JPH11343334A - Method for producing resin composition - Google Patents

Abstract

(57) [Problem] To provide a method for easily producing a resin composition comprising a polyester and a polyimide having a difference in melt viscosity. SOLUTION: A method for producing a resin composition, which comprises, in producing a resin composition comprising a polyimide and a polyester, performing polyester polymerization in the presence of the polyimide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a resin composition comprising a polyimide and a polyester. More specifically, the present invention relates to a method for efficiently producing a resin composition composed of both, when the difference between the melt viscosity of polyimide and the melt viscosity of polyester is so large that kneading is difficult.

[0002]

2. Description of the Related Art It has been known that polyethylene terephthalate (PET) is compatible with ULTEM, which is an amorphous poly (ether) imide, and that it is known that the glass transition temperature of PET is improved. (For example, USP4
141927, Japanese Patent Publication No. 3-58384, J. Appl. Polym. Sci.
(1993) vol.48 p.935, Polymer Bulletin (1994) vol.3
3p.113, Macromolecules (1995) vol. 1.28 2845, etc.). The same applies to polybrylene terephthalate (PBT) (for example, US Pat. No. 4,141,927). Similar reports have already been made on polyethylene naphthalate (PEN) (for example, ANTEC 1995 p.1453, POLYMER Vol.3).
6 Number23 1995 p.4449, RESEARCH DISCLOSURE 1987
p.677, JP-A-7-228761).

However, the above polyester and ULTE
M has a large difference in melt viscosity due to a considerable difference between the glass transition temperature of the polyester and the glass transition temperature of ULTEM, so that it is usually difficult to blend both. Therefore, in order to improve the mixing of both, it is necessary to increase the mixing efficiency with an extruder or the like, and also to lengthen the mixing time at a high temperature. However, such a method causes inconvenience such as thermal degradation of the polymer. was there.

On the other hand, an alicyclic aromatic polyimide comprising an alicyclic diamine and an aromatic dicarboxylic anhydride (eg, Japanese Patent Application Laid-Open No. 48-60194) has no ether bond in the molecular structure. It has a higher glass transition temperature than such amorphous polyetherimides, which makes it increasingly difficult to mix it with polyester.

In particular, when the glass transition temperature of the polyimide is higher than the molding temperature of the polyester used, kneading of the polyimide and the polyester was substantially impossible.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for producing a resin composition comprising a polyester and a polyimide.

It is another object of the present invention to provide a method for easily producing a resin composition comprising a polyester and a polyimide having a difference in melt viscosity. In particular, it is an object of the present invention to provide a method for easily producing a resin composition comprising a polyester and a polyimide, wherein the glass transition temperature of the polyimide is significantly higher than that of the polyester.

Another object of the present invention is to provide a method for efficiently obtaining a heat-resistant polyester composition and a polyimide resin composition having significantly improved moldability.

[0009]

Means for Solving the Problems The present inventors polymerize polyester by melt polycondensation in the presence of polyimide to obtain a polyester having a melt viscosity difference and a polyimide or a polyimide having a glass transition temperature of polyester. It has been found that polyimide and polyester, which are significantly higher than the temperature, can be easily mixed, and a resin composition comprising them can be obtained.

That is, the present invention provides a method for producing a resin composition comprising a polyester and a polyimide, wherein the polyester polymerization is carried out by melt polycondensation in the presence of the polyimide. It is a manufacturing method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester in the present invention means that the main acid component is an aromatic dicarboxylic acid component and / or an aliphatic dicarboxylic acid component having 6 to 15 carbon atoms, and the aromatic dicarboxylic acid is the main acid component. Are preferred.
Such aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, methyl terephthalic acid, methyl isophthalic acid, chloroterephthalic acid, Nitroterephthalic acid can be exemplified. Two or more dicarboxylic acid components can be used in combination.

The diol component constituting the polyester includes diols having 2 to 30 carbon atoms, for example, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, methylene glycol, decamethylene glycol, dodecamethylene glycol. Aliphatic glycols such as 1,4-cyclohexylene dimethanol; alicyclic glycols such as 1,4-cyclohexylene dimethanol;
And hydroquinone, methylhydroquinone, butylhydroquinone, amylhydroquinone, resorcinol,
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl)
Aromatic dihydroxy compounds such as cyclohexane [bisphenol Z] and bis (4-hydroxyphenyl ether) can be mentioned. Two or more glycol components can be used in combination.

Further, the polyester may contain a hydroxycarboxylic acid component such as oxybenzoic acid, oxynaphthoic acid, β-hydroxyethoxybenzoic acid, in addition to the dicarboxylic acid component and the diol component.

The polyester in the present invention preferably comprises the above-mentioned dicarboxylic acid component and the above-mentioned diol component. In particular, polyethylene terephthalate, polytetramethylene terephthalate and poly (1,2-ethylene-
2,6-naphthalenedicarboxylate) and the like. The polyester in the present invention may be used alone or in combination of two or more.

The polyimide in the present invention is, for example, a compound represented by the following formula (1)

[0016]

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And those comprising a repeating unit represented by the formula:

Here, R ₁ is an aromatic organic group having 3 to 30 carbon atoms or an alicyclic alkylene group in which the polyimide may contain a substituent (eg, an alkyl group or an alkoxy group) which is non-reactive with the polyester. Or an aliphatic alkylene group is preferable. These can be used in combination of two or more. Specifically, as the aromatic organic group, -O-,
-S -, - SO ₂ - carbon atoms which may have a like 6-3
A divalent a hydrocarbon group of 0, for example

[0019]

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Preferred examples include the following. Among them, the following formula (3)

[0021]

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A group derived from m-phenylenediamine represented by the following formula is particularly preferred.

Specific examples of the aliphatic and alicyclic alkylene groups include those derived from the following diamine compounds or diisocyanates to form an imide bond. For example, isophoronediamine, cyclohexanediamine, 1,8-diamino-p-menthane,
2,4- or 2,4,4-trimethylhexamethylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine , Dodecamethylenediamine, or those obtained by replacing these diamines with diisocyanates (for example, isophorone diisocyanate). In this, an alicyclic alkylene group derived from isophoronediamine, isophoronediisocyanate or 1,8-diamino-p-menthane, and a derivative derived from 2,2,4- or 2,4,4-trimethylhexamethylenediamine Aliphatic alkylene groups are more preferred.

Ar is an aromatic residue having 6 to 45 carbon atoms which may contain a substituent (eg, an alkyl group or an alkoxy group) which is not reactive with the polyester. As Ar, for example,

[0025]

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[0026]

In the above formula, R ₂ is a divalent aromatic group having 6 to 30 carbon atoms which may contain a substituent. Here, as R ₂ , for example,

[0028]

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Here, Ar is a group derived from pyromellitic anhydride and the following formula (2)

[0030]

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The group represented by the following is more preferred.

Here, R ₂ is represented by the following formula (4)

[0033]

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The group represented by the formula is particularly preferred.

Accordingly, a preferred polyimide used in the present invention is a polyimide comprising a repeating unit represented by the following formula obtained from isophoronediamine (or isophorone diisocyanate) and pyromellitic anhydride;

[0036]

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A polyimide comprising a repeating unit represented by the following formula and obtained from 2,2,4- or 2,4,4-trimethylhexamethylenediamine and pyromellitic anhydride;

[0038]

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And Ar in the above formula (1) is the following formula (2)

[0040]

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R ₁ is represented by the following formula (3)

[0042]

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R ₂ in the above formula (2) is represented by the following formula (4)

[0044]

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And the like.

Among them, the following equation (5)

[0047]

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Particularly preferred is a polyimide comprising a repeating unit represented by the following formula.
Commercially available under the trade name "TEM".

The method for producing a polyimide according to the present invention comprises:
It can be carried out using a generally known method. For example, the polyamic acid obtained first from the dicarboxylic anhydride and diamine of the above-mentioned raw materials is heated to be closed, or acetic anhydride and pyridine, carbodiimide, and chemically closed using a chemical dehydrating agent such as triphenyl phosphite. Alternatively, a dicarboxylic anhydride was converted into a partial ester or a whole ester with a lower alcohol such as methanol or ethanol in the middle, then acidified with thionyl chloride, chlorine, phosphorus pentachloride, etc., and reacted with the corresponding diamine. Thereafter, a cyclization reaction may be performed. In the case of a polyimide containing an aromatic ether, polymerization may be performed by an etherification reaction from an aromatic nitro group and a phenolic hydroxyl group.

The molecular weight of the polyimide used in the present invention is not particularly limited. When the amount of addition of the polyimide is small, it may be of a low molecular weight as long as the mechanical properties of the molded body are not impaired. . Generally, the polyimide is a phenol / tetrachloroethane mixed solvent (weight ratio).
60/40), 35 ° C, polymer fried 1.2g / d
The viscosity measured and determined in l is 0.15 or more, preferably
It is 0.25 or more. The upper limit is not particularly limited, but is practically about 5.

In the present invention, the use amount (preparation amount) of the polyimide is not particularly limited, but the ratio of the polyester to the polyimide is 95: 5 to 5:95 in terms of parts by weight based on 100 parts by weight of the whole obtained resin composition. It is preferable to make the following so that the glass transition temperature of the polyester is improved or the moldability as a polyimide is improved. When the amount of the polyimide is less than 5 parts by weight, the effect of improving the glass transition temperature of the polyester is small, and the effect of improving the heat resistance is also small. When using the method of the present invention for the purpose of improving the heat resistance of the polyester, when 10 parts by weight of the polyimide is added as 100 parts by weight of the entire resin composition, the glass transition temperature of the polyester is improved by 5 ° C. or more. Preferably, the ratio of polyester to polyimide is 95: 5 to 40:60 by weight, preferably 90:10 to 50:50.
It is.

When the amount of the polyester is less than 5 parts by weight, the effect of improving the moldability of the polyimide is not sufficient. When obtaining a resin composition having greatly improved moldability as a polyimide, the total resin composition is 100 parts by weight and the ratio of polyester to polyimide is 60:40 to 5:95, preferably 50:50 to 100 parts by weight. 5:95.

Further, the resin composition of the present invention comprising a polyimide and a polyester preferably has an intrinsic viscosity of 0.2 or more measured at 35 ° C. in a phenol / tetrachloroethane mixed solvent (weight ratio 60/40). If it is less than 0.2, the mechanical properties of the obtained resin composition will be insufficient. A more preferred range is 0.25 or more. The upper limit is not particularly limited, but is practically about 6 in consideration of moldability and the like.

The polyester polymerization in the present invention may be a generally known production method by melt polycondensation, and is not particularly limited. For example, a method of directly esterifying a dicarboxylic acid and a glycol, a method of performing a transesterification reaction of a dicarboxylic acid ester derivative and a glycol, and then performing a polycondensation, a method of polycondensing a dicarboxylic acid ester derivative composed of a dicarboxylic acid and a glycol And the like.

More specifically, each of the above-mentioned raw materials is placed in a reaction vessel, an ester exchange reaction or an esterification reaction is carried out in the presence of a catalyst, and a polycondensation is carried out in the presence of a catalyst under a high vacuum to obtain a desired product. A method for producing a polyester having an intrinsic viscosity can be used. Examples of the polycondensation catalyst include compounds such as titanium, niobium, germanium, tin, and antimony, and two or more of these can be used in combination. The above-mentioned polyester polymerization is carried out in the presence of a polyimide.

In the present invention, the term "polyester polymerization in the presence of a polyimide" means that the polyimide is added before the start of the polymerization or until the intrinsic viscosity of the polyester is 0.3 or less after the polymerization starts to polymerize the polyester. The intrinsic viscosity of the polyester referred to herein is a value of 35 in a phenol / tetrachloroethane mixed solvent (weight ratio 60/40).
Intrinsic viscosity measured in ° C. When a polyimide is added when the intrinsic viscosity of the polyester is higher than 0.3, since the viscosity of the polyester itself during polymerization is high, it is difficult to efficiently proceed with polymerization and resin composition production due to poor solubility of the polyimide. . The intrinsic viscosity of the polyester upon addition of the polyimide is more preferably 0.25 or less. More preferably, in the case of a polyester polymerization method that requires a transesterification reaction, it is preferable to add polyimide at the time of raw material charging or at the end of transesterification, and in the case of a production method that does not require a transesterification reaction, polyimide is added at the time of raw material charging. Is a preferred specific example.
That is, it is most preferable to add the polyimide at a time when the solubility of the polyimide to be added is most efficient.

Further, various additives can be further added to the resin composition of the present invention, if necessary. Such additives include glass fibers, metal fibers, aramid fibers, ceramic fibers, potassium whisker titanate, carbon fibers, fibrous reinforcing agents such as asbestos,
Various fillers such as talc, calcium carbonate, mica, clay, titanium oxide, aluminum oxide, glass flakes, milled fiber, metal flakes, metal powders, heat stabilizers represented by phosphoric acid esters and phosphites or oxidizing agents Examples include stabilizers, light stabilizers, ultraviolet absorbers, lubricants, pigments, flame retardants, flame retardant aids, plasticizers, and crystal nucleating agents.

[0058]

According to the present invention, since there is a difference in melt viscosity,
A resin composition comprising a polyester and a polyimide in which a polyester and a polyimide which are usually difficult to mix can be easily and efficiently mixed can be obtained. Further, according to the present invention, polyimide can be easily mixed with polyester. Further, the glass transition temperature of the polyester is improved from the production method of the present invention, and a resin composition as a polyester having significantly improved heat resistance can be easily and stably prepared. Can be produced to a minimum.

The resin composition obtained by the method of the present invention can be applied to various molded products such as fibers, films, beverage bottles and the like, and its industrial significance is extremely large.

[0060]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the examples, the intrinsic viscosity of the polymer was determined from the value measured at 35 ° C. using a phenol / tetrachloroethane mixed solvent (weight ratio 60/40). The differential scanning calorimeter (DSC) was used to measure the polymer at a rate of 20 ° C./min to the melting point (Tm) + 30 ° C. In order to ensure accuracy, a sample was taken out, quenched with dry ice, and then cooled again. The temperature was raised at a rate of ° C./min to determine the glass transition temperature (Tg).

Example 1 In a reactor equipped with a stirrer and a vacuum distillation system, 10.98 g (0.045 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester and 5.86 g (0.0945 mol) of ethylene glycol were added. , UL
After charging 10.89 g of TEM1000 (manufactured by General Electric Company: intrinsic viscosity 0.68) and 4.6 mg (0.0135 mmol) of tetrabutyl titanate, the ester exchange reaction was carried out at 200 ° C. for 30 minutes in a nitrogen atmosphere under normal pressure, and then 240 ℃, 15 minutes under normal pressure, 20mmH
The mixture was stirred for 15 minutes at 200 gHg, heated to 290 ° C. under 200 mmHg, 15 minutes at 200 mmHg and 15 minutes at 20 mmHg.
For 30 minutes at 0.3 mmHg.

The obtained resin composition comprising ULTEM and polyethylene naphthalate has an intrinsic viscosity of 0.72, Tg
163.2 ° C.

Claims (2)

[Claims] 1. A method for producing a resin composition, comprising: in producing a resin composition comprising a polyimide and a polyester, performing polyester polymerization by melt polycondensation in the presence of the polyimide. 2. The polyimide is represented by the following formula (1). (Where R ₁ is a divalent aromatic organic group, an aliphatic alkylene group or an alicyclic group having 3 to 30 carbon atoms which may contain a substituent which is non-reactive with the polyester and which may contain a substituent. Wherein Ar is an aromatic residue having 6 to 45 carbon atoms which may contain a substituent which is non-reactive with the polyester.) A method for producing a resin composition.