JPH083435A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a PPE resin composition which gives a molding retaining the mechanical strength and which, when heated for, e.g. granulation or molding, scarcely causes foaming, generates little amine odor and undergoes less discoloration and less increase in viscosity by incorporating a specified aliphatic primary monoamine into a polyphenylene ether(PPE) having specified terminal structures. CONSTITUTION:This PPE rein composition contains 100 pts.wt. PPE (A) containing an average of 0.01 to 10 terminal structures of formula I (wherein R1 to R5 are each independently H, halogen, a 1-20C alkyl, an alkenyl, an alkynyl, an aryl, etc.; R6 is a 1-6C alkylene, etc.; and R7 to R11 are each independently H, halogen, a 1-6C alkyl, a 1-6C alkoxy, a phenyl, a phenoxy, nitro or cyano) for 100 phenylene ether units and having a number-average degree of polymerization of 10 to 10,000 and 0.01-1 pt.wt. aliphatic primary monoamine (B) substituted by an aromatic ring and represented by formula II (wherein R6 to R11 are the same as in formula I).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a polyphenylene ether having a stabilized terminal structure (polyphenylene ether may be hereinafter referred to as PPE) and an aromatic ring-substituted aliphatic primary monoamine. Regarding

[0002]

2. Description of the Related Art PPE is known to be a useful resin, and in particular, a polymer alloy of this and polystyrene or polyamide has excellent thermal properties, mechanical properties and electrical properties. As a molding material for automobiles, electricity,
Applications to the electronic field are expanding. It has been widely known that PPE is conventionally obtained by oxidative polymerization of nuclear-substituted phenols using a complex catalyst of manganese, copper, cobalt or the like. For example, Japanese Patent Publication No. 5-23291 and U.S. Pat. No. 4,092,294 can be cited. Furthermore, it is also known that PPE polymerized in the presence of a secondary monoamine contains a terminal structure represented by the following general formula (3), and Macromolecules 1990, 2
3 , 1318-1329. However, the PPE containing this terminal structure has a problem of increased coloration and increased viscosity during heating such as granulation and molding.

Embedded image (In the formula, R _{1 to} R ₅ are each independently hydrogen, a halogen atom,
An alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group, R ₁₂
And R ₁₃ are each independently an alkyl group having 1 to 12 carbon atoms or a substituted alkyl group. )

Japanese Unexamined Patent Publication No. 4-253725 discloses a first method.
It is described that PPE polymerized in the presence of a primary monoamine contains a terminal structure represented by the general formula (4).

[Chemical 4] (In the formula, R ₁₄ is a lower alkyl group.)

However, US Pat.
92,294 and US Pat. No. 4,477,651.
In the publication, only alkylamine is exemplified as the primary monoamine, and in US Pat. No. 4,092,294, PP polymerized in the absence of the secondary monoamine.
It is described that E is highly colored and that the thermal stability and mechanical properties of the mixture with styrene resin are deteriorated.
Further, JP-A-5-239323 discloses a modified polyphenylene ether formed by reacting PPE with a primary amine. However, if the primary amine is PPE
Alkylamines are the only examples which do not have a polymerizable carbon-carbon double bond or triple bond capable of reacting with, and are not sufficient to improve the increase in coloration upon heating. On the other hand, Japanese Examined Patent Publication No. 3-69946 discloses a resin composition composed of PPE and an aromatic primary monoamine with little deterioration in mechanical properties during high temperature processing and having good surface gloss. However, the aromatic primary monoamine is a compound in which an aromatic ring and an amino group are directly bonded to each other, and the increase in coloration upon heating is not suppressed. In addition, JP-A-6-25525 discloses a resin composition containing PPE and a primary amine (0.01 to 5 parts by weight), which has an improved resistance to light discoloration and is used as a primary amine. A PPE composition containing 5 parts by weight of benzylamine is exemplified. However, when the amount of benzylamine added is large, there have been problems such as deterioration of mechanical strength of the molded product, inclusion of bubbles in the molded product, and generation of amine odor during molding. Further, there is no description about improvement of coloring and viscosity at the time of molding.

[0005]

The object of the present invention is to maintain the mechanical strength of a molded product, to reduce foaming and amine odor during heating such as granulation and molding, and to increase the amount of coloring during heating. Another object of the present invention is to provide a PPE resin composition having an extremely small increase in viscosity.

[0006]

The inventors of the present invention have made extensive studies for this reason, and as a result, PPE containing a terminal structure having an aromatic ring-substituted aliphatic primary monoamine bonded thereto and an aromatic ring-substituted fat A PPE resin composition containing a group 1 primary monoamine in a specific range maintains the mechanical strength of a molded article,
The present invention has been completed by finding that foaming and amine odor are less likely to occur during heating such as granulation and molding, and that the increase in coloring and the increase in viscosity during heating are significantly suppressed.

That is, the present invention is the invention described below. (I) General formula (1)

Embedded image (In the formula, R _{1 to} R ₅ are each independently hydrogen, a halogen atom,
An alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group, R ₆
Is an alkylene group having 1 to 6 carbon atoms or a substituted alkylene group, and R _{7 to} R ₁₁ are each independently hydrogen, a halogen atom,
It is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, a nitro group or a cyano group. ) Containing an average of 0.01 or more terminal structures per 100 phenylene ether units,
With respect to 100 parts by weight of polyphenylene ether having a number average degree of polymerization of 10 to 10,000, the general formula (2)

[Chemical 6] (In the formula, R _{6 to} R ₁₁ are the same as defined in the general formula (1).) 0.01 to 1 part by weight of an aromatic ring-substituted aliphatic primary monoamine represented by the formula And a polyphenylene ether resin composition.

(II) The polyphenylene ether resin composition according to (I), which contains 0.01 to 1 part by weight of an aromatic ring-substituted aliphatic primary monoamine represented by the general formula (2). . (III) The polyphenylene ether resin composition according to (I) or (II), wherein the polyphenylene ether having a terminal structure represented by the general formula (1) is a powder having an average particle size of 1000 μm or less. (IV) The polyphenylene ether having the terminal structure represented by the general formula (1) is represented by the general formula (2) in the step of drying the polyphenylene ether powder obtained by oxidative polymerization of the nucleus-substituted phenol derivative. The polyphenylene ether resin composition according to (III), which is obtained by adding an aromatic ring-substituted aliphatic primary monoamine and performing heat treatment at a temperature lower than the melting point of the polyphenylene ether.

The PPE in the present invention is a polymer containing a phenylene ether unit as a repeating unit except for its terminal structure and is not particularly limited. A typical example of PPE in the present invention is a unit (repeating unit) represented by the general formula (5)

[Chemical 7] (In the formula, the definitions of R _{1 to} R ₅ are the same as the definition in the general formula (1).) A homopolymer or copolymer which is composed of at least one kind of 1,4-phenylene ether unit represented by the formula (1). However, 1,4 in which the hydroxyl group of general formula (1) or general formula (3) is an ether bond
-A phenylene ether unit or the like may be included.

The 1,4-phenylene ether unit is preferably 2,6-dimethyl-1,4-phenylene ether, 2,6-diethyl-1,4-phenylene ether, 2-ethyl-6-methyl-1. , 4-phenylene ether, 2-methyl-6- (2-octyl) -1,4
-Phenylene ether, 2-allyl-6-methyl-1,
4-phenylene ether, 2- (4- [1-butenyl])-6-methyl-1,4-phenylene ether, 2
-(4- [1-butynyl])-6-methyl-1,4-phenylene ether, 2-methyl-6-phenyl-1,4
-Phenylene ether, 2,3,6-trimethyl-1,
4-phenylene ether, 3-bromo-2,6-dimethyl-1,4-phenylene ether and the like can be mentioned. More preferably, 2,6-dimethyl-1,4-phenylene ether is used. The number average degree of polymerization of PPE in the present invention is 10 to 10,000, preferably 20 to 2,000.

The stabilized terminal structure in the present invention is represented by the general formula (1). Preferably,
In the general formula (1), R ₁ is a methyl group or a phenyl group, one of R ₂ and R ₃ is hydrogen, the other is a methyl group, R ₄ and R ₅ are hydrogen, and R ₆ is Methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2
-Propylene group, 1,3-propylene group, etc., with 1 carbon atom
~ 6 alkylene group or a substituted alkylene group, R
_{7 to} R ₁₁ are each independently hydrogen; a halogen atom; a methyl group,
An alkyl group having 1 to 6 carbon atoms such as ethyl group and n-propyl group; an alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, and n-propoxy group; phenyl group; phenoxy group; nitro group or cyano group Is. More preferably, in the general formula (1), R ₁ is a methyl group and R ₁ is
_{2 to} R ₅ and R _{7 to} R ₁₁ are both hydrogen, and R ₆ is a methylene group.

The PPE in the present invention means the general formula (1)
The end structure represented by is the polyphenylene ether unit.
An average of 0.01 to 10 per 100, preferably
Is PPE containing 0.05 to 5. In addition, other
As the terminal component, the terminal structure of the general formula (3) or the general formula
A terminal structure in which the ether bond of (5) is substituted with a hydroxyl group, etc.
May be included. As a specific example, the general formula (3)
R₁Is a methyl group or a phenyl group, and R₂, R₃
One of which is hydrogen and the other is a methyl group, R_Four, R
_FiveIs hydrogen and R₁₂, R₁₃Is a methyl group or n-butyl
In the terminal structure which is a group and in the general formula (5)₁
Is a methyl group or a phenyl group, and R ₂, R₃One of
Is hydrogen and the other is a methyl group, R_Four, R_FiveBut water
Examples include elementary terminal structures. Particularly preferably,
R in general formula (3)₁Is a methyl group, and R₂~ R_Five
Are both hydrogen and R₁₂, R₁₃Both ends are n-butyl groups
In the structure and the general formula (5), R₁Is a methyl group
R₂~ R_FiveA terminal structure in which both are hydrogen
It

Aromatic Ring Substituted Aliphatic 1 in the Present Invention
The primary monoamine is represented by the general formula (2)

Embedded image (In the formula, the definitions of R _{6 to} R ₁₁ are the same as the definition of the general formula (1).). Preferably, in the general formula (2), R ₆ is methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,
An alkylene group having 1 to 6 carbon atoms such as a 3-propylene group or a substituted alkylene group, wherein R _{7 to} R ₁₁ are each independently hydrogen; a halogen atom; a methyl group, an ethyl group, an n-propyl group or the like having 1 carbon atom An alkyl group having 6 to 6; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and an n-propoxy group; a phenyl group; a phenoxy group; a nitro group or a cyano group.

Specifically, benzylamine, o-, m-
Or p-chlorobenzylamine, o-, m- or p-methylbenzylamine, o-, m- or p-
Methoxybenzylamine, o-, m- or p-phenylbenzylamine, o-, m- or p-phenoxybenzylamine, o-, m- or p-nitrobenzylamine α- or β-phenylethylamine, α
-, Β- or γ-phenyl-1-propylamine,
Examples thereof include α-, β-, γ-, or δ-phenyl-1-butylamine. More preferably, benzylamine is used.

The PPE resin composition of the present invention means that the terminal structure represented by the general formula (1) is contained in an average of 0.01 to 10 and preferably an average of 0.05 to 5 per 100 phenylene ether units. And the number average degree of polymerization is 10 to 1
PPE10 which is 0000, preferably 20-2000
0.01 to 1 part by weight, preferably 0.01 to 1 part by weight, based on 0 part by weight, as the free amount in which the aromatic ring-substituted aliphatic primary monoamine represented by the general formula (2) is not bound to the polymer. It contains 0.6 parts by weight. When the amount of the aliphatic primary monoamine substituted with a free aromatic ring is less than 0.01 part by weight, the increase in coloring and the increase in viscosity upon heating are not preferable. Further, when the amount of the aliphatic primary monoamine substituted with free aromatic ring is more than 1 part by weight, the mechanical strength of the molded product is lowered, an amine odor is generated during molding, and air bubbles are mixed in the molded product. This is not preferable because it causes problems such as

There is no particular limitation on the method for producing the PPE resin composition of the present invention. As a typical production method, the average number of terminal structures represented by the general formula (3) is 0.01 to 10 per 100 phenylene ether units.
PPE100 containing 50, preferably 0.05-5
With respect to parts by weight, the aromatic ring-substituted aliphatic primary monoamine represented by the general formula (2) is added to [0.55 × (XY /
Z) +0.01] parts by weight or more, [1.7 × (XY / Z)
+1] parts by weight or less, preferably [0.55 × (XY /
Z) +0.01] parts by weight or more, [1.7 × (XY / Z)
+0.6] parts by weight or less [where X is the number of terminal structures represented by the general formula (3) per 100 phenylene ether units in PPE, and Y is a substitution of the aromatic ring represented by the general formula (2). Is the molecular weight of the aliphatic primary monoamine, and Z is the chemical formula weight of the phenylene ether unit in PPE. ] And heat treatment is mentioned.

The PPE used here is Japanese Patent Publication No. 5-232.
No. 91, U.S. Pat. No. 4,092,294, and the like, which are obtained by a method of oxidatively polymerizing a nuclear-substituted phenol described in the presence of a complex catalyst such as manganese, copper, or cobalt and a secondary monoamine. The temperature at which the PPE and the aromatic ring-substituted aliphatic primary monoamine are heat-treated is preferably 100 to 320 ° C., more preferably 120 to 30 ° C.
0 ° C. As a specific production method, PPE and an aromatic ring-substituted aliphatic primary monoamine are mixed and melt-kneaded by using a Banbury mixer, a roll, a kneader, an extruder or the like, or heated by a heat press machine. A method of compression may be used. Further, a method in which an aliphatic primary monoamine having an aromatic ring substituted is added to a dryer attached to the polymer production process and the mixture is heated and stirred is also included.

A method of adding an aromatic ring-substituted aliphatic primary monoamine to the drying step, which will be described in detail below, and performing heat treatment is as follows.
It is slightly superior to other methods in that it allows uniform and large-scale processing in the manufacturing process of PPE. The dryer used is not particularly limited, and a commonly used fluid dryer, rotary dryer, multi-fin type agitator dryer, etc. are applied. The temperature at which the aromatic primary monoamine substituted with an aromatic ring is added and allowed to react may be lower than the melting temperature of PPE, but is preferably in the range of 100 to 170 ° C. in consideration of drying efficiency. The time is not particularly limited, but is usually 0.5 to
A range of 10 hours is chosen. The contact treatment with the aliphatic primary monoamine in which the aromatic ring is substituted may be either batch system or continuous system.

The PPE used in the drying step may be powdered after purifying the polymerization reaction liquid, but more preferably the average particle size of the PPE powder is 1000 μm or less. For example, when the polymerization reaction liquid is in a solution state, it is treated with water containing each purifying agent to perform liquid-liquid separation, and then PPE in the organic phase is precipitated with a poor solvent such as methanol to give a solid-
PPE powder obtained by liquid separation; or PPE powder obtained by solid-liquid separation after precipitation from a polymerization liquid with a poor solvent such as methanol. The PPE powder contains an aromatic hydrocarbon such as benzene, toluene or xylene and an alcohol such as methanol or water.
It is subjected to a drying step for removing these solvents.
In the drying step, the solvent and the like are removed and a contact treatment with an aliphatic primary monoamine having an aromatic ring substituted is performed. The aromatic ring-substituted aliphatic primary monoamine used in the present invention may be mixed with the PPE wet powder in advance, or may be directly supplied to the dryer as it is. When it is directly supplied to the dryer, it can be supplied in a liquid state, a mist state, or a gas state.

[0020]

EXAMPLES The present invention will be described in detail below with reference to examples, but these examples are merely for exemplification,
The present invention is not limited in any way. PPE or PP
The heat molding of the E composition was carried out by placing PPE or the powder of the PPE composition in a mold having a thickness of 1 mm and at 250 ° C. for 10 to 10 ° C.
It was carried out by press molding for 10 minutes under 0 kg / cm ² . As a measure of the coloring amount of the PPE composition, a spectrophotometer (Hitachi, Ltd.) using a quartz cell with an optical path length of 10 mm for a chloroform solution in which PPE or PPE composition powder or a press sheet having a concentration of 0.25 g / dl is dissolved is used. Absorbance at 340 nm (hereinafter, abbreviated as ABS ₃₄₀ ) by U-3500 manufactured by Seisakusho Co., Ltd. was used.

The amount of color increase of the PPE composition upon heating is P
ABS of PE composition press sheet ₃₄₀And PPE pow
Dar's ABS₃₄₀Difference (below, △ ABS₃₄₀Stands for
You ). Viscosity of PPE or PPE composition
The degree of PPE or PPE composition is 0.5 g / d
l or chloro dissolved powder or press sheet
Reduced viscosity (hereinafter,
η_spAbbreviated as / C. ) Was used. Viscosity of PPE composition when heated
The degree of increase is η of the press sheet of the PPE composition._sp/ C and P
PE powder η_spDifference from / C (hereinafter, Δη_spAbbreviated as / C
You ).

The bending strength of the press-molded product was measured using a Autograph AG5000D (manufactured by Shimadzu Corporation) on a 35 mm × 11 mm test piece obtained by cutting a 1 mm-thick press sheet. The number of bubbles in the press molded body is
The number of bubbles of 1 mmφ or more per 35 mm × 35 mm test piece was determined by counting with the naked eye. The molecular weight of PPE is a standard polystyrene conversion value by gel permeation chromatography using RI-8011 manufactured by Tosoh Corporation as a detector. The amount of free amine not bound to the polymer in the PPE composition was quantified by a nitrogen-phosphorus detector (NPD) using gas chromatography (HP-589OA manufactured by Hewlett Packard).

The terminal structure of PPE was determined and quantified by measuring the nuclear magnetic resonance (hereinafter referred to as NMR) spectrum of a sample obtained by reprecipitating PPE to remove free amine. For reprecipitation of PPE, 2 g of PPE was dissolved in 40 ml of chloroform, and this solution was added with 160 m of methanol.
The resulting precipitate was filtered, and 20 ml of methanol was added.
After being washed twice with, filtered and dried under reduced pressure at 100 ° C. for 3 hours. The NMR spectrum is AMX6 manufactured by Bruker
00, ¹ H-NMR spectrum, HMQC spectrum (J. Am. Chem. Soc. 1986, 10
8, 4285) and HMBC spectrum (J.A.
m. Chem. Soc. 1986, 108, 2093).

Example 1 An autoclave equipped with a stirrer, a thermometer, a condenser and an air inlet tube and having a capacity of 100 liters was used. 35.7 kg of xylene, 12.2 kg of methanol,
After charging 2.2-kg (100 mol) of 2,6-dimethylphenol and 320 g (8 mol) of sodium hydroxide into a uniform solution, 220 g (3.6 mol) of monoethanolamine and 129 g of dibutylamine ( 1
Mol) and manganese chloride tetrahydrate 8.9 g (0.045
Mol) in 1000 g of methanol was added. Then, while vigorously stirring, air is supplied at a flow rate of 10 liters / under a temperature of 40 ° C. and a pressure of 9 kg / cm ^2.
It was blown in for 10 hours to react. Reaction temperature is 7.5
The temperature was kept at 30 ° C for a while. The polymerization reaction liquid at this time was in a viscous solution state. 22.5 kg of methanol was added to this polymerization reaction to make a slurry state in a solution state. The slurry was filtered with a vacuum filter, washed with 24.0 kg of methanol, and similarly filtered to obtain a wet solid.

This wet solid was added to 48 liters of water and 147 g (0.33 mol) of sodium pyrophosphate decahydrate in a 100-liter stirring tank equipped with a stirrer, a thermometer, a condenser and a steam introducing tube at the bottom. And 196 g (1.03 mol) of sodium pyrosulfite were treated with stirring at 70 ° C. for 1 hour. After that, the solvent was blown at a flow rate of 3 kg / h for 8 hours for desolvation.
Then, the dispersion was extracted and solid-liquid separated with a basket centrifuge to obtain a polymer. Next, 48 liters of water was added to this polymer, which was washed with water at 70 ° C. for 30 minutes, and then solid-liquid separated by a basket type centrifugal separator to obtain a PPE wet powder.
The PPE wet powder was charged into a jacketed fluidized tank having a capacity of 40 liters having a porous plate at the bottom, and the temperature was 120 ° C.
Blow at ℃, nitrogen flow rate of 175 Nm ³ / h and dry for 3 hours, 11.5 kg of PPE powder (number average molecular weight: 1
2,400, the number average degree of polymerization: 103) was obtained.

From the ¹ H-NMR spectrum analysis of the sample obtained by reprecipitating this PPE powder, Macromol
The following terminal structure (7) identified in Ecules 1990, 23, 1318-1329 is 2,6-
Dimethyl-1,4-phenylene ether unit 100
An average of 1 was contained for each.

[0027]

[Chemical 9] 8.0 g of this PPE powder and 160 mg of benzylamine dissolved in methanol (2 parts by weight with respect to PPE powder) were mixed, stirred at room temperature for 1 hour, dried under reduced pressure to remove methanol, and then pressed at 250 ° C. Molded to obtain a PPE composition. No amine odor was felt during press molding. From the NMR spectrum analysis of the sample obtained by reprecipitating the press-molded product of the PPE composition, the PPE in the composition was obtained by averaging the following terminal structure (6) with respect to 2,6-dimethyl-1,4-phenylene ether unit 100. It contained 0.6 pieces.

[Chemical 10]

In the ¹ H-NMR spectrum of the sample, the main peaks are 2.10 ppm and 6.48 ppm showing the repeating unit 2,6-dimethyl-1,4-phenylene unit. 3.80 ppm and 3.8 with respect to Comparative Example 1 without addition of amine.
New peaks appeared at 2 points of 8 ppm ( ¹ H-N
The MR spectrum is shown in FIG. ). From the analysis of the HMQC spectrum and the HMBC spectrum, these two peaks were assigned to the methylene proton bonded to the 1′-position and the methylene proton bonded to the 2-position of the structure (6), respectively. The structure (6) is a terminal structure,
The chemical shifts of carbon 13 at the 1st, 2nd, and 3rd positions identified from the proton peak at 3.88 ppm and the long-range spin coupling are 150.4 ppm, 122.3 ppm, and 11 respectively.
It was determined to be 1.7 ppm, which was in good agreement with the chemical shift of the terminal structure (7). Structural quantification was carried out by ¹ H-NMR of this sample in which the peak at 3.80 ppm, which is the methylene proton bonded to the 1′-position of the structure (6), and 3 of the 2,6-dimethyl-1,4-phenylene ether unit. , And the area intensity ratio of the peak at 6.48 ppm, which is the proton at the 5-position. Regarding the press-molded product, the average molecular weight of PPE was 13,000 (number average degree of polymerization = 108, and the amount of free benzylamine in the composition was 0.50 wt%. The evaluation results of are shown in Table 1.

Examples 2-5, Comparative Examples 1-6 A PPE composition or a PPE press-molded product was obtained in the same manner as in Example 1 except that the addition amount of benzylamine was changed. Table 1 shows the evaluation results of the obtained molded body.

Example 6 PPE wet powder was obtained in the same manner as in Example 1 up to solid-liquid separation using a basket centrifuge. To this PPE wet powder, 89 g of benzylamine (0.8 parts by weight based on PPE dry powder) was added and mixed. Then, this was placed in a jacketed fluidized vessel having a capacity of 40 liters having a perforated plate at the bottom, and the temperature was 120 ° C. and the nitrogen flow rate was 175 Nm ³ / h.
And dry it for 3 hours to obtain P with an average particle size of 300 μm.
11.5 kg of PE composition powder (number average molecular weight of PPE: 13,500, number average degree of polymerization: 112) was obtained.
NMR of sample reprecipitating this PPE composition powder
From the spectrum, the PPE shows that the terminal structure (6) is 2,6
-Dimethyl-1,4-phenylene ether unit 10
An average of 0.1 was contained for 0. In addition, PPE
The amount of free benzylamine in the composition powder was 0.
It was 02% by weight. Increase in heat coloration of PPE composition △
ABS ₃₄₀ is 0.03, heating viscosity increase Δη _sp / C
Was 0.04 dl / g. Further, the bending strength of the press-molded product of the PPE composition was 1200 kgf / cm ² , the number of bubbles of 1 mmφ or more in the press-molded product was 0, and no amine odor was felt during press molding.

Comparative Example 7 Example 1 except that benzylamine was changed to aniline (an aromatic primary monoamine having an amino group directly bonded to an aromatic ring).
The same procedure as in (1) was performed to obtain a press-molded body. The amount of increase in heat coloring ΔABS ₃₄₀ of the obtained press-molded product was 0.11. The addition of the aromatic primary monoamine further increased the amount of color increase upon heating.

[0032]

[Table 1]

[0033]

The PPE resin composition of the present invention has a terminal structure in which PPE is stabilized, and a free aromatic ring-substituted aliphatic primary monoamine is limited to a specific range amount. The mechanical strength of the molded product is maintained, foaming and amine odor are less likely to occur, and the amount of increase in coloring and the amount of increase in viscosity upon heating are significantly suppressed, which is very useful in practice.

[Brief description of drawings]

FIG. 1 ¹ H-NMR spectrum of PPE of Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akihiko Okada 6 Kitahara, Tsukuba-shi, Ibaraki, Sumitomo Chemical Co., Ltd. (72) Inventor Kazutoshi Ohashi 6 Kitahara, Tsukuba-shi, Ibaraki, In-house (72) Invention Ryuhei Matsui 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. Yokkaichi Research Institute (72) Inventor Shigeki Kiriyama 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. Yokkaichi Research Institute

Claims (4)

[Claims] 1. A general formula (1): (In the formula, R _{1 to} R ₅ are each independently hydrogen, a halogen atom,
An alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group, R ₆
Is an alkylene group having 1 to 6 carbon atoms or a substituted alkylene group, and R _{7 to} R ₁₁ are each independently hydrogen, a halogen atom,
It is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, a nitro group or a cyano group. The average number of the terminal structures represented by the formula (1) is 0.01 to 10 per 100 phenylene ether units, and the general formula (2) is used with respect to 100 parts by weight of polyphenylene ether having a number average degree of polymerization of 10 to 10,000. ) [Chemical 2] (In the formula, R _{6 to} R ₁₁ are the same as defined in the general formula (1).) 0.01 to 1 part by weight of an aromatic ring-substituted aliphatic primary monoamine represented by the formula And a polyphenylene ether resin composition. 2. The polyphenylene ether resin according to claim 1, which contains 0.01 to 0.6 part by weight of an aromatic ring-substituted aliphatic primary monoamine represented by the general formula (2). Composition. 3. The polyphenylene ether resin composition according to claim 1, wherein the polyphenylene ether having a terminal structure represented by the general formula (1) is a powder having an average particle diameter of 1000 μm or less. Stuff. 4. A polyphenylene ether having a terminal structure represented by the general formula (1) is represented by the general formula (2) in a step of drying a polyphenylene ether powder obtained by oxidative polymerization of a nucleus-substituted phenol derivative. The polyphenylene ether resin composition according to claim 3, wherein the polyphenylene ether resin composition is obtained by adding the aromatic ring-substituted aliphatic primary monoamine to a heat treatment at a temperature lower than the melting point of the polyphenylene ether.