JPH0532878A - Thermoplastic resin composition having improved melt flowability - Google Patents

Abstract

PURPOSE:To improve the melt flowability of a polyphenylene ether resin by melt mixing it with a specified amt. of an additive prepd. by copolymerizing a mixture of at least two phenol derivs. CONSTITUTION:99-10wt.% at least one phenol deriv. of formula II (wherein R5 is H, 1-4C alkyl, vinyl, or phenyl; and R<6> and R<7> are each 1-4C alkyl, vinyl, or phenyl)(e.g. 2,6-dimethylphenol) and 1-90wt.% at least one phenol deriv. of formula III (wherein R<8> and R<9> are each 1-4C alkyl, vinyl, or phenyl)(e.g. 3,5- dimethylphenol) are copolymerized in the presence of a CuCl catalyst to give an additive having a number-average mol.wt. of 1,000-100,000. 5-60wt.% the additive is melt mixed with a polyphenylene ether resin of formula I (wherein R1, Rz<2> R<3>, and R<4> are each H, halogen, or a hydrocarbon group; and n is an integer) to give a polyphenylene ether resin compsn. having an improved melt flowability.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a thermoplastic resin composition,
In particular, the present invention relates to a polyphenylene ether resin composition having improved fluidity, and provides a material suitable for the automobile field, OA equipment field, etc. either alone or as a polymer blend with other resins.

[0002]

2. Description of the Related Art Polyphenylene ether has attracted attention as an extremely useful engineering plastic material because it has excellent electrical and mechanical properties, high heat distortion temperature and self-extinguishing property. However, it has low impact strength and is slightly brittle. Further, since this resin has a high melting temperature and a high melt viscosity, a high molding temperature and pressure are required for the molding process, which makes the molding process by melting difficult.

As one method for improving the molding processability of polyphenylene ether, that is, the fluidity, a method of blending another resin has been attempted. For example, Shokoku Sho 4
JP-A-3-17812 describes blending a high-impact polystyrene resin with polyphenylene ether. This composition has improved moldability and impact resistance, but with respect to moldability,
It is said that it is still insufficient.

As another method for improving the fluidity of polyphenylene ether, a method of adding a plasticizer to polyphenylene ether has been studied, for example, Japanese Patent Publication No.
No. 9-5220, an aromatic organic acid ester having good compatibility with a polyphenylene ether resin, a polyester having an aromatic group, an organic phosphoric acid ester having an aromatic group, and a chlorinated aromatic hydrocarbon are selected. It has been shown that molding processability is improved by blending these compounds with polyphenylene ether or a composition of polyphenylene ether and styrene resin.

However, when a plasticizer (for example, an organic phosphoric acid ester having an aromatic group) is blended with the polyphenylene ether or the composition of the polyphenylene ether and the styrene resin, the molding processability is improved, but the thermal processability is improved. Performance is significantly reduced. This is because the blended plasticizer is extremely uniformly dispersed (molecularly dispersed) in a matrix composed of a composition of polyphenylene ether or polyphenylene ether and a styrene resin, so that the glass transition point (Tg) of the matrix is It is considered that the heat resistance decreases as a result.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a thermoplastic resin in which melt flowability (molding processability) is greatly improved while suppressing the above-mentioned deterioration of thermal performance (heat resistance). To do.

[0007]

That is, the present invention provides the following general formula A

[Chemical 4] (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and n is an integer), and at least 1 is added to the polyphenylene ether. The following formula B of the seed

[Chemical 5] (In the formula, R ₅ is selected from a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a vinyl group and a phenyl group, and R ₆
And R ₇ are each independently selected from a lower alkyl group having 1 to 4 carbon atoms, a vinyl group and a phenol group), and at least one of the following formulas C

[Chemical 6] (Provided that R ₈ and R ₉ are independently selected from a lower alkyl group having 1 to 4 carbon atoms, a vinyl group and a phenyl group) and an additive D obtained by polymerizing a mixture with a phenol derivative. The present invention provides a thermoplastic resin composition having improved melt fluidity, which comprises a polyphenylene ether resin composition obtained by mixing The mixing ratio of the additive D to the polyphenylene ether A is D
/(A+D)=0.05-0.60 (weight ratio) is preferable. Further, it is optimal that the phenol derivative B is 2,6-dimethylphenol (2,6-xylenol) and the phenol derivative C is 3,5-dimethylphenol (3,5-xylenol).

The present invention will be described in more detail below.

The thermoplastic resin composition of the present invention with improved melt fluidity is obtained by mixing the polyphenylene ether A with the additive D which is a polymer of a mixture of the phenol derivatives B and C. The resin composition may be used alone or in combination with another resin.

The additive D of the present invention is obtained by polymerizing a mixture of at least one phenol derivative represented by the above formula B and at least one phenol derivative represented by the above formula C.

Typical examples of the phenol derivative B are 2,6-dimethylphenol, 2,6-diethylphenol, 2-methyl-6ethylphenol, 2-methyl-6-propylphenol and 2,6-diphenol. Propylphenol, 2-ethyl-6-propylphenol, 2,6
-Dibutylphenol, 2,6-dipropenylphenol, 2,6-dilaurylphenol, 2,6-diphenylphenol, 2,6-dimethoxyphenol, 2,6
-Diethoxyphenol, 2-methoxy-6-ethoxyphenol, 2,3,6-trimethylphenol, 2,
3,6-triethylphenol, 2-methyl-3,6-
Diethylphenol, 2,3-dimethyl-6-ethylphenol, 2,6-dimethyl-3-ethylphenol,
2-ethyl-3,6-dimethylphenol, 3-methyl-2,6-diethylphenol, 6-methyl-2,3-
There is diethylphenol and equivalents.

Typical examples of the phenol derivative C include 3,5-dimethylphenol, 3,5-diethylphenol, 3,5-dipropylphenol, 3,5-dibutylphenol and 3-methyl-5-ethyl. There are phenol, 3-methyl-5-propylphenol, 3-methyl-5-butylphenol, 3-ethyl-5-propylphenol, 3-ethyl-5-butylphenol, 3-propyl-5-butylphenol and the like.

In these phenol derivatives B and C,
And particularly preferable substituents are in terms of polymerization reaction rate.
R_Five A hydrogen atom and / or a methyl group as R
₆ , R ₇ , R₈ , R₉ When selecting a methyl group as
is there. That is, as the phenol derivative B, 2,6-
Dimethylphenol or 2,3,6-trimethylphenol
Enol as the phenol derivative C
The best choice is tylphenol.

The composition ratio of the phenol derivative B and the phenol derivative C constituting the above-mentioned additive D is B / (B + C) = 0.99 to 0.10 (weight ratio), preferably B / (B + C) = 0. 0.95 to 0.10 (weight ratio) More preferably, the range is B / (B + C) = 0.95 to 0.20 (weight ratio).

When the content of the phenol derivative B is higher than the above ratio, the effect of improving the molding processability is not sufficient, and when the content of the phenol derivative C is high, the heat resistance is significantly lowered. At the same time, it becomes difficult to increase the molecular weight.

Phenol derivative B and phenol derivative C
Is carried out by a so-called oxidative coupling polymerization method, and a known catalyst such as a combination of a cuprous chloride or cupric chloride ion, a halogen ion and at least one amine (US Pat. No. 3,306,874, etc.) ) Or a combination of divalent manganese, halogen ions and alkoxides or phenoxides (JP-A-63-
No. 54428 etc.) as a catalyst and nitrobenzene, benzene, toluene, tetrahydrofuran as a solvent, and the mixture is stirred while blowing an oxygen-containing gas such as pure oxygen or air into the solution to perform polymerization. it can.

The polymerization proceeds by copolymerizing the phenol derivative B and the phenol derivative C. Since the produced polymer is amorphous and is dissolved in the polymerization solvent, it can be recovered by adding the reaction product to a poor solvent such as hydrochloric acid methanol, precipitating and drying. This polymer is additive D
And usually contains 10 to 10 units based on the phenol derivative B.
99 (wt%), 1 unit based on phenol derivative C
~ 90 (wt%) contained. The number average molecular weight is in the range of about 1000 to 100,000.

Such an additive D is mixed with the polyphenylene ether resin to fulfill the function of improving the fluidity without significantly impairing the heat resistance of the resin.

The mixing ratio is D / (A + D) = 0.
05-0.60 (weight ratio) is preferable. When the content of the additive D is higher than the above ratio, the heat resistance is remarkably lowered, and when it is low, the effect of improving the fluidity is not sufficient.
A more preferable mixing ratio is D / (A + D) = 0.
It is in the range of 20 to 0.50 (weight ratio).

As a method for mixing the additive D with the polyphenylene ether A, there can be adopted a melt mixing method and a wet mixing method. In the case of melt mixing, it is easily carried out by using a device such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, a roll mill or the like, and melt-kneading at a temperature not lower than the melting temperature of the polyphenylene ether A, usually 250 to 350 ° C. be able to.

In the case of wet mixing, halogen type such as carbon tetrachloride, hydrocarbon type such as benzene, toluene, xylene and cyclohexane, oxygen type such as diethyl ether and tetrahydrofuran, triethylamine, γ-butylamine, nitrobenzene and the like are included. If necessary, the polyphenylene ether A and the additive D are uniformly dissolved in a good solvent of the polyphenylene ether A and the additive D such as a nitrogen solvent or a carbon disulfide solvent, and then the reprecipitation method and the centrifugal thin film are used. A uniform composition can be recovered by appropriately adopting a method such as a vacuum drying method, a reduced pressure drying method, or a flash drying method.

The melting temperature of the polyphenylene ether resin composition of the present invention is not particularly limited, but practically 10,
It is desirable that the temperature having 000 poise is 320 ° C. or lower. This is because a resin having such a melting temperature can be easily molded by a general-purpose injection molding machine or extruder.

In addition to the above polyphenylene ether resin composition, various additives may be added to the thermoplastic resin composition of the present invention for the purpose of imparting further performance. Such additives include various thermoplastic resins, inorganic fillers, organic fillers, rubbers and the like.

Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate and polyphenylene sulfide.
Examples of the inorganic filler include glass fiber, glass beads, talc, mica, wollastonite, and black smoke. Examples of the organic filler include aramid fiber and phenol resin beads, and the rubber component,
Examples thereof include butadiene rubber, styrene-butadiene rubber, styrene-ethylene-butylene-styrene rubber, and nitrile rubber.

The polyphenylene ether used in the present invention also includes modified products of epoxy compounds, acid anhydrides, imide compounds, olefinic compounds and the like for various purposes. Such modification is carried out, for example, by modifying the polyphenylene ether resin composition of the present invention and the olefin compound together with the radical generator when modifying with the olefin compound.

[0026]

EXAMPLES The present invention will be described in detail below with reference to examples, but these examples do not limit the scope of the present invention in any respect.

(Measurement methods for physical properties) (1) Measurement of number average molecular weight Using toluene as a solvent and UV as a detector,
GPC (Column: Toso TSK2000 + 2500 + 3
000 + 4000) in terms of polystyrene. (2) Measurement of melting temperature Elevated flow tester (CFT-5, Shimadzu Corporation)
0), the viscosity was measured at the same time as the temperature was raised, and the temperature-
A viscosity curve was obtained. The temperature at 10,000 poise was calculated from this curve and defined as the melting temperature. The lower the melting temperature,
Good fluidity.

(Example 1) 2,6-dimethylphenol (50 parts by weight) was mixed with the coal tar fraction (50 parts by weight) shown in Table 1 to obtain 15 g of a phenol derivative mixture. In a 500 ml separable flask equipped with an oxygen blowing device, thermometer and stirring device, 1 g of cuprous chloride, 70 ml of pyridine, 200 ml of nitrobenzene.
Was charged, and the mixture was stirred at 35 ° C. for 30 minutes while blowing oxygen at 300 ml / min. After that, 15 g of the above phenol derivative mixture was added to the flask, and the mixture was further reacted for 4 hours under the same oxygen blowing amount and reaction temperature.

The resulting reaction mixture was added to 500 ml of hydrochloric acid-methanol to reprecipitate the polymer. This polymer was purified by repeating the reprecipitation operation with chloroform and hydrochloric acid-acidic methanol three times. As a result, 11.4 g of a yellowish brown polymer was obtained. The number average molecular weight, melting temperature and glass transition temperature of this polymer were measured and shown in Table 2 (see Additive DI).

The additive DI (20 parts by weight) and polyphenylene ether (80 parts by weight) were melt mixed using a twin-screw extruder. The mixing temperature was 260 ° C. As a result, a light yellow uniform composition was obtained. The temperature dependence of the melt viscosity of this composition is shown in FIG. Figure 2 shows the DSC curve.
It was shown to.

Example 2 A composition was obtained by performing melt mixing in the same manner as in Example 1 except that the additive DII shown in Table 2 was used.

Example 3 The mixing ratio of the additive DI and the polyphenylene ether was as follows: (additive DI) :( polyphenylene ether) = 50:
The same procedure as in Example 1 was repeated except that the number was changed to 50.

Example 4 The mixing ratio of the additive DI and the polyphenylene ether was as follows: (additive DI) :( polyphenylene ether) = 10:
The same procedure as in Example 1 was repeated except that the ratio was changed to 90.

(Example 5) As a phenol derivative B,
Example 1 was repeated except that 2,3,6-trimethylphenol was used.

(Example 6) The additive DI (20
(Parts by weight) and polyphenylene ether (80 parts by weight) are dissolved in nitrobenzene (500 parts by weight) by heating, cooled to room temperature, and poured into a large amount of chloroform and hydrochloric acid-acidic methanol to precipitate, followed by filtration and drying. A yellow, uniform composition was obtained. Melt viscosity measurement and DSC measurement were performed on the obtained composition in the same manner as in Example 1 to obtain Example 1
There was almost no change.

Comparative Example 1 The procedure of Example 1 was repeated except that the additive DI was changed to polystyrene.

(Comparative Example 2) In Example 1, the additive D
Example 1 was repeated except that the amount of I was changed to 3 parts by weight and 65 parts by weight.

As clearly shown in FIG. 1, the melt mixture of polyphenylene ether (PPE) with polystyrene (PS) and the mixture of polyphenylene ether with the additive DI showed good flow characteristics. On the other hand, polyphenylene ether alone without addition of both did not show fluidity even when the temperature was raised, and gelation occurred at 350 ° C. Thus, it can be said that the liquidity has been greatly improved.

FIG. 1 shows a typical example of 20 parts by weight of additive to polyphenylene ether.
Similar results were obtained for Nos. 4 and 5.

FIG. 2 shows the glass transition temperature. The glass transition temperature of polyphenylene ether (PPE) alone is 221 ° C., whereas the glass transition temperature of Comparative Example 1 added with polystyrene (PS) (20%) decreases to 177 ° C. On the other hand, the additive D of Example 1
When I (20%) is added, the glass transition temperature is 202
It has dropped only to ℃. This glass transition temperature is specifically one of the evaluation criteria showing heat resistance, and the higher the glass transition temperature, the better the heat resistance. Therefore, it is clear that Example 1 is superior in heat resistance to Comparative Example 1.

On the other hand, from the examination of Comparative Example 2, when 3 parts by weight of the additive DI was added, the melt viscosity exceeded 100,000 poise, and sufficient fluidity was not exhibited. On the other hand, the addition of 65 parts by weight markedly reduced the heat resistance.

From the above, the fluidity of polyphenylene ether, which had a problem in molding fluidity, was significantly improved by adding and mixing 5 to 60 parts by weight of additive D, and at the same time, heat resistance Also in the above, it was possible to make a great improvement compared with the case of adding polystyrene which is a known method.

[0043] 1) 3,5-XL = 3,5-xylenol 2,4-XL = 2,4-cyclenol 3,4-XL = 3,4-cyclenol m-CR = m-cresol p-CR = p-cresol 2 ) Analysis results by gas chromatography

[0044]

[Table 1]

[0045]

According to the thermoplastic resin composition of the present invention, that is, the polyphenylene ether resin composition, a polyphenylene ether resin composition having improved moldability (flowability) without impairing the thermal properties is provided. can do. Therefore, it is possible to provide a useful material in a field that requires precision molding, thin-wall molding, large-scale molding, and the like.

[Brief description of drawings]

FIG. 1 is a diagram showing the temperature dependence of melt viscosity of polyphenylene ether when additive D and polystyrene are mixed.

FIG. 2 is a diagram showing the influence of additives on the DSC analysis of polyphenylene ether.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuya Takemura             1 Kawasaki-cho, Chiba-shi, Chiba Kawasaki Steel Co., Ltd.             Corporate Technology Research Division (72) Inventor Waku I Masahiro             1 Kawasaki-cho, Chiba-shi, Chiba Kawasaki Steel Co., Ltd.             Corporate Technology Research Division

Claims (5)

[Claims] 1. The following general formula A: (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and n is an integer), and at least 1 is added to the polyphenylene ether. The following formula B of the species (In the formula, R ₅ is selected from a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a vinyl group and a phenyl group, and R ₆
And R ₇ are each independently selected from a lower alkyl group having 1 to 4 carbon atoms, a vinyl group and a phenol group), and at least one of the following formulas C: (However, R ₈ and R ₉ are independently selected from a lower alkyl group having 1 to 4 carbon atoms, a vinyl group and a phenyl group), and an additive D obtained by polymerizing a mixture with a phenol derivative A thermoplastic resin composition having improved melt fluidity, which comprises a polyphenylene ether resin composition obtained by mixing. 2. The method according to claim 1, wherein the additive D is mixed with the polyphenylene ether A in a mixing ratio range of D / (A + D) = 0.05 to 0.60 (weight ratio). A thermoplastic resin composition having improved melt flowability as described. 3. The phenol derivative B is 2,6-dimethylphenol (2,6-xylenol), and the phenol derivative C is 3,5-dimethylphenol (3,5-).
Xylenol), The thermoplastic resin composition with improved melt fluidity according to claim 1 or 2. 4. The thermoplastic resin composition with improved melt flowability according to claim 1, which is obtained by melt-mixing the additive D with polyphenylene ether. 5. The thermoplastic resin composition with improved melt fluidity according to any one of claims 1 to 3, which is obtained by wet mixing the additive D with polyphenylene ether.