JP2861735B2 - Modified polyphenylene ether, method for producing the same, and thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel modified polyphenylene ether having a structural unit in which the methyl group at the 2- and / or 6-position of the phenylene group of the polyphenylene ether is substituted with an aminomethyl group, and a process for producing the same. Things. The present invention relates to a novel thermoplastic resin composition that can be used for molded articles by injection molding or extrusion molding.

[0002]

2. Description of the Related Art In general, polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability, and mechanical and electrical properties. Bad, poor chemical resistance,
It has disadvantages such as low impact resistance. Alloying of polyphenylene ether with another resin or modification of polyphenylene ether has been conventionally performed to improve such a defect of polyphenylene ether.

For example, Japanese Patent Application Laid-Open No. 52-897 discloses a method for modifying polyphenylene ether using an aliphatic secondary amine as one component of a polymerization catalyst.
JP-A-4-68024 discloses a method for producing a polyphenylene ether having a terminal secondary amination by reacting polyphenylene ether with a polyfunctional isocyanate. JP-A-1-313523 discloses a secondary or tertiary amino acid. Methods for making polyphenylene ethers having functional end groups containing groups are described. JP-A 1-2974
No. 28 describes a polyphenylene ether copolymer having a tertiary amine substituted with an alkyl group at the methylene group at the 2-position. Japanese Patent Application Laid-Open No. Hei 1-234421 discloses 2
A polyphenylene ether copolymer having a tertiary amine partially substituted with an aryl group in the side chain methylene group is described. JP-A-63-503364 discloses that
A polyphenylene ether having a polyalkylene dicarboxylate is described. 2-37
Japanese Patent Publication No. 365 exemplifies a polyphenylene ether having a primary amino group in a propylene group in a side chain.

[0004] Unlike crystalline polyesters such as polyethylene terephthalate and polybutylene terephthalate, liquid crystal polyesters do not entangle even in the molten state due to their rigid molecules, form polydomains having a crystalline state, and form molecular chains due to low shear. Shows a behavior of remarkably aligning in the flow direction, and is generally called a molten liquid crystal (thermotropic liquid crystal) polymer. Due to this unique behavior, the melt fluidity is extremely excellent, and a thin molded product of about 0.2 to 0.5 mm can be easily obtained, and this molded product has high strength and high rigidity. However, there is a disadvantage that the anisotropy is extremely large and the weld strength is extremely low.

Another problem is that liquid crystal polyesters are generally expensive. Inexpensive liquid crystal polyester resin compositions which retain the excellent heat resistance and mechanical properties of liquid crystal polyester, improve the weld strength of molded articles, and are inexpensive have been strongly demanded from the market. Japanese Patent Application Laid-Open No. 56-115357 discloses an attempt to improve the moldability and strength of a liquid crystal polyester by adding an amorphous polymer to the liquid crystal polyester. There is a description of improving the melt processability of the liquid crystal polyester by blending them. Japanese Patent Application Laid-Open No. 2-97555 discloses a liquid crystal polyester mixed with various polyarylene oxides for the purpose of improving solder heat resistance.

[0006]

However, the modified polyphenylene ether obtained by the above-mentioned production method is easily decomposed at the time of processing to cause a bad smell or a decrease in physical properties, and the modified polyphenylene ether of the functional group introduced into the molecular chain. The reactivity was insufficient or expensive. An inexpensive modified polyphenylene ether having a structural unit in which the methyl group of polyphenylene ether is substituted with a highly reactive aminomethyl group has not been obtained so far, and has been strongly desired in the market.

In general, a composition comprising a liquid crystal polyester having a high molding temperature and an amorphous polymer such as polyphenylene ether having a lower molding temperature is blended, even if the melt processability of the composition is improved. During the molding process, there was a problem that the appearance of the molded article was poor due to the thermal decomposition of the compounded resin. Further, there is a problem that the mechanical properties, heat resistance and the like of the composition are insufficient. In addition, it is an effective method to improve the compatibility of the liquid crystal polyester by blending a modified polyphenylene ether having a functional group introduced into the molecule of the polyphenylene ether, but this not only increases the cost but also increases the cost. In some cases, a monomer or oligomer containing a functional group remains in the composition, which may cause a problem in that the physical properties of the composition may be deteriorated.

There is a strong demand from the market for a thermoplastic resin composition containing a highly reactive functional group such as a primary amine in the molecule and comprising excellent properties, which is composed of inexpensive modified polyphenylene ether and liquid crystal polyester. Was about to be done.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to improve these problems, and as a result, have reached the present invention. That is, the present invention is the following invention. (I) The following structural unit (1)

[0010]

Embedded image Wherein R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.
In a polyphenylene ether having a number average degree of polymerization of 20 to 1200, when the number average degree of polymerization is represented by X, 0.02 of the methyl group at the 2-position and / or 6-position of the phenylene group is represented by X2.
A modified polyphenylene ether, wherein / X to 1 / X are substituted with an aminomethyl group.

(II) The following general formula (2)

Embedded image (Wherein R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms), and is polymerized using an oxidation coupling catalyst. In the method, the general formula (3)

Embedded image (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. Not included, and also includes those wherein Q ₁ and Q ₂ are alkylene groups which are linked to each other to form a ring.)
A method for producing a modified polyphenylene ether, wherein polymerization is carried out in the presence of from 0.1 to 0.2 mol, and the obtained polyphenylene ether is melt-kneaded.

(III) (A) The following structural unit (1)

Embedded image Wherein R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.
In a polyphenylene ether having a number average degree of polymerization of 20 to 1200, when the number average degree of polymerization is represented by X, 0.02 of the methyl group at the 2-position and / or 6-position of the phenylene group is represented by X2.
A modified polyphenylene ether having a ratio of / X to 1 / X substituted with an aminomethyl group, and (B) a liquid crystalline polyester, wherein component (A) is 1 to 75% by weight, component (B)
Is 99 to 25% by weight.

First, the modified polyphenylene ether of the present invention will be described. The present invention relates to novel modified polyphenylene ethers having 2-position and / or 6-position of the structural units substituted methyl group aminomethyl group (-CH ₂ NH ₂₎ phenylene group in the polyphenylene ether. The structural unit substituted by the aminomethyl group may be a terminal structural unit of polyphenylene ether, or may be not at the terminal but at the middle of the main chain. In particular, the structural unit substituted with the aminomethyl group is
It is preferable because it is easy to obtain a terminal structural unit of polyphenylene ether.

The modified polyphenylene ether of the present invention comprises
When the number average polymerization degree is X, 0.02 / X to 1 / X, preferably 0.05 / X to 1 / X of the methyl group at the 2-position and / or 6-position of the phenylene group is an aminomethyl group. It is characterized by being replaced. The aminomethyl group is 0.0 of the methyl group at the 2- and 6-positions of the phenylene group.
If it is less than 2 / X, when used as a component of the polymer alloy, heat resistance and mechanical properties are not sufficiently improved, which is not preferable.

As the modified polyphenylene ether of the present invention, the structural unit represented by the general formula (1) has a number average of 20 to 20.
Those having a molecular weight of 1200, more preferably 30 to 1,000 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 polymer alloy component, polyphenylene ether composed of only the structural unit represented by the general formula (1) has insufficient reactivity with other resins, but methyl at the 2-position and / or 6-position of the phenylene group in the polyphenylene ether. A modified polyphenylene ether having a structural unit in which a group is substituted with an aminomethyl group has high reactivity and is preferred as a polymer alloy component.

Next, a method for producing the modified polyphenylene ether of the present invention will be described. As a method for producing the modified polyphenylene ether of the present invention, the following general formula (2)

[0017]

Embedded image (Wherein R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms), and is polymerized using an oxidation coupling catalyst. In the method, the general formula (3)

Embedded image (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. Not included, and also includes those wherein Q ₁ and Q ₂ are alkylene groups which are linked to each other to form a ring.)
A method for producing a modified polyphenylene ether, characterized in that polymerization is carried out in the presence of 01 to 0.2 mol, and the obtained polyphenylene ether is melt-kneaded.

More specifically, in a method of polymerizing a nucleus-substituted phenol represented by the general formula (2) using an oxidative coupling catalyst, polymerization is carried out in the presence of an amine represented by the general formula (3). I do. The amines are used in an amount of 0.001 to 1 mol per nucleus-substituted phenol used.
0.2 mol, preferably 0.005 to 0.05 mol is present. If the use ratio is less than 0.001 mol per mol of the nucleus-substituted phenol, it is not preferable because a high-quality polyphenylene ether cannot be obtained. Is not preferred since Thus, a polyphenylene ether having the amines in the side chain can be obtained. Next, the nucleus-substituted phenols here are those represented by the general formula (2), and the nucleus-substituted phenols can be used alone or in combination of two or more. Preferred nuclear-substituted phenols include 2,6-dimethylphenol and 2,3,6-trimethylphenol. 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, etc.
And secondary amines such as diethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-iso-butylamine, di-n-octylamine, piperidine, and 2-pipecholine. The general formula (3)
Is also equivalent to the amine represented by the general formula (3). Examples of such polyamines include ethylenediamine, piperazine, and 1,3-dipiperidylpropane. And the like.

Specifically, it is possible to use 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. preferable. For example, JP-A-53-
No. 79993, a method of oxidatively coupling a phenolic monomer with oxygen in the presence of a catalyst comprising a manganese salt, a basic reaction medium and a secondary amine, or JP-A-63-54424. As described in
A method in which a nucleus-substituted phenol is oxidatively polymerized with an oxygen-containing gas in an organic solvent in the presence of a catalyst. As a catalyst, a manganese compound containing one or more divalent manganese salts, a metal of 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 and oxides, alkanolamines, and amines.

Thus, the following general formula (4)

Embedded image (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 Q ₁ and Q ₂ are both hydrogen. Not included, and also includes those in which Q ₁ and Q ₂ are alkylene groups which are linked to each other by forming a ring.) The methyl group at the 2- and / or 6-position of the phenylene group is converted to Can be obtained.

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

Next, the polyphenylene ether having a secondary or tertiary amine bonded to the methyl group at the 2- and / or 6-position of the phenylene group thus obtained is devolatilized.
The modified polyphenylene ether of the present invention can be obtained by melt-kneading while performing the above. It is preferable that the raw material such as polyphenylene ether is charged into a kneading apparatus under a nitrogen atmosphere. The melt kneading is performed by setting the cylinder set temperature to 200 to 300 ° C, preferably 230 to 280.
It is good to carry out at ° C. If the cylinder set temperature is less than 200 ° C., the moldability of the raw material polyphenylene ether is poor, and if the cylinder set temperature exceeds 300 ° C., decomposition and gelation of the polyphenylene ether may occur, which is not preferable . Melting extruder uniaxially or biaxially are commonly used for kneading, it is preferable to use various kneading apparatus kneaders.

At the time of melt-kneading, a radical initiator may be blended for melt-kneading. Further, a radical initiator may be previously blended with the polyphenylene ether and melt-kneaded. Preferred radical initiators include cumene hydroperoxide, t
-Butyl hydroperoxide, dimethyl-2,5-
Bis (hydroperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-
Butyl peroxide, 2,6-di-t-butyl-4methylphenol and the like.

Next, the thermoplastic resin composition of the present invention will be described. The component (A) of the thermoplastic resin composition of the present invention is the above-mentioned modified polyphenylene ether. If necessary, unmodified polyphenylene ether, styrene-grafted polyphenylene ether, polystyrene, or the like can be blended with the modified polyphenylene ether of the component (A) in the thermoplastic resin composition of the present invention.

Component (A) of the thermoplastic resin composition of the present invention
Modified polyphenylene ether and reduced viscosity η _{SP /} c (0.5 g / dl) of the raw material polyphenylene ether
Is measured at 25 ° C. for a chloroform solution of
The range of 0.30 to 0.65 dl / g is preferred. η _SP /
When c is less than 0.30 dl / g, the heat resistance of the composition is remarkably reduced, and when η _SP / c exceeds 0.65 dl / g, the moldability of the composition deteriorates, which is not preferable.

Component (B) of the thermoplastic resin composition of the present invention
Is a polyester called a thermotropic liquid crystal polymer. Specifically, (1) a material composed of a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid (2) a material composed of different aromatic hydroxycarboxylic acids (3) an aromatic dicarboxylic acid and a nucleus (4) Polyester such as polyethylene terephthalate reacted with an aromatic hydroxycarboxylic acid, and the like, which form an anisotropic melt at a temperature of 400 ° C. or lower. is there. In addition, in place of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, ester-forming derivatives thereof may be used. Examples of the repeating structural unit of the liquid crystal polyester include, but are not limited to, the following. Repeating structural unit derived from aromatic dicarboxylic acid:

[0028]

Embedded image

[0029]

Embedded image Repeating structural unit derived from aromatic diol:

[0030]

Embedded image

[0031]

Embedded image Repeating structural unit derived from aromatic hydroxycarboxylic acid:

[0032]

Embedded image A liquid crystal polyester which is particularly preferable from the balance of heat resistance, mechanical properties and processability is

[0033]

Embedded image In particular, combinations of repeating structural units include the following (I) to (IV).

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image The liquid crystal polyesters (I), (II), (III),
Regarding (IV), for example, JP-B-47-4
No. 7,870, JP-B-63-3888, JP-B-63-3891, and JP-B-56-18016.

In the present invention, the desired thermoplastic resin composition can be obtained by setting the composition ratio of the component (A) and the component (B) within a specific range. In the present invention, the ratio of component (A) to component (B) is preferably 1 to 75% by weight for component (A) and 99 to 25% by weight for component (B). When component (A) is less than 1% by weight,
The cost is less advantageous, and if it exceeds 75% by weight, the heat resistance and strength of the composition become insufficient, which is not preferable.

In the thermoplastic resin composition of the present invention,
More preferably, component (A) is a dispersed phase and component (B) is a continuous phase. This case is preferable because the composition has excellent chemical resistance, heat resistance, mechanical properties, and the like.

Although the reason why the thermoplastic resin composition of the present invention exhibits excellent physical properties is not necessarily clear, the primary amine contained in the modified polyphenylene ether has a great effect of exerting a chemical action on the liquid crystal polyester. It is considered something.

In the thermoplastic resin composition of the present invention,
If desired, an inorganic filler is used. 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 inhibitor. Various additives such as a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a mold release improving agent such as a fluororesin can be added during the manufacturing process or in the subsequent processing process.

As a method for producing the thermoplastic resin composition of the present invention, for example, a polyphenylene ether is melt-kneaded using a kneader to prepare a modified polyphenylene ether of the component (A) in advance, and the component (B) is added thereto. )
The liquid crystalline polyester is blended and kneaded to prepare the composition, or the modified polyphenylene ether of the component (A) and the liquid crystalline polyester of the component (B) obtained as described above are dissolved in a solvent. Then, the two are mixed in a solution state, and the solvent is evaporated, or the solution is poured into a solvent in which the resin component is not dissolved to precipitate the resin composition.

Further, 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 ( After producing the modified polyphenylene ether of A), the liquid crystal polyester of the component (B) and the like are charged from the second feed port of the extrusion kneader, and the modified polyphenylene ether and the liquid crystal polyester are melt-kneaded in the kneading extruder. To produce a resin composition.

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 or polyphenylene is prepared from the composition by using a solvent. It can also be confirmed by extracting and reprecipitating the ether and quantifying the amine species in the extracted component by potentiometric titration or the like.

The reason why the thermoplastic resin composition of the present invention exhibits excellent physical properties is not necessarily clear, but can be considered as follows.

That is, since the polyphenylene ether comprising only the structural unit (1) does not contain a reactive functional group, the reactivity with the liquid crystal polyester is insufficient. Therefore, the composition comprising the polyphenylene ether and the liquid crystal polyester is excellent. Does not show physical properties. On the other hand, the modified polyphenylene ether substituted with an aminomethyl group contains a highly reactive primary amine, so that a reaction occurs between the modified polyphenylene ether and the liquid crystal polyester, and as a result, the composition exhibits excellent physical properties. it is conceivable that.

[0049]

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 number average molecular weight, amine quantification, and NMR measurement were measured by the following methods. (Number average molecular weight) It was determined by gel permeation chromatography (hereinafter sometimes referred to as GPC method) according to a conventional method.

(Quantitative Determination of Amine in Raw Polyphenylene Ether and Modified Polyphenylene Ether) Nitrogen content in all amines: About 1 g of sample was weighed, dissolved in 50 cc of chloroform, and 5 cc of acetic acid was added.
Potentiometric titration was performed using a potentiometric titrator AT-310 (Kyoto Electronics Co., Ltd., glass-calomel electrode, titrant 0.1 mol perchloric acid, (acetic acid solution)), 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 (cc) S: Sample amount (g) C ₁ : Concentration of perchloric acid solution ( Mol / l)

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

Nitrogen content in secondary amine: about 1 g of sample
Was weighed, dissolved in 50 cc of chloroform, 0.5 cc of salicylaldehyde was added, and after standing, the titration reagent was changed to a 0.1 mol / l hydrochloric acid 2-propanol solution. , And the nitrogen content N ₂ , ₃ (%) of (secondary amine + tertiary amine) in the sample was determined according to the following equation. N ₂ , ₃ = 0.014 × C × D × 100 / SC: concentration of titrated hydrochloric acid (mol / liter) D: titration (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 primary amine: The nitrogen content N ₁ (%) of the primary amine in the sample was determined according to the following equation. _{N 1 = N T -N 2 -N} 3

(NMR measurement) AMX600 manufactured by Bruker
Using a mold spectrometer, the resonance frequency of the ¹ H 60
0.14 MHz, ¹³ C resonance frequency is 150.92 MH
Measurements were made at z. The sample was dissolved in CDCl ₃ and the measurement temperature was 40 ° C. In the case of ¹ H-NMR, the chemical shift is set such that the peak of CHCl ₃ is 7.24 ppm, and ¹³ C-
In the case of NMR, the calculation was performed with the peak of ¹³ CDCl ₃ being 77.1 ppm. The assignment of the peak of R-1 is mainly based on Macromolecules, Macromolecules,
3, pages 1318 to 1329 (1990).

(Method of measuring physical properties of molded article) The physical properties were measured by kneading the composition at a cylinder set temperature of 300 to 340 ° C using a PCM-30 type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd.
Using a PS40E5ASE type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd., a molding temperature of 300 to 340 ° C. and a mold temperature of 11
The test was performed on a molded product injection-molded at 0 to 130 ° C.

(Tensile strength, deflection temperature under load (TDU)
L)) ASTM No. 4 tensile dumbbell and TDUL measurement test piece (127 mm length × 12.7 mm width × 6.4 mm thickness) were formed, and ASTM D638 and ASTM D6, respectively.
Tensile strength according to No.48, TDUL (load 18.6kg)
Was measured.

(Flexural Strength) A test piece (6.4 mm thick) was measured according to ASTM D790.

(Weld strength, non-weld strength) Test pieces shown in FIG. 1 were molded from the composition of the present invention. This test piece had a thickness of 3 mm, an outer dimension of 64 mm, and an inner dimension of 38 mm. From this, a hatched portion (64 × 13 mm) including the weld line shown in FIG. 1 is cut out, and the distance between the spans is 40 m.
m, and the bending strength was measured at a bending strength of 2 mm / min. Also,
Non-weld part (64 × 13mm) from test piece of same shape
Was cut out, and the bending strength was measured in the same manner.

(Appearance of Injection Molded Article) The appearance of the injection molded article was evaluated according to the following criteria. ：: The appearance is beautiful, and no change in color tone is observed. ×: A change in color tone or the like is observed on the surface of the molded product.

(Observation of Form of Molded Product) The injection molded product is cut with a microtome and etched with carbon tetrachloride. It was observed using a scanning electron microscope and classified as follows. A: The polyphenylene ether portion (modified PPE and unmodified PPE) is a dispersed phase, and the liquid crystal polyester portion is a continuous phase. B: The polyphenylene ether portion is a continuous phase, and the liquid crystal polyester portion is a dispersed phase.

Reference Example 1 3420 g of xylene was placed in a 10-liter jacketed autoclave equipped with a stirrer, a thermometer, a condenser, and an air inlet tube reaching the bottom of the autoclave.
1366 g of methanol, 2,6-dimethylphenol 1
222 g (10.02 mol) and sodium hydroxide 2
After charging 4 g to make a uniform solution, the solution was diluted with 33.8 g of diethanolamine and 27.7 g of di-n-butylamine.
(0.233 mol, 0.0233 mol per 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 the contents were vigorously stirred, 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 a lapse of 7 hours from the start of air blowing, the supply of air was stopped, and the reaction mixture was poured into a mixture of 66 g of acetic acid and 4,900 g of methanol. The resulting slurry was filtered under reduced pressure to isolate wet polyphenylene ether. After washing the isolated polyphenylene ether with 7,200 g of methanol, it was dried under reduced pressure at 150 ° C. overnight to obtain 1160 g of dry polyphenylene ether. The number average molecular weight of this polyphenylene ether is 6
000, and the number average degree of polymerization was 50. Hereinafter, the present polyphenylene ether may be abbreviated as R-1. Table 1 shows the nitrogen content of various amines of R-1. This indicates that 0.43% of the substituted methyl groups at the 2- and 6-positions of the polyphenylene ether are substituted with tertiary dibutylamino groups.

Example 1 100 parts by weight of polyphenylene ether R-1 and a radical initiator Samperox T0 (trade name, Sanken Kako Co., Ltd.)
0.2 parts by weight, antioxidant Irganox 1330
(Trade name) 0.3 parts by weight, 2,6-di-t-butyl-4
After mixing 0.2 parts by weight of methylphenol with a Henschel mixer, using a twin screw extruder PCM-30 manufactured by Ikegai Iron Works Co., Ltd., the hopper was put under a nitrogen atmosphere, and the cylinder temperature was 273 ° C. and the screw was Rotation speed 80r
At pm, kneading was performed while devolatilizing. The obtained pellet was dissolved in chloroform, then reprecipitated in methanol and dried. The number average molecular weight of this modified polyphenylene ether was 6,800, and the number average degree of polymerization was 56.7. Hereinafter, the present modified polyphenylene ether may be abbreviated as A-1. Table 1 shows the nitrogen content of various amines of A-1. Compared with the raw material polyphenylene ether, it can be seen that the modified polyphenylene ether in which the tertiary amine was significantly reduced and the primary amine was significantly increased was obtained.

[0064]

[Table 1]

From this, it can be seen that 0.30% of the substituted methyl groups at the 2- and 6-positions of the polyphenylene ether were substituted with aminomethylene groups. R-1 and A-
Thermogravimetric analysis was performed to compare the thermal stability of 1. The thermogravimetric analysis was performed using TGA-50 manufactured by Shimadzu Corporation.
And at a heating rate of 10 ° C./min. Note that R
In order to eliminate the difference in surface area between A-1 and A-1, A-1 was finely crushed (42 mesh) until the particle size dependence of the sample was not recognized in the weight-temperature curve. FIG. 2 shows the results of thermogravimetric analysis measured in a nitrogen atmosphere. FIG. 2A shows the measurement result for R-1, and FIG. 2B shows the measurement result for A-1. Note that the main decomposition temperature in the figure was determined at the intersection of the baseline and the tangent at the most inclined point of the baseline shift, and the decomposition start temperature was the temperature at which the weight decreased by 2%. FIG. 2 shows the decomposition starting temperature and the main decomposition temperature. As can be seen from FIG. 2, the weight loss of R-1 began to occur at about 350 ° C., and the decomposition onset temperature was as low as 405 ° C., whereas A-1 showed almost no weight loss up to 400 ° C. Was 438 ° C., which was 30 ° C. or more higher than that of R-1. Also, looking at the main decomposition temperature, R-1 was 435 ° C, whereas A-1 was as high as 450 ° C, indicating that the modified polyphenylene ether of the present invention had improved thermal stability. .

Two-dimensional HMQC N of R-1 and A-1
The MR spectra are shown in FIGS. 3 and 4, respectively. In FIG. 3, the vertical axis indicates the chemical shift of ¹³ C, and the horizontal axis indicates the chemical shift of ¹ H. In this spectrum,
^{Since 13} C is not decoupled, one signal is observed as two peaks split along the ¹ H axis. The ¹³ C-NMR chemical shift of the signal is given at the peak position. ^{The 1} H-NMR chemical shift is given at the midpoint of the two split peak positions. In the figure, it is indicated by an arrow. In FIG. 4, the vertical axis indicates the chemical shift of ¹³ C, and the horizontal axis indicates 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. ^{The 1} H-NMR chemical shift is given at the midpoint of the two split peak positions.
This is indicated by an arrow in the figure.

The assignment of the main peaks is as follows.
In the two-dimensional HMQC NMR spectrum of R-1, ¹³ C:
A signal having a chemical shift of 58.1 ppm, ¹ H: 3.62 ppm is described in Macromolecule in the literature.
s, 23 , 1318 (1990), the phenylene group 2 of the diphenylamine-bonded polyphenylene ether.
Attributable to carbon and hydrogen of the methylene group at the 6th or 6th position. The intensity of this signal was greatly reduced in A-1, and new ¹³ C: 36.3 ppm and ¹ H: 3.89.
A signal with a chemical shift of ppm is observed. Literature 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 bonded is 39.4 ppm, and that the literature Aldrich Library of NMR
According to Spectra, II , 1066 (1983), it is known that the chemical shift of hydrogen of the methylene group of the benzyl group to which the primary amine is bonded 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- or 6-position of the phenylene group of the polyphenylene ether to which the primary amine is bonded. This result is consistent with the result of analysis of the amino group by the previous titration.

Reference Example 2 10.8 kg (60 mol) of p-acetoxybenzoic acid, 2.49 kg (15 mol) of terephthalic acid, 0.83 kg (5 mol) of isophthalic acid and 5.45 kg of 4,4'-diacetoxydiphenyl (20.2 mol) was charged into a polymerization tank having a comb-shaped stirring blade, and the temperature was increased while stirring under a nitrogen gas atmosphere, and polymerization was performed at 330 ° C. for 1 hour. During this time, the polymerization was carried out under vigorous stirring while removing acetic acid produced as a by-product. Thereafter, the system was gradually cooled, and the reaction mixture was taken out of the system at 200 ° C. This reaction mixture was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less.
This is further reduced in a rotary kiln under a nitrogen gas atmosphere for 2 hours.
By treating at 80 ° C. for 3 hours, the flow temperature becomes 32
A wholly aromatic polyester comprising the following repeating structural units in the form of particles at 4 ° C. was obtained. Hereinafter, the liquid crystal polyester is referred to as B-
Abbreviated as 1. This polymer showed optical anisotropy at 340 ° C. or more under pressure. The repeating structural units of the liquid crystal polyester B-1 are as follows.

[0069]

Embedded image

Examples 2 and 3 and Comparative Examples 1 and 2 The components shown in Table 2 were blended together with a stabilizer and kneaded to measure various physical properties. Table 2 shows the obtained results.

Examples 4 and 5, Comparative Examples 3 and 4 The components shown in Table 3 were blended together with a stabilizer, kneaded, and various physical properties were measured. Table 3 shows the obtained results.

[0072]

[Table 2]

[0073]

[Table 3] Refluxing the composition of Example 2 in chloroform for 72 hours;
Modified PPE which is dissolved in chloroform (hereinafter referred to as the modified PP
E may be abbreviated as A-2). Further, the same treatment was performed on the composition of Comparative Example 1, and the amount of amine species in the PPE (hereinafter, the PPE was sometimes abbreviated as R-2) was determined. Table 4 shows the results of these amine species determinations.

[0074]

[Table 4] It can be seen that the thermoplastic resin composition of the present invention is an inexpensive resin composition having excellent properties such as heat resistance and mechanical properties, excellent melt processability, good molded appearance, and low cost.

[0075]

The modified polyphenylene ether of the present invention contains a highly reactive primary amine in the side chain of the polymer.
It can be widely and preferably used as a component of various compositions or as a polymer alloy, and is inexpensive. The thermoplastic resin composition of the present invention is a resin composition having excellent heat resistance, mechanical properties, appearance and gloss, and molded articles, sheets, tubes and films by injection molding or extrusion utilizing such properties. , Fibers, laminates, coating materials and the like.

[Brief description of the drawings]

FIG. 1 is a plan view of a test piece for measuring weld strength.

FIG. 2 is a graph showing a change in weight of a polyphenylene ether by heating in a nitrogen atmosphere.

FIG. 3 shows two-dimensional H of polyphenylene ether (R-1)
MQC NMR spectrum diagram.

FIG. 4 is a two-dimensional HMQC NMR spectrum of the modified polyphenylene ether (A-1).

[Explanation of symbols]

 1. Weld line 2. 2. Cut-out part including weld line (hatched part) Gate

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-297428 (JP, A) JP-A-2-218739 (JP, A) JP-A-3-95261 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C08G 65/34-65/48 C08L 71/08-71/12 C08L 67/00-67/08

Claims (6)

(57) [Claims] 1. 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 a polyphenylene ether having a number average degree of polymerization of 20 to 1200, when the number average degree of polymerization is represented by X, 0.02 of the methyl group at the 2-position and / or 6-position of the phenylene group is represented by X2.
/ X~1 / X is modified polyphenylene ether, wherein the substituted amino methyl group (-CH ₂ NH _2). 2. The following general formula (2) (Wherein R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms), and is polymerized using an oxidation coupling catalyst. In the method, the general formula (3) (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. Not included, and also includes those wherein Q ₁ and Q ₂ are alkylene groups which are linked to each other to form a ring.)
The method for producing a modified polyphenylene ether according to claim 1, wherein the polymerization is carried out in the presence of 01 to 0.2 mol, and the obtained polyphenylene ether is melt-kneaded while devolatilizing. 3. The following general formula (2) (Wherein R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms), and is polymerized using an oxidation coupling catalyst. In the method, the general formula (3) (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. Not included, and also includes those wherein Q ₁ and Q ₂ are alkylene groups which are linked to each other to form a ring.)
The polymerization is carried out in the presence of from 0.1 to 0.2 mol, and the obtained polyphenylene ether is melt-kneaded while being charged into a kneading apparatus under a nitrogen atmosphere and devolatilized, and the modified polyphenylene ether according to claim 1, Production method. 4. The method according to claim 2, wherein a radical initiator is blended and melt-kneaded during the melt-kneading. (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 a polyphenylene ether having a number average degree of polymerization of 20 to 1200, when the number average degree of polymerization is represented by X, 0.02 of the methyl group at the 2-position and / or 6-position of the phenylene group is represented by X2.
/ X~1 / X ratio aminomethyl group (-CH ₂ NH ₂₎
And (B) a liquid crystalline polyester, wherein component (A) is 1 to 7
A thermoplastic resin composition comprising 5% by weight and 99 to 25% by weight of the component (B). 6. The liquid crystal polyester (B), The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin composition contains a repeating structural unit represented by the following formula: