 9,000 to the weight average molecular weight measured in the Examples section below. 30,000 is preferred. This is because the current linear PPE has a weight average molecular weight of about 30,000, and if it is less than the above lower limit, film formation tends to be difficult. If the upper limit is exceeded, the melt viscosity at the time of injection molding becomes too high, and the cylinder This is because burns may occur in the interior.

  Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured in the Examples section below is usually 1 to 5, preferably 1 to 3.5, more preferably 1 to 2. The glass transition temperature by DSC method is more preferably 150 to 220 ° C, particularly 170 to 210 ° C. When the glass transition temperature is less than 150 ° C., the heat resistance tends to decrease, and when it exceeds 220 ° C., the resin fluidity during molding tends to decrease.

[Production method of star-shaped PPE]
Although there is no restriction | limiting in particular as a method of manufacturing the above-mentioned star-shaped PPE of this invention, Preferably, it manufactures as follows according to the manufacturing method of the star-shaped PPE of this invention.

  In the method for producing a star PPE of the present invention, first, bromomethylbenzene having bromomethyl at a site where a PPE chain is introduced is prepared. For example, 1,3,5-trisbromomethylbenzene (1,3,5-trisbromomesitylene) is prepared to produce star-shaped PPE having PPE chains at the 1-position, 3-position and 5-position of the benzene ring. To do. This bromomethylbenzene can be produced according to a conventional method using methylbenzene as shown in Reference Example 3 described later.

  Separately, a linear PPE that becomes a PPE chain is produced. The production of the linear PPE can be performed according to a conventional method. The method for producing the linear PPE will be described in the section of the PPE mixture of the present invention described later.

  The linear PPE used as this PPE chain is manufactured so that the weight average molecular weight becomes the weight average molecular weight of the PPE chain per one star PPE of the present invention described above.

  Next, bromomethylbenzene and linear PPE are reacted in the presence of a catalyst, and the bromine atom portion of bromomethylbenzene is replaced with the PPE chain to introduce the PPE chain.

The catalyst used in this reaction is not particularly limited as long as it pulls out the hydrogen of the hydroxyl group at the end of the PPE chain. In addition to inorganic base catalysts such as cesium carbonate, potassium carbonate, sodium carbonate, pyridine, 4, Organic base catalysts such as 4-dimethylaminopyridine and diazabicycloundecene can be used. These catalysts may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The catalyst is preferably used in an amount of about 1.1 to 2 mol relative to the OH terminal of the PPE chain from the viewpoint of reaction efficiency and economy.

The reaction is usually carried out in the presence of a solvent. Examples of the solvent used include aromatic solvents such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and methylpyrrolidone, and organic solvents such as tetrahydrofuran, nitrobenzene and chlorobenzene. A solvent can be used. These solvents may be used alone or in a combination of two or more.
In particular, a mixed solvent of an aromatic hydrocarbon-based toluene and an amide-based solvent is convenient and recommended for promoting the nucleophilic reaction together with the solubility of the polymer.
Although there is no restriction | limiting in particular in the usage-amount of a solvent, it is preferable from the surface of reaction efficiency and handling property to use to such an extent that the PPE density | concentration in a reaction system will be 1-20 weight%.

  The reaction temperature is preferably 50 to 200 ° C, particularly preferably 70 to 150 ° C. If the reaction temperature is too low, the reaction rate is low, and if it is too high, the polymer is likely to be colored due to decomposition of the amide solvent used.

  The reaction time is usually about 12 to 72 hours. If the reaction time is too short, a star-shaped PPE in which the desired number of PPE chains are introduced cannot be obtained. If the reaction time is too long, no further improvement in reaction results is observed, which is not efficient.

In addition, it is preferable to perform reaction in inert gas atmosphere, such as nitrogen, at the point which suppresses the coloring by the oxidative degradation of a polymer.
After the reaction, the product is separated and recovered according to a conventional method and purified by recrystallization or the like.

  In the star PPE of the present invention thus obtained, the PPE chain subjected to the reaction is substituted with a bromine atom of bromomethylbenzene, and the PPE chain is bonded to the carbon atom on the benzene ring via the oxymethylene group. It is a combination.

  In the above reaction, there may be a case in which no PPE chain is introduced into all bromomethyl groups. That is, for example, when 1,3,5-trisbromomesitylene and linear PPE are reacted, those having only one PPE chain and those having only two PPE chains are also three-stranded stars. Generate with PPE. Thereby, the weight average molecular weight of the obtained three-chain star PPE does not necessarily become a weight average molecular weight of about 3 times the weight average molecular weight of the linear PPE used for introducing the PPE chain. However, such a product is not particularly problematic in the application of the star PPE of the present invention, and can be used as it is together with the target product. However, if necessary, such a product can be separated by column chromatography or the like.

  The star-shaped PPE of the present invention can be sufficiently used for the intended application as long as the purity is 0.7 or more, particularly 0.8 or more, as measured in the Examples section below.

[PPE mixture / PPE fluidity improver]
The star PPE of the present invention has excellent characteristics equivalent to linear PPE derived from the PPE chain in terms of its mechanical properties, thermal properties, insulation properties, dimensional stability, etc. Is much better than linear PPE due to its star shape. Therefore, it can be effectively used as a fluidity improver for mixing with linear PPE and improving fluidity and improving molding processability without impairing the original properties of PPE.

  Below, the linear PPE for blending the star PPE of the present invention as a fluidity improver to obtain a PPE mixture will be described.

  The linear PPE itself may be one that has been conventionally provided and is usually a polymer or copolymer having an ortho-substituted phenylene structure represented by the following general formula (I) as a structural unit.

(In the general formula (I), two R ^{1 s} may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and two R ^{2 s} may be the same or different. Represents a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, provided that two R ^{1 s} are not hydrogen atoms.)

Examples of the hydrocarbon group for R ¹ and R ² in the general formula (I) include a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and the number of carbon atoms. A 6-30 aryl group, a C7-30 aralkyl group, etc. are mentioned. In the present invention, “the number of carbon atoms” refers to the total number of carbon atoms including the number of carbon atoms of the substituent when the hydrocarbon group has a substituent.

Specific examples of the hydrocarbon group for R ¹ and R ² include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n -Pentyl group, isopentyl group, cyclopentyl group, hexyl group, octyl group, 1-ethylpropyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2-, 3- or 4-methylpentyl group or heptyl group, Examples include benzyl group, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

The substituted hydrocarbon group in R ¹ and R ² in the general formula (I) represents, for example, a hydrocarbon group substituted with a halogen atom, an alkoxy group, a haloalkoxy group, an amino group or the like. Examples of the hydrocarbon group to be substituted with the substituted hydrocarbon group include the same as those exemplified for the hydrocarbon groups of R ¹ and R ² above. Examples of the hydrocarbon group substituted with a hydrocarbon group include 1-methylphenyl group, 2-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group and the like.

R ¹ is preferably a primary or secondary alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 8 carbon atoms.
Preferable examples of the primary alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl, isopentyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2- , 3- or 4-methylpentyl group or heptyl group.
Preferable examples of the secondary alkyl group include isopropyl group, sec-butyl group, and 1-ethylpropyl group.
R ¹ is more preferably a primary or secondary alkyl group having 1 to 4 carbon atoms or a phenyl group, and particularly preferably a methyl group.

R ² is preferably a hydrogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 8 carbon atoms.
Preferable examples of the primary alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl, isopentyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2- , 3- or 4-methylpentyl group or heptyl group.
Preferable examples of the secondary alkyl group include isopropyl group, sec-butyl group, and 1-ethylpropyl group.
R ² is more preferably a hydrogen atom, a primary or secondary alkyl group having 1 to 4 carbon atoms, or a phenyl group, and particularly preferably a hydrogen atom.

  Two or more ortho-substituted phenylene structures represented by the general formula (I) contained in the linear PPE used in the present invention may be used, but usually one is preferable.

  The linear PPE of the present invention may be linear or branched, but is preferably linear. Whether it is linear or branched can be adjusted by selecting an appropriate catalyst type, such as the atmosphere during oxidative coupling polymerization, solvent type, catalyst type, reaction temperature, reaction time, etc. . In order to improve the regioselectivity of oxidative coupling polymerization and suppress the branching of PPE, it is preferable to use a copper-amine catalyst described later as a catalyst.

  The molecular weight of the linear PPE mixed with the star PPE of the present invention is 20,000 to 1,000,000, particularly 30,000 to 200,000 as the weight average molecular weight measured in the Examples section below. It is preferable.

  If the molecular weight of the linear PPE is too small, heat resistance and mechanical properties tend to be impaired. If it is too large, sufficient fluidity cannot be obtained even when the star PPE of the present invention is mixed, which is not preferable.

  This linear PPE can be produced by oxidative coupling polymerization of at least a 2,5-disubstituted phenol represented by the following general formula (II).

(In the general formula (II), two R ^{3 s} may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and two R ^{4 s} may be the same or different. Represents a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, provided that two R ^{3 s} are not hydrogen atoms.)

Examples of the hydrocarbon group or substituted hydrocarbon group for R ³ in general formula (II) include the same as those exemplified for the hydrocarbon group or substituted hydrocarbon group for R ¹ in general formula (I). The same applies to the preferred examples.
Examples of the hydrocarbon group or substituted hydrocarbon group for R ⁴ in formula (II) include the same as those exemplified for the hydrocarbon group or substituted hydrocarbon group for R ² in formula (I). The same applies to the preferred examples.

  The reaction is carried out by adjusting the polymerization conditions such as atmosphere, solvent species, catalyst species, reaction temperature, reaction time and the like so as to obtain the desired linear PPE.

  Examples of the catalyst include a catalyst composed of a heavy metal compound such as copper, manganese, and cobalt and an amine compound. In particular, in order to obtain a PPE having a sufficient molecular weight, copper obtained by coordinating a copper compound with an amine compound. It is preferred to use an amine catalyst.

  Examples of the copper compound used for the copper-amine catalyst include cuprous chloride, cuprous bromide, cuprous iodide, cuprous acetate, cuprous sulfate, cuprous nitrate, cupric chloride, Examples include cupric bromide, cupric iodide, cupric acetate, cuprous sulfate, cupric nitrate, and the like, and two or more of these may be used in combination. Of these, cuprous halides such as cuprous chloride, cuprous bromide and cuprous iodide are preferred.

Examples of amine compounds include aliphatic amine compounds and aromatic amine compounds.
Aliphatic amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine, etc. Aliphatic tertiary amines including tertiary amines, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, dioctyl Aliphatic secondary amines including alicyclic secondary amines such as amine, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, tetramethylethylenediamine, tetraethyl Ethylene diamine, tetra ethylenediamine, tetrabutyl ethylenediamine, include tetraalkyl ethylenediamine such as tetrapentyl ethylenediamine, it may be used in combination of two or more. Of these, tetraalkylethylenediamine such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, and tetrapentylethylenediamine are preferable.

  Examples of the aromatic amine compound include 2-phenylpyridine, 2-toluylpyridine, 2-nitrophenylpyridine, 2-methoxypyridine, 2-methylpyridine, 2-ethylpyridine, 2-n-propylpyridine, 2-isopropyl. Pyridine, 2,6-dimethylpyridine, 2,6-diethylpyridine, 2,6-n-propylpyridine, 2-methyl-6-phenylpyridine, 2-methylquinoline, 2-ethylquinoline, 2-n-propylquinoline The amine compound which has pyridine rings, such as these, is mentioned, These may use 2 or more types together. Of these, 2-phenylpyridine, 2-toluylpyridine, 2-nitrophenylpyridine, and 2-methoxypyridine are preferable.

  Among the above aliphatic and aromatic amine compounds, the coordination ability of the amine compound to the copper ion in the copper compound is high, a catalyst having sufficient activity is formed, and the polymerization reaction of PPE proceeds efficiently, Furthermore, tetramethylethylenediamine, tetraethylethylenediamine, and tetrapropylethylenediamine are particularly preferable from the viewpoint that linear PPE is easily obtained by improving the regioselectivity of polymerization.

The copper-amine catalyst can be produced by reacting a copper compound and an amine compound in an appropriate solvent, and isolating and purifying the copper compound. When the amine compound is an aliphatic amine compound, the ratio of the amine compound to the copper ion derived from the copper compound used for the reaction is preferably 0.01 to 50 equivalents relative to the copper ions, and 0.1 to 40 equivalents. It is more preferable that it is 1-30 equivalent. If the ratio of the aliphatic amine compound is less than 0.01 equivalent, the regioselectivity in the oxidative coupling polymerization tends to decrease, and if it exceeds 50 equivalents, the oxidative coupling polymerization may not proceed rapidly. Moreover, when an amine compound is an aromatic amine compound, it is preferable that it is 50-300 equivalent with respect to a copper ion, It is more preferable that it is 60-200 equivalent, It is further more preferable that it is 70-150 equivalent. . If the ratio of the aromatic amine compound is less than 50 equivalents, the regioselectivity in the oxidative coupling polymerization tends to decrease, and if it exceeds 300 equivalents, the oxidative coupling polymerization may not proceed rapidly.
The copper-amine catalyst can also be used by coordinating the copper compound to the amine compound in a reaction solvent used for oxidative coupling polymerization.

  In the oxidative coupling polymerization, the copper-amine catalyst can be used in an arbitrary amount, but generally 0.01 to 5 mol% as a molar amount of copper ions with respect to all phenolic monomers used in the oxidative coupling polymerization. It is preferable to use so that it may become, It is more preferable to use so that it may become 0.1-4.5 mol%, It is further more preferable to use so that it may become 1-4 mol%. If the molar amount of copper ions relative to the total phenolic monomer is less than 0.01 mol%, the oxidative coupling polymerization tends to be difficult to proceed, and if it exceeds 5 mol%, the regioselectivity in the oxidative coupling polymerization may be reduced. is there.

  The oxidative coupling polymerization may be performed in the presence or absence of a reaction solvent, but is preferably performed in the presence of a reaction solvent in order to obtain a sufficient molecular weight. The solvent is preferably inert to the phenolic monomer and liquid at the reaction temperature. For example, benzene, o-dichlorobenzene, toluene, xylene, chlorobenzene, nitrobenzene, acetonitrile, benzonitrile, methanol, Ethanol, n-propyl alcohol, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, N, N-dimethylformamide and the like may be mentioned, and these may be used in combination of two or more. Of these, o-dichlorobenzene, toluene, xylene, chlorobenzene, and nitrobenzene are preferable.

  As the oxidative coupling polymerization atmosphere, oxygen, air, or the like can be employed.

  The reaction temperature of the oxidative coupling polymerization is not a problem as long as the reaction medium is kept in a liquid state, but is preferably 15 to 100 ° C, more preferably 15 to 60 ° C, and more preferably 20 to 40 ° C. It is particularly preferred. If the reaction temperature is less than 15 ° C., the oxidative coupling polymerization tends not to proceed rapidly. If the reaction temperature exceeds 100 ° C., the regioselectivity in the oxidative coupling polymerization is reduced, or the heat resistance and gel of the resulting PPE are reduced. Tends to occur.

  The reaction time for oxidative coupling polymerization is preferably 1 to 24 hours, and more preferably 1 to 12 hours. If the reaction time is less than 1 hour, PPE having a sufficient molecular weight may not be obtained. If it exceeds 24 hours, PPE having high regioselectivity in oxidative coupling polymerization tends to be difficult to obtain.

  In the PPE mixture of the present invention, the mixing ratio of the linear PPE and the star PPE of the present invention is not particularly limited and can be arbitrarily set according to the purpose. That is, since the star-shaped PPE of the present invention is derived from the PPE chain and has excellent compatibility with ordinary linear PPE, the linear PPE can be mixed at an arbitrary mixing ratio. Therefore, the mixing ratio of the star PPE of the present invention may be increased or decreased according to the intended fluidity. Usually, the star PPE of the present invention is used in the range of 0.05 to 20% by weight, particularly 0.1 to 10% by weight, based on 100% by weight of the total of linear PPE and star PPE.

  The PPE mixture of the present invention may be one obtained by dry blending linear PPE and the star PPE of the present invention, or may be one obtained by dry blending and then melt-kneading. A mixer such as a tumbler, a Henschel mixer, or a ribbon blender can be used for dry blending, and a uniaxial or multiaxial kneading extruder, roll, Banbury mixer, or the like can be used for melt kneading. The kneading temperature is usually 150 to 350 ° C., preferably 180 to 320 ° C., although it depends on the molecular weight of the star PPE of the present invention in the PPE mixture, the mixing ratio thereof and the molecular weight of the linear PPE.

  In addition, the PPE mixture of this invention can be further used as a resin composition which mix | blended other resin and additive as needed.

  Examples of other resins include thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polystyrene resins such as polystyrene, high-impact polystyrene, poly (acrylonitrile-butadiene-styrene) (ABS resin), polyethylene terephthalate, polybutylene terephthalate, poly Polyester resins such as (ethylene-2,6-dinaphthalate), polyamide 6, polyamide 66, polymetaxylylene adipamide, polyamide 6I / 6T, polyamide 6/66 and other polyamide resins, polycarbonate, polyoxymethylene , Polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyimide, polyetherimide, and polyphenylene ether other than the linear and star PPE of the present invention Le, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyacrylonitrile, and the like. These may be used alone or may be used in combination of two or more.

  Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, and epoxy resin. These may use only 1 type and may mix and use 2 or more types.

  These other resins are usually used by mixing at a ratio of 50% by weight or less, preferably 40% by weight, based on the total amount of the PPE mixture of the present invention, that is, linear PPE and star PPE. it can.

  Examples of additives include those commonly used for thermoplastic resins, such as heat stabilizers, mold release agents, antioxidants, weather resistance improvers, impact resistance improvers, inorganic fillers, and nucleating agents. Agents, foaming agents, flame retardants, lubricants, plasticizers, fluidity improvers, colorants, dispersants, conductive agents, slidability improvers and the like.

  The PPE mixture of the present invention or a PPE resin composition containing the same is a molding method generally used for thermoplastic resins, that is, injection molding, gas assist injection molding, injection compression molding, hollow molding, extrusion molding, sheet molding, heat It can be molded by various molding methods such as molding, rotational molding, laminate molding, press molding, etc., to obtain various molded products. A particularly preferable molding method is injection molding from the viewpoint of fluidity. In the injection molding, the resin temperature is preferably controlled to 270 to 320 ° C., for example.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the examples shown below unless it exceeds the gist.

  In the following, methods for measuring physical properties of the obtained polymer and the like are as follows.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn):
For the target product obtained in each example, absolute weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn) under the following conditions by gel permeation chromatography connected light scattering device (GPC-LALLS). ) Was measured.
Apparatus: Two columns shown below (diameter 5 mmφ, length 30 mm) were connected to “HLC-8220” manufactured by Tosoh Corporation, and “T-60A” manufactured by Viscotek was further connected. The detector includes a refractometer, a viscometer, and a light scatterometer. The refractive index increment is 0.185, and the flow rate and temperature of tetrahydrofuran (THF) as an eluent are 1.0 mL / min, 40 ° C.
Column: “TSK-GEL GMHHR-M and GMHHR-N” manufactured by Tosoh Corporation (packed with polystyrene gel as a filler)
Calibration curve: Standard polystyrene manufactured by Polymer Laboratories (molecular weight: 580 (Mw / Mn = 1.14), 950 (Mw / Mn = 1.13), 1250 (Mw / Mn = 1.10), 1700 (Mw / Mn = 1.06), 2450 (Mw / Mn = 1.05), 3250 (Mw / Mn = 1.04), 5050 (Mw / Mn = 1.05), 7000 (Mw / Mn = 1.04) 11600 (Mw / Mn = 1.03), 22000 (Mw / Mn = 1.03), 37900 (Mw / Mn = 1.01), 96400 (Mw / Mn = 1.01), 107000 (Mw / Mn = 1.05) and 514000 (Mw / Mn = 1.02)).
The number average molecular weight (Mn) was determined as a value in terms of polystyrene using GPC measurement under the above-described conditions and using the calibration curve prepared by the above method. The refractive index increment is 0.185.
The weight average molecular weight (Mw) was measured by the light scattering method under the conditions described above.
The molecular weight distribution (Mw / Mn) was calculated from the number average molecular weight determined with a gel permeation chromatography refractometer and the weight average molecular weight determined with a light scatterometer.

(2) ¹ H- and ¹³ C-NMR spectra:
Using 400 MHz ( ¹ H) nuclear magnetic resonance apparatus (“Bruker AC-400P” manufactured by Bruker) for the target product obtained in each example, deuterated chloroform as a solvent and tetramethylsilane (TMS) as an internal standard, NMR Measurements were made.
The number average molecular weight of the target product was calculated from the integral ratio of terminal hydrogen of polyphenylene ether and aromatic hydrogen of repeating units of PPE in NMR spectrum.

(3) Purity of three-stranded star PPE:
The purity of the three-chain star PPE can be represented by the ratio of the weight average molecular weight obtained by the above (1) GPC-LALLS measurement to the theoretical molecular weight. For example, in the case of Example 1, it can obtain | require with the following method.
In the reaction of Example 1, theoretically, since three PPE chains having a weight average molecular weight of 3,000 react with one TBM molecule of the central molecule, the theoretical molecular weight is 3,000 × 3 = 9,000. Become. However, since there are actually double- and single-chain polymers in addition to the three-chain polymer, the value of the weight average molecular weight obtained by GPC-LALLS measurement is lower than the theoretical molecular weight. Therefore, the purity of the triple-stranded PPE of Example 1 is
Weight average molecular weight / theoretical molecular weight obtained by GPC-LALLS measurement = 7,500 / (3,000 × 3) = 0.83
Is calculated.

(4) Intrinsic viscosity:
Wash the Cannon Fenceke viscometer with chloroform, and put 10 mL of chloroform into the viscometer with a whole pipette. This is transferred to a thermostat and heated to 30 ° C. After 30 minutes, the falling time t ₀ of chloroform was measured three times with a stopwatch, taking the average value. However, the error range is ± 0.3 seconds. Next, 0.100 g of PPE obtained in each example is precisely weighed and placed in a 50 mL sample bottle. Chloroform 20mL is added here using a whole pipette, and it stoppers and dissolves completely (concentration c = 0.500g / dL). The solution is drawn up with a syringe and injected into another sample bottle using a Teflon filter. 10 mL of this solution is weighed with a whole pipette, transferred to the previously used Canon Fenceke viscometer, and warmed in a thermostatic bath at 30 ° C. for 30 minutes. The fall time t _0.5 is measured three times, and the average value is obtained. Similarly, the drop time when c = 0.1, 0.2, 0.3, 0.4 g / dL is measured. From these, the reduced viscosity (η _sp / c) and the concentration were plotted (Huggins plot), and the intrinsic viscosity (extreme viscosity) was obtained from the extrapolated value.

(5) Thermogravimetry (TG):
The three-chain star PPE of Example 1 and the linear PPE of Comparative Example 1 were measured using a thermogravimetric apparatus (“SCC 5200 system” manufactured by Seiko Instruments Inc.). The temperature was raised under the conditions of 40 to 800 ° C. and 10 ° C./min in air, and the temperature (T _d10 ) at which a weight reduction of 10% was confirmed from the weight before the start of temperature raising was measured. It can be judged that the higher the thermal decomposition temperature, the higher the heat resistance.

(6) Glass transition temperature:
About PPE obtained in each example, using a differential scanning calorimetry (DSC) apparatus (“Shimadzu DSC-60” manufactured by Shimadzu Corporation), the temperature was increased at a rate of 40 to 300 ° C. and 20 ° C./min in a nitrogen atmosphere. Then, the glass transition temperature was measured.

  In addition, 2,6-dimethylphenol (26-DMP), cuprous chloride-N, N, N ′, N′-tetramethylethylenediamine complex (Cu-TMEDA), N, N, N ′ used in each example , N′-tetramethylethylenediamine (TMEDA), toluene, methanol, and other reagents were used as they were.

[Reference Example 1: Synthesis of 1-substituted model]

  In a 100 ml eggplant flask, 1.230 g (10.1 mmol) of 2,6-DMP, 1.714 g (10.0 mmol) of benzyl bromide, 4.897 g (15.0 mmol) of cesium carbonate, 17 ml of toluene, and dimethylformamide (DMF) 17 ml was added and stirred at 50 ° C. for 6.5 hours. After completion of the reaction, hydrochloric acid was added and transferred to a separatory funnel to extract the oil layer. Magnesium sulfate was added to the oil layer to remove moisture, and magnesium sulfate was removed by natural filtration. Thereafter, the solvent was removed by an evaporator to obtain an orange oily product (yield: 2.11 g, yield: 99.3%). This product was difficult to isolate because it was liquid at room temperature.

¹ H NMR (400 MHz, CDCl ₃ ): δ 2.29 (s, 9H, CH ₃ ), 4.77 (s, 2H, O—CH ₂ ), 7.00 (t, 1H, Ar—H),
7.02 (t, 2H, Ar-H), 7.36 (t, p-1H, Ar-H), 7.37 (t, m-2H, Ar-H),
7.45 (d, 2H, o-Ar-H)

[Reference Example 2: Synthesis of 3-substitution model]

  Dimroth condenser was attached and dissolved in a 100 ml two-necked flask in a nitrogen atmosphere by adding 0.367 g (3.0 mmol) of 2,6-DMP, 1.141 g (3.5 mmol) of cesium carbonate, 15 ml of toluene, and 15 ml of DMF. I let you. After dissolution, 0.357 g (1.0 mmol) of 1,3,5-trisbromomesitylene (TBM) synthesized in Reference Example 3 described later was added and reacted at 70 ° C. for 40 hours. Diethyl ether and methylene chloride were added to the reaction solution and filtered while hot. Water and chloroform were added to the filtrate, the oil layer was extracted with a separatory funnel, and magnesium sulfate was added to remove moisture. Then, after removing the solvent with an evaporator, the mixture was cooled, and the precipitated crystals were recrystallized using a toluene / hexane mixed solvent to obtain a yellow needle crystal product (yield: 85.6%). It was.

¹ H NMR (400 MHz, CDCl ₃ ): δ 2.34 (s, 18H, CH ₃ ), 4.90 (s, 6H, CH ₂ ), 6.96 (t, 3H, Ar—H),
7.05 (d, 6H, Ar-H), 7.61 (s, 3H, Ar-H)
¹³ C NMR (101 MHz, CDCl ₃ ): δ16.5,73.6,76.7,77.0,77.4,124.1,126.2,128.9,131.1,
138.5,155.8
Anal.Calcd for C ₃₃ H ₃₆ O ₃ ; C: 82.46%, H: 7.55%
Found; C: 82.26%, H: 7.54%

[Reference Example 3: Synthesis of central molecule]

Synthesized according to the reference (Jiuyan Li et al., Chem. Mater. 2005, 17, 1208-1212).
A 300 ml eggplant flask equipped with a Dimroth condenser was charged with 6.000 g (0.0499 mol) of 1,3,5-mesitylene, 26.708 g (0.1501 mol) of N-bromosuccinimide (NBS), benzoyl peroxide (BPO) 0 .242 g (0.99991 mmol) and benzene 150 ml were added and heated. Spontaneous boiling started around 85 ° C., and after the boiling subsided, the mixture was refluxed at 100 ° C. for 6 hours. The precipitated white by-product was filtered off, and the filtrate was washed with water. When the oil layer was concentrated with an evaporator, a brown liquid was obtained. When ethanol was added to this and left in a refrigerator, a white needle-like crystal product 1,3,5-trisbromomesitylene (TBM) (yield: 2.51 g, yield: 17.6%) was obtained. It was.

¹ H NMR (400 MHz, CDCl ₃ ): δ 4.48 (s, 6H, -CH _2- ), 7.38 (s, 3H, Ar-H)
¹³ C NMR (101 MHz, CDCl ₃ ): δ32.0, 129.4, 138.9
FT-IR (KBr (cm ^-1 )): 1604 (C = C), 1212 (CH ₂ ), 582 (C-Br)
Anal.Calcd for C ₉ H ₉ Br ₃ ; C: 30.29%, H: 2.54%
Found; C: 30.29%, H: 2.58%

[Comparative Example 1: Synthesis of linear PPE]

  A 300 ml eggplant flask equipped with an oxygen balloon was charged with 12.216 g (100 mmol) of 2,6-DMP, 1.393 g (3 mmol) of Cu-TMEDA, 3.486 g (30 mmol) of TMEDA, and 100 ml of toluene and a stirrer. The mixture was stirred for 3 hours for polymerization. Thereafter, the reaction solution was poured into methanol to which a small amount of hydrochloric acid was added, the precipitate was filtered off, and dried under reduced pressure at 60 ° C. for 6 hours. After drying, it was dissolved in a small amount of chloroform and reprecipitated with methanol. The deposited precipitate was suction filtered and dried under reduced pressure at 80 ° C. for 8 hours to obtain a white powder product (yield: 4.10 g, yield: 34%).

¹ H NMR (400 MHz, CDCl ₃ ): δ2.12 (s, 6H, CH ₃ ), 4.27 (s, 1H, OH),
6.50 (s, 2H, Ar-H)
FT-IR (Film (cm ^-1 )): 2953 (CH), 1604 (C = C), 1189 (CO), 856 (Ar-H)

[Comparative Examples 2 to 6: Synthesis of linear PPE]
Oxidative coupling polymerization was performed in the same manner as in Comparative Example 1 except that the polymerization time was changed to the time shown in Table 1.

Table 1 shows the measurement results of the yield, molecular weight, glass transition temperature (Tg), and _Td10 of the linear PPE obtained in Comparative Examples 1-6.

[Example 1: Synthesis of three-stranded star PPE]

  In a 300 ml eggplant flask equipped with a Dimroth condenser and a nitrogen balloon, 0.901 g (Mw = 3,000: 0.3 mmol) of PPE synthesized in Comparative Example 1 and 50 ml of toluene were added and dissolved, and further synthesized in Reference Example 3. 0.036 g (0.1 mmol) of TBM, 0.147 g (0.45 mmol) of cesium carbonate, and 50 ml of DMF were added and reacted at 90 ° C. for 40 hours. After the reaction, hydrochloric acid was added, the oil layer was extracted with a separatory funnel, and magnesium sulfate was added to remove water. After removing magnesium sulfate by natural filtration, toluene was removed by an evaporator and added to methanol. The precipitated crude product was dried under reduced pressure at 60 ° C. for 6 hours, dried, dissolved in chloroform, and reprecipitated with methanol to collect the precipitate. This was dried under reduced pressure at 80 ° C. for 10 hours to obtain a white powdery product.

¹ H NMR (400 MHz, CDCl ₃ ): δ2.11 (s, 6H, CH ₃ ), 6.49 (d, 2H, Ar—H)

[Examples 2 to 4: Synthesis of three-stranded star PPE]
The reaction was carried out in the same manner as in Example 1 except that the raw material PPE having the molecular weight shown in Table 2 was used.

Table 2 shows the measurement results of the molecular weight, glass transition temperature (Tg), and _Td10 of the triple-stranded star PPE obtained in Examples 1 to 4.

[Evaluation]
<NMR>
As an example of the linear PPE, the ¹ H-NMR spectrum of the linear PPE obtained in Comparative Example 1 is shown in FIG. 1, and the triple-stranded star PPE obtained in Example 1 is shown as an example of the triple-stranded star PPE. The ¹ H-NMR spectrum of is shown in FIG. Further, the linear PPE obtained in Comparative Example 1, the 3-substitution model obtained in Reference Example 2, and the 7.2-H of the ¹ H-NMR spectrum of the three-chain star PPE obtained in Example 1 were used. Enlarged views around 7.8 ppm are shown in FIGS.

  This linear PPE is a polymer obtained by oxidative coupling of 2,6-dimethylphenol. That is, 2,6-dimethylphenol is one-electron oxidized to generate radical species. This becomes a dimer by coupling with another radical species. In this case, there are three possible coupling positions: oxygen at the 1st position (OO), oxygen and carbon at the 1st and 4th positions (OC), and carbon at the 4th position (CC). In the case of O—O coupling, the generated peroxide is low in stability, so that it is uniformly dissociated again to become the original two radical species. Therefore, there are two former reactions that need to be considered in practice. Hay et al. Reported that CC coupling can be substantially suppressed by adding pyridine more than 100 times to copper chloride (Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 36, 505-517 (1998)). . In the case of a copper chloride-tetramethylethylenediamine (TMEDA) complex, it has been reported that the amount of TMEDA added is at least twice that of copper chloride and that C—C coupling can be suppressed.

  As shown in FIG. 1, large signals are observed at 0, 2.09 (e), 6.47 (f), and 7.25 ppm. These are obtained by partially hydrogenating tetramethylsilane (internal standard substance), methyl hydrogen of PPE, aromatic nucleus hydrogen of PPE, and deuterated chloroform as a solvent. In addition to these, small signals are observed at 1.59, 2.17 (c, g), 4.24 (j), 6.36 (d), 7.09 (h), and 7.35 (i) ppm. Is done. These are water in NMR solvent, methyl hydrogen (c, g) at both terminal units of the polymer, OH (j) at the terminal, aromatic hydrogen at the phenol terminal (d), aromatic hydrogen at the phenylene ether terminal (h) And the aromatic nucleus hydrogen (i) of the biphenyl unit. Therefore, it can be seen that not only the C—O coupling but also a small amount of C—C coupling occurs. Since a C-C coupling produces a telechelic polymer with both terminal OHs, the molar ratio of the one-terminal OH polymer and the telechelic polymer is 0.88: 0.12 calculated from the signal intensity of h and i. It becomes. In addition, in consideration of the terminal group hydrogen h, the repeating unit hydrogen f, and the abundance of the telechelic polymer, the number average molecular weight calculated from NMR is 2,100, which is a relative value estimated from GPC in Table 1. It shows a good agreement with the molecular weight. Since the molecular weight distribution is 1.5, the weight average molecular weight is 3,150, which is in good agreement with the absolute weight average molecular weight 3,000 determined by the light scattering method.

  In the three-stranded star PPE of FIG. 2, signals derived from the PPE main chain skeleton are observed as in FIG. 1, and 4.24 (j), 4.82 (b), 7.09 (h ), 7.34 (i), 7.55 (a) ppm, a small signal was observed. These are the terminal OH (j), the central benzylic hydrogen (b) of the three-stranded star polymer, the aromatic nuclear hydrogen (h) at the phenylene ether terminal, the aromatic nuclear hydrogen (i) of the biphenyl unit, and the three-stranded star, respectively. The central aromatic hydrogen (a) of the shaped polymer.

  The linear PPE of Comparative Example 1 as a raw material was mixed with 12% biphenyl skeleton. From the integrated values in FIG. 2, it is shown that the integrated values of h and i are almost unchanged between the raw material and the product, and no more CC coupling occurs when the three-chain star PPE is generated. Yes. When the number of hydrogens in h is considered to be 3, the number of terminal OHs of the raw material PPE is 1.04 (a little more because it contains telechelic), and the product of the three-chain star PPE The OH number is 0.3. That is, about 71% of the terminal OH of the raw linear PPE reacts with 1,3,5-trisbromomesitylene, which is the central molecule, and the remaining 29% remains unreacted. Considering that the telechelic polymer has OH at both ends, it becomes a three-chain star PPE: linear PPE = 0.8: 0.2 (molar ratio). From the above, it can be said that the purity of the three-stranded star PPE obtained by this reaction is 0.8 (80%). This value is in good agreement with the purity 0.83 of the triple-stranded star PPE calculated from light scattering, and it can be seen that the calculated value from light scattering is useful for determining the purity.

  Thus, the purity of the three-chain star PPE obtained in the same manner as in Examples 2 to 4 was also found to be 0.83, 0.88, and 0.78, respectively.

<Thermal characteristics>
FIG. 4 shows the results of thermogravimetry of the three-stranded star PPE obtained in Example 1 under air. The 10% thermogravimetric loss temperature is 446 ° C., approximately equal to that of linear PPE. In DSC measurement, the glass transition temperature of star-shaped PPE was 195 to 200 ° C., which was almost equal to that of linear PPE. These facts suggest that the physical heat resistance (softening temperature) of PPE is largely dependent on the rotational motion of the main chain phenylene ether and is not significantly affected by intermolecular interactions. That is, in general, the linear shape is easier to take an intermolecular packing structure than the star shape, and it is thought that the thermal motion is small due to aggregation, but in the case of PPE, the packing structure is not so dense due to the influence of the dimethyl group, The magnitude of thermal motion is the same for both linear and star shapes. In addition, regarding the chemical heat resistance of PPE, the thermogravimetric reduction temperature is almost equal, so it can be said that the molecule is decomposed from one point regardless of the star-shaped or linear molecular shape.

<Intrinsic viscosity>
FIG. 5 shows a Huggins plot of the linear PPE obtained in Comparative Examples 1, 3, 4, and 5 and the three-stranded star PPE obtained in Example 3. All the plots were approximated by a straight line, and the reduced viscosity at a concentration of 0 was determined and used as the intrinsic viscosity (intrinsic viscosity).
In linear PPE (Comparative Examples 1, 3, 4, and 5), the intrinsic viscosity increases as the molecular weight increases. The weight average molecular weight of the three-chain star PPE of Example 3 is 16,000, and the weight average molecular weight of the linear PPE having the same intrinsic viscosity as this is 9,000 (linear PPE of Comparative Example 4). Met.
This indicates that the intrinsic viscosity of the three-chain star PPE is significantly lower than that of the linear PPE when compared with the same molecular weight, and the processability is remarkably excellent.

  FIG. 6 shows a Mead-Fuoss plot and a Huggins plot of the triple-stranded star PPE obtained in Example 3.

Moreover, the Huggins constant was calculated | required from the following formula.
η _sp / c = [η] + Kh [η] ² c

  The Huggins constant indicates the interaction force between molecules, and the smaller the value, the weaker the interaction and the smaller the aggregation of the molecular chains. The Huggins constant value 0.26 of the three-stranded star PPE of Example 3 is clearly smaller than 0.31 of the linear PPE, and it can be said that the intermolecular interaction is low.

FIG. 7 is a plot of the relationship between the weight average molecular weight and the intrinsic viscosity of the linear PPE obtained in Comparative Examples 1 to 5 and the three-chain star PPE obtained in Examples 1 to 4. This plot is approximated by the Mark-Howink-Sakurada equation shown below.
[Η] = K [Mw] ^α

The slope of the plot is α in the formula, and this value represents the shape of the molecule in a certain solvent. When the value of α is 0.5, it is a bendable chain in the θ state, when it is 0.7 to 0.8, it is a bendable chain that has undergone an excluded volume effect, and when it is 0.8 or more, it is semi-flexible or rigid. Is a chain.
For triple-stranded star PPE, α = 0.52 and for linear PPE, 0.68. That is, it can be said that the three-strand star PPE is forcibly bonded by the central molecule, and therefore the cohesive force in the molecule is larger than that of the linear PPE.

  The results are summarized in Table 3.

  From the above examination results of intrinsic viscosity (solution viscosity at 30 ° C in chloroform), the three-chain star PPE has a strong cohesive force and a bulky skeleton due to forced binding by the central molecule. It can be said that the interaction between the polymers is reduced, and as a result, the solution viscosity is greatly reduced.

FIG. 8 shows a linear PPE having a weight average molecular weight of 188,000 obtained in Comparative Example 6, (A) a linear PPE having a weight average molecular weight of 9,000 obtained in Comparative Example 4, or (B) Example 2. The transition of the intrinsic viscosity when the three-chain star-shaped PPE having a weight average molecular weight of 10,000 obtained in the above was mixed was shown.
It can be seen from FIG. 8 that the three-chain star PPE functions as a viscosity reducing agent more efficiently than that of the linear PPE. This shows that the star PPE more effectively blocks the interaction between PPE molecules in solution. It is considered that the viscosity can be reduced more drastically because the intermolecular interaction becomes more prominent during melting.

Claims (9)

  A star-shaped polyphenylene ether having a benzene ring as a nucleus and having three or more polyphenylene ether chains extending from carbon atoms on the benzene ring.   2. The star-shaped polyphenylene ether according to claim 1, wherein the polyphenylene ether chain has an oxymethylene group and is bonded to a carbon atom on the benzene ring via an oxymethylene group.   3. The star-shaped polyphenylene ether according to claim 1, wherein the polyphenylene ether chain per one has a weight average molecular weight of 1,000 or more.   The star-shaped polyphenylene ether according to any one of claims 1 to 3, wherein the weight average molecular weight is 7,000 to 20,000.   5. The star-shaped polyphenylene ether according to claim 1, wherein the polyphenylene ether chain is bonded to the 1-position, 3-position and 5-position carbon atoms on the benzene ring.   6. The production of star-shaped polyphenylene ether according to any one of claims 1 to 5, wherein bromomethylbenzene substituted with 3 or more bromomethyl groups is reacted with polyphenylene ether in the presence of a catalyst. Method.   The method for producing a star-shaped polyphenylene ether according to claim 6, wherein the bromomethylbenzene is 1,3,5-trisbromomethylbenzene.   A polyphenylene ether mixture comprising the star-shaped polyphenylene ether according to any one of claims 1 to 5 and polyphenylene ether.   A fluidity improver for polyphenylene ether comprising the star-shaped polyphenylene ether according to any one of claims 1 to 5.

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