JPH07102169A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition composed of a modified polyphenylene ether and an ethylene-copolymer consisting of respective specific structural units, having excellent heat-resistance, moldability, mechanical properties and impact strength, producible at a low cost and useful for sheet, etc. CONSTITUTION:This thermoplastic resin composition is composed of (A) 100 pts.wt. of a modified polyphenylene ether containing the structural unit of the formula (R1 and R2 are H or 1-20C hydrocarbon group), having a number- average degree of polymerization of 20-1,200 and obtained by replacing the 2-and 6-methyl groups of the phenylene group with aminomethyl groups at a ratio of (0.02-1)/X wherein X is the number-average degree of polymerization and (B) 0.1-70 pts.wt. of an ethylene copolymer containing epoxy group and composed of (i) 50-99wt.% of ethylene unit, (ii) 0.1-30wt.% of unsaturated carboxylic acid glycidyl ester unit or unsaturated glycidyl ether unit and (iii) 0-50wt.% of ethylenic unsaturated ester compound unit.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used for molded articles by injection molding or extrusion molding.

[0002]

2. Description of the Related Art Polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability, and mechanical and electrical properties. However, its high melt viscosity makes it extremely processable. It has the drawbacks of poor heat resistance, poor chemical resistance and low thermal shock resistance.

As an attempt to improve the molding processability of polyphenylene ether, a method of blending polyphenylene ether with polystyrene is known. However, although this method improves the moldability of the polyphenylene ether, it causes a problem that the heat resistance of the polyphenylene ether is significantly reduced.

JP-A-57-108153 describes that a composition having excellent impact resistance can be obtained by blending polyphenylene ether with a copolymer of olefin and glycidyl methacrylate and / or glycidyl acrylate. However, problems still remain in the molding processability and heat resistance of the composition.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to make use of the excellent mechanical properties and heat resistance of polyphenylene ether, and to improve the molding processability and impact resistance of an inexpensive thermoplastic resin. To provide a composition.

[0006]

The present inventors have arrived at the present invention as a result of intensive studies to solve these problems. That is, the present invention comprises the inventions described below.

[I] (A) The following structural unit (1)

[Chemical 2] (Wherein R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms),
In the polyphenylene ether having a number average degree of polymerization of 20 to 1200, when the number average degree of polymerization is X, 0.02 of the methyl group at the 2-position and / or the 6-position of the phenylene group.
/ X to 1 / X modified polyphenylene ether modified to an aminomethyl group, and (B) (a) ethylene unit of 50 to 99% by weight, (b) unsaturated carboxylic acid glycidyl ester unit or unsaturated glycidyl The epoxy unit-containing ethylene copolymer comprises 0.1 to 30% by weight of an ether unit and 0 to 50% by weight of an ethylenically unsaturated ester compound unit (c), and the component (A) is added to 100 parts by weight of the component (A). A thermoplastic resin composition in which B) is 0.1 to 70 parts by weight.

Next, the present invention will be described in detail. The component (A) used in the thermoplastic resin composition of the present invention is a part of the methyl group at the 2-position and / or the 6-position of the phenylene group in the polyphenylene ether represented by the general formula (1) is an aminomethyl group. a modified polyphenylene ether having a modified structure units (-CH ₂ NH _2). The structural unit substituted with the aminomethyl group may be a terminal structural unit of the polyphenylene ether, or may be in the middle of the main chain instead of the terminal. In particular, it is preferable that the structural unit substituted with the aminomethyl group is a terminal structural unit of polyphenylene ether, since it is easy to obtain.

The modified polyphenylene ether of the component (A) has a phenylene group of 2 when the number average degree of polymerization is X.
0.02 / X to 1 / of the methyl group at position 6 and / or 6
X, preferably 0.05 / X to 1 / X, is modified to an aminomethyl group. The aminomethyl group is a methyl group at positions 2 and 6 of the phenylene group and 0.
When it is less than 02 / X, when used as a component of the resin composition, heat resistance and mechanical properties are not sufficiently improved, which is not preferable.

As the modified polyphenylene ether of the component (A), those having a number average number of structural units represented by the general formula (1) of 20 to 1200, and more preferably 30 to 1000 are used. If the number of structural units represented by the general formula (1) is out of this range, the processability of the resin becomes poor, or the mechanical properties become insufficient, which is not preferable. As a component of the thermoplastic resin composition of the present invention, polyphenylene ether consisting only of the structural unit represented by the general formula (1) has insufficient reactivity with the epoxy group-containing ethylene copolymer of the component (B). Is at the 2-position and / or 6 of the phenylene group in the polyphenylene ether.
The modified polyphenylene ether having a structural unit in which the methyl group at the position is denatured to an aminomethyl group is preferable because it is highly reactive with the epoxy group-containing ethylene copolymer of the component (B).

Next, a method for producing the modified polyphenylene ether of the component (A) will be described. The modified polyphenylene ether of the component (A) can be produced by the following general formula (2).

[0012]

[Chemical 3] (In the formula, R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.) A nucleus-substituted phenol represented by the formula is polymerized using an oxidation coupling catalyst. In the method of formula (3)

[Chemical 4] (In the formula, Q ₁ and Q ₂ are each independently selected from hydrogen, an alkyl group having 1 to 24 carbon atoms and an aralkyl group having 7 to 24 carbon atoms, provided that both Q ₁ and Q ₂ are hydrogen. And an amine represented by Q ₁ and Q _{2 each} being an alkylene group which is linked to form a ring).
A method for producing a modified polyphenylene ether, which comprises polymerizing the polyphenylene ether in an amount of 01 to 0.2 mol and melt-kneading the obtained polyphenylene ether, is preferable. More specifically, in the method of polymerizing the nuclear-substituted phenols represented by the general formula (2) using an oxidative coupling catalyst, the amines represented by the general formula (3) are
Polymerize when present. The amines are present in an amount of 0.001 to 0.2 mol, preferably 0.005 to 0.05 mol, based on 1 mol of the nuclear-substituted phenols used. If the amount used is less than 0.001 mol with respect to 1 mol of the nuclear-substituted phenols, polyphenylene ether of excellent quality cannot be obtained, and if it is more than 0.2 mol, a polyphenylene ether having a practical molecular weight is used. Is not preferable because it cannot be obtained. In this way, a polyphenylene ether having the amines in its side chain can be obtained. Next, the nucleus-substituted phenols are those represented by the general formula (2), and the nucleus-substituted phenols can be used alone or in combination of two or more kinds.

Preferred nuclear-substituted phenols are 2,
6-dimethylphenol, 2,3,6-trimethylphenol and the like can be mentioned. Particularly, 2,6-dimethylphenol is preferable.

Next, as the amines represented by the general formula (3), specifically, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-hexylamine, n-
1 such as octylamine, 2-ethylhexylamine, cyclohexylamine, laurylamine, benzylamine
And secondary amines such as diethylamine, di-n-propylamine, di-n-butylamine, di-iso-butylamine, di-n-octylamine, piperidine and 2-pipecoline. The general formula (3)
A polyvalent amine that is considered to contain a repeating unit is equivalent to the amine represented by the general formula (3), and examples of such a polyvalent amine include ethylenediamine, piperazine, and 1,3-dipiperidylpropane. Etc.

Specifically, a catalyst system in which an amine represented by the general formula (3) is combined with a known copper compound, manganese compound or cobalt compound and a ligand selected from bases is used. preferable. For example, JP-A-53-
As described in JP-A-79999, a method of oxidatively coupling a phenolic monomer and oxygen in the presence of a catalyst composed of a manganese salt, a basic reaction medium and a secondary amine, or JP-A-63-54424. As described in
A method of oxidatively polymerizing a nuclear-substituted phenol with an oxygen-containing gas in an organic solvent in the presence of a catalyst, wherein the catalyst comprises a manganese compound containing one or more divalent manganese salts, a Group IA metal of the periodic table. Examples include a method using a catalyst system containing at least one basic compound selected from hydroxides, alkoxides or phenoxides, hydroxides of Group IIA metals, oxides, alkanolamines, and amines.

Thus, the following general formula (4)

[Chemical 5] (Wherein Q ₁ and Q ₂ are each independently selected from hydrogen, an alkyl group having 1 to 24 carbon atoms and an aralkyl group having 7 to 24 carbon atoms. Provided that both Q ₁ and Q ₂ are hydrogen. excluding, also by groups Q _1, Q ₂ is represented by including.) which are linked to form a ring an alkylene group, a methyl group at the 2-position and / or 6-position of the phenylene group is modified A polyphenylene ether having the defined structural unit can be obtained.

The structural unit to which the secondary or tertiary amine is bonded may be the terminal structural unit of the polyphenylene ether, or may be not the terminal but the middle of the main chain. In particular, it is preferable that the structural unit is a terminal structural unit of polyphenylene ether because it is easy to obtain.

Then, the polyphenylene ether having a secondary or tertiary amine bonded to the methyl group at the 2-position and / or the 6-position of the phenylene group thus obtained is melt-kneaded while being devolatilized. The modified polyphenylene ether of the component (A) of the thermoplastic resin composition of the present invention can be obtained. The melt-kneading may be performed at a cylinder set temperature of 200 to 300 ° C, preferably 230 to 280 ° C. If the cylinder set temperature is lower than 200 ° C, the moldability of the raw material polyphenylene ether is poor, and if the cylinder set temperature exceeds 300 ° C, the polyphenylene ether is decomposed, which is not preferable. For melt kneading, it is preferable to use a generally used kneading device such as a single-screw or twin-screw extruder and various kneaders.

It is also possible to mix a radical initiator when melt-kneading and melt-knead. Further, the polyphenylene ether may be blended with a radical initiator in advance and melt-kneaded. Radical initiators preferably used include cumene hydroperoxide and t
-Butyl hydroperoxide, dimethyl-2,5-
Bis (hydroperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-
Butyl peroxide, 2,6-di-t-butyl-4 methylphenol and the like can be mentioned.

Component (A) of the thermoplastic resin composition of the present invention
Of the modified polyphenylene ether and its raw material polyphenylene ether η _{SP /} c (0.5 g / dl
Value measured at 25 ° C. for the chloroform solution of
The range of 0.30 to 0.65 dl / g is preferable. η _SP /
When c is less than 0.30 dl / g, the heat resistance of the composition remarkably decreases, and when η _SP / c exceeds 0.65 dl / g, the moldability of the composition deteriorates, which is not preferable. If necessary, an unmodified polyphenylene ether can be added to the polyphenylene ether as the component (A) of the thermoplastic resin composition of the present invention.

The epoxy group-containing ethylene copolymer (B) which is a constituent of the thermoplastic elastomer composition of the present invention means (a) an ethylene unit of 50 to 99% by weight and (b) an unsaturated carboxylic acid glycidyl ester. 0.1 to 30% by weight, preferably 0.5 to 20% by weight of units or unsaturated glycidyl ether units, and 0 to 50% by weight of (c) ethylenically unsaturated ester compound units, an epoxy group-containing ethylene copolymer. Is. The compounds which give the unsaturated carboxylic acid glycidyl ester unit and the unsaturated glycidyl ether unit (b) in the epoxy group-containing ethylene copolymer (B) are represented by the following general formulas (5) and (6), respectively.

[Chemical 6] (R is a C2-C13 hydrocarbon group having an ethylenically unsaturated bond.)

[Chemical 7] (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or

[Chemical 8] Is. ) Specific examples include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

The epoxy group-containing ethylene copolymer of the present invention includes a terpolymer of carboxylic acid glycidyl ester or unsaturated glycidyl ether, ethylene and (c) an ethylenic unsaturated ester compound, which is a ternary or more terpolymer. Can also be used. Examples of the ethylenically unsaturated ester compound (c) include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, carboxylic acid vinyl esters such as butyl methacrylate, Examples include α, β-unsaturated carboxylic acid alkyl esters and the like. Particularly, vinyl acetate, methyl acrylate, and ethyl acrylate are preferable.

The epoxy group-containing ethylene copolymer (B) used in the present invention includes, for example, a copolymer consisting of ethylene units and glycidyl methacrylate units, a copolymer consisting of ethylene units, glycidyl methacrylate units and methyl acrylate units, Examples thereof include copolymers composed of ethylene units, glycidyl methacrylate units and ethyl acrylate units, copolymers composed of ethylene units, glycidyl methacrylate units and vinyl acetate units.

The melt index (JIS K6760) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 5
It is 0 g / 10 minutes. The melt index may be outside this range, but the melt index is 100 g / 1
When it exceeds 0 minutes, it is not preferable in terms of mechanical properties when it is made into a composition, and when it is less than 0.5 g / 10 minutes, the compatibility with the modified polyphenylene ether of the component (A) is poor.

The epoxy group-containing ethylene copolymer is usually an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 at 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a method of copolymerizing below. It can also be produced by a method of mixing an unsaturated epoxy compound and a radical generator with polyethylene and performing melt graft copolymerization in an extruder.

In the thermoplastic resin composition of the present invention, the composition ratio of the modified polyphenylene ether of the component (A) and the epoxy group-containing ethylene copolymer of the component (B) is the component (A).
0.1 to 70 parts by weight of the component (B) per 100 parts by weight,
Preferably 1-40 parts by weight, more preferably 3-30
Parts by weight. If the amount of the component (B) is less than 0.1 part by weight, the impact resistance improving effect of the composition is not recognized, and if the amount of the component (B) exceeds 70 parts by weight, the heat resistance of the composition decreases. Not preferable.

In the thermoplastic resin composition of the present invention,
Inorganic fillers are used if desired. Such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass fiber, carbon fiber, alumina fiber,
Examples thereof include aluminum borate whiskers and potassium titanate fibers.

If necessary, the thermoplastic resin composition of the present invention may further contain an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant, and a rust preventive agent. Various additives such as a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a release improving agent such as a fluororesin can be added during the manufacturing process or in the subsequent processing process.

As the method for producing the thermoplastic resin composition in the present invention, for example, a modified polyphenylene ether of the component (A) is produced in advance by melt-kneading while devolatizing the polyphenylene ether using a kneader, The epoxy group-containing ethylene copolymer of the component (B) is blended with the above and the mixture is kneaded together to produce the composition, or the modified polyphenylene ether of the component (A) obtained as described above, the component (B Method of dissolving each of the epoxy group-containing ethylene copolymers in a solvent and mixing the components in a solution state to evaporate the solvent or to add the solvent to a solvent in which the resin component does not dissolve to precipitate the resin composition, etc. Is mentioned.

Further, the polyphenylene ether is charged from the first feed port of the kneading extruder, and the polyphenylene ether is melt-kneaded in the kneading extruder between the first feed port and the second feed port to obtain the component (in the present invention). After the modified polyphenylene ether of A) is produced, the epoxy group-containing ethylene copolymer or the like of the component (B) is charged from the second feed port of the extrusion kneader, and the modified polyphenylene ether and the epoxy group-containing ethylene copolymer are added. A method of producing a resin composition by melt-kneading the coalesced product in the kneading extruder is also included.

In any case, the fact that the component (A) constituting the obtained resin composition is a modified polyphenylene ether containing a primary amine means that a modified polyphenylene ether and / or a modified polyphenylene ether containing a primary amine is used. Alternatively, it can be confirmed by extracting and reprecipitating polyphenylene ether and then quantifying the amine species in the extracted component by a potentiometric titration method or the like.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. The quantitative determination of the amine, the NMR measurement, and the physical properties of the molded product were measured by the following methods.

(Determination of amine in raw material polyphenylene ether and modified polyphenylene ether) Nitrogen content in total amine: About 1 g of a sample was weighed and dissolved in 50 cc of chloroform, and 5 cc of acetic acid was added,
Potentiometric titration was performed using a potentiometer AT-310 (glass-calomel electrode, titrant 0.1 mol perchloric acid, (acetic acid solution)) manufactured by Kyoto Electronics Co., Ltd., and nitrogen in all amines was calculated according to the following formula. The content was determined. N _T = 0.0014 × A × C ₁ × 100 / S N _T : Nitrogen content (%) of all amines A: Titration amount (cc) S: Sample amount (g) C ₁ : Concentration of perchloric acid solution ( Mol / liter)

Nitrogen content in tertiary amine: about 1 g of sample
Was dissolved in 50 cc of chloroform, added with 5 cc of acetic anhydride, allowed to stand, added with 5 cc of acetic acid, and then subjected to potentiometric titration as in the case of titration of nitrogen content in all amines. The nitrogen content in it was determined. N ₃ = 0.0014 × B × C ₂ × 100 / S N ₃ : Nitrogen content in tertiary amine (%) B: Titration amount (cc) S: Sample amount (g) C ₂ : Perchloric acid solution Concentration (mol / liter)

Nitrogen content in secondary amine: about 1 g of sample
Was dissolved in 50 cc of chloroform, 0.5 cc of salicylaldehyde was added, the mixture was allowed to stand, and the titration reagent was changed to 0.1 mol / liter hydrochloric acid in 2-propanol. Then, the potentiometric titration was carried out, and the nitrogen content N ₂ , ₃ (%) of (secondary amine + tertiary amine) in the sample was first determined according to the following formula. N ₂ , ₃ = 0.014 x C x D x 100 / S C: Titration concentration of hydrochloric acid (mol / liter) D: Titration amount (cc) S: Sample amount (g) The nitrogen content N ₂ (%) of the secondary amine was determined. N ₂ = N ₂ , _3- N ₃

Nitrogen content in the primary amine: The nitrogen content N ₁ (%) of the primary amine in the sample was determined according to the following formula. N ₁ = N _T −N ₂ −N ₃

(NMR measurement) AMX600 manufactured by Bruker
Resonance frequency of ¹ H is 60
0.14MHz, resonance frequency of ¹³ C is 150.92MH
Measurements were made at z. The sample was dissolved in CDCl ₃ , and the measurement temperature was 40 ° C. Chemical shifts are a case peak of CHCl ₃ in ¹ H-NMR and 7.24 ppm, ¹³ C-
In the case of NMR, the peak of ¹³ CDCl ₃ was calculated as 77.1 ppm. Note that the R-1 peaks are mainly attributed to Macromolecules, 2
Volume 3 1318-1329 (1990).

(Measurement of Physical Properties of Molded Articles) Physical properties were measured by kneading the composition at a cylinder set temperature of 260 to 330 ° C. using a PCM-30 type twin screw extruder manufactured by Ikegai Tekko KK
Using a PS40E5ASE type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd., a molding temperature of 260 ° C to 330 ° C, a mold temperature of 70
It performed about the molded article injection-molded at -130 degreeC.

(MF of ethylene copolymer containing epoxy group
R) Measured according to JIS K6760 under a load of 2.16 kg, a temperature of 190 ° C., and g / 10 min. (Tensile strength) ASTM No. 4 tensile dumbbell is molded and
The tensile strength was measured according to TM D638.

(Bending strength, flexural modulus) Test piece (6.4
mm thickness) was measured according to ASTM D790. (Thermal deformation test (TDUL)) Test piece (6.4 mm thickness)
Was measured according to ASTM D648 with a load of 18.6 kg.

(Izod impact strength) Test piece (6.4 m
m thickness) with a notch according to JISK7110,
It was measured at room temperature.

Reference Example 1 [Modified polyphenylene ether as component (A)] 3420 g of xylene was added to a 10 liter capacity jacketed autoclave equipped with a stirrer, a thermometer, a condenser, and an air introduction tube reaching the bottom of the autoclave.
Methanol 1366 g, 2,6-dimethylphenol 1
222 g (10.02 mol) and sodium hydroxide 2
After charging 4 g to make a uniform solution, 33.8 g of diethanolamine and 27.7 g of di-n-butylamine were added to the solution.
(0.233 mol, 0.0233 mol based on 1 mol of 2,6-dimethylphenol) and 0.99 g of manganese chloride tetrahydrate were added to a solution of 100 g of methanol.

Then, while vigorously stirring the contents, air was blown into the contents at a flow rate of 5 l / min. The reaction temperature and pressure were maintained at 35 ° C. and 9 kg / cm ² , respectively. After 7 hours from the start of blowing air, the air supply was stopped and the reaction mixture was thrown into a mixture of 66 g of acetic acid and 4,900 g of methanol. The obtained slurry was filtered under reduced pressure to isolate wet polyphenylene ether. The isolated polyphenylene ether was washed with 7,200 g of methanol and then dried under reduced pressure at 150 ° C. overnight to obtain 1160 g of dried polyphenylene ether. The synthesis of polyphenylene ether was repeated 4 times by the completely same operation to obtain a total of 4640 g of dry polyphenylene ether. This polyphenylene ether had a number average molecular weight of 6000 and a number average degree of polymerization of 50. Hereinafter, the polyphenylene ether may be abbreviated as R-1. Table 1 shows the nitrogen contents of various amines of R-1. From the 2nd and 6th position of polyphenylene ether
It can be seen that 0.43% of the substituted methyl group at the position is substituted with the tertiary dibutylamino group.

100 parts by weight of polyphenylene ether R-1 and antioxidant Irganox 1330 (trade name)
After mixing 0.3 parts by weight and 0.2 parts of 2,6-di-t-butyl-4-methylphenol with a Henschel mixer,
Using a twin-screw extruder PCM-30 manufactured by Ikegai Iron Works Co., Ltd., the hopper was put into a place under a nitrogen atmosphere, the cylinder set temperature was 273 ° C., and the screw rotation speed was 80 rpm.
Then, kneading was performed while devolatilization was performed. The modified polyphenylene ether thus obtained had a number average molecular weight of 6,800 and a number average degree of polymerization of 56.7. Hereinafter, this modified polyphenylene ether may be abbreviated as A-1. A- in Table 1
1 shows the nitrogen content of various amines of 1. Compared with the raw material polyphenylene ether, the tertiary amine is greatly reduced,
It can be seen that a modified polyphenylene ether having a significantly increased primary amine was obtained.

[0045]

[Table 1]

From this, it is understood that 0.30% of the substituted methyl groups at the 2- and 6-positions of the polyphenylene ether are substituted with aminomethylene groups.

Two-dimensional HMQC N of R-1 and A-1
The MR spectra are shown in FIGS. 1 and 2, respectively. In FIG. 1, the vertical axis shows a chemical shift of ¹³ C, and the horizontal axis shows a chemical shift of ¹ H. In this spectrum, at the time of observation
^{Since 13} C is not decoupled, one signal is observed as two peaks split in the ¹ H axis direction. The ¹³ C-NMR chemical shift of the signal is given at the peak position. ¹ H-NMR chemical shifts are given at the midpoints of the two split peak positions. This is indicated by an arrow in the figure. In FIG. 2, the vertical axis shows the chemical shift of ¹³ C, and the horizontal axis shows the chemical shift of ¹ H. In this spectrum, one signal is observed as two peaks split in the ¹ H axis direction because ¹³ C is not decoupled at the time of observation. The ¹³ C-NMR chemical shift of the signal is given at the peak position. ¹ H-NMR chemical shifts are given at the midpoints of the two split peak positions.
Indicated by arrows in the figure.

The attributions of main peaks are as follows.
In the two-dimensional HMQC NMR spectrum of R-1, ¹³ C:
Signals with chemical shifts of 58.1 ppm, ¹ H: 3.62 ppm were found in the literature Macromolecule
s, 23 , 1318 (1990), a diphenylamine-bonded polyphenylene ether having a phenylene group of 2
Assigned to carbon and hydrogen of the methylene group at position 6 or 6 respectively. The intensity of this signal is significantly reduced in A-1, and ¹³ C: 36.3 ppm and ¹ H: 3.89 are newly added.
A signal with a chemical shift of ppm is observed. Reference Phytochem. , 18 , 1547 (1979)
Shows that the chemical shift of the carbon of the methylene group of the benzyl group to which the primary amine is bound is 39.4 ppm, and the literature Aldrich Library of NMR
It is known from Spectra, II , 1066 (1983) that the chemical shift of hydrogen of the methylene group of the benzyl group to which the primary amine is bound is 3.9 ppm. Therefore, ¹³ C found in A-1: 36.3 pp
m, ¹ H: A signal having a chemical shift of 3.89 ppm is assigned to carbon and hydrogen of the methylene group at the 2-position or 6-position of the phenylene group of the polyphenylene ether having a primary amine bonded thereto. This result is in agreement with the analysis result of the amino group by the above titration.

Reference Example 2 [Epoxy group-containing ethylene copolymer of component (B)] The abbreviation and composition of the epoxy group-containing ethylene copolymer produced by the high-pressure radical copolymerization method are as follows.

[Table 2] Here, E: ethylene, GMA: glycidyl methacrylate, MA: methyl acrylate, and VA: vinyl acetate are shown.

Examples 1 to 7 and Comparative Examples 1 and 2 The components shown in Table 3 were mixed together with a stabilizer in a Henschel mixer, and then kneaded and molded. Table 3 shows the physical properties of the obtained composition. From Table 3, it can be seen that the thermoplastic resin composition of the present invention is a thermoplastic resin composition having excellent heat resistance, mechanical properties, moldability and the like.

[0051]

[Table 3]

[0052]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is excellent in heat resistance, molding processability, mechanical properties, particularly impact strength, and is inexpensive, and by utilizing such characteristics, injection molding, extrusion molding, etc. Thus, it can be used for molded articles, sheets, tubes, films, fibers, laminates, coating materials and the like.

[Brief description of drawings]

FIG. 1 Two-dimensional H of polyphenylene ether (R-1)
MQC NMR spectrum.

FIG. 2 is a two-dimensional HMQC NMR spectrum diagram of modified polyphenylene ether (A-1).

Claims (1)

[Claims] (A) The following structural unit (1): (Wherein R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms),
In the polyphenylene ether having a number average degree of polymerization of 20 to 1200, when the number average degree of polymerization is X, 0.02 of the methyl group at the 2-position and / or the 6-position of the phenylene group.
/ X to 1 / X modified polyphenylene ether modified to an aminomethyl group, and (B) (a) ethylene unit of 50 to 99% by weight, (b) unsaturated carboxylic acid glycidyl ester unit or unsaturated glycidyl The epoxy group-containing ethylene copolymer comprises 0.1 to 30% by weight of ether unit and 0 to 50% by weight of (c) ethylenically unsaturated ester compound unit, and the component (A) is added to 100 parts by weight of the component ( A thermoplastic resin composition in which B) is 0.1 to 70 parts by weight.