JPH06184306A - Aromatic copolyeterimide - Google Patents

Abstract

PURPOSE:To obtain an arom. copolyesterimide which is melt-moldable at a relatively low temp. and gives a molded article excellent in heat resistance. CONSTITUTION:This arom. copolyesterimide comprises repeating units of formulae I, II, III, IV, V, and VI (wherein Ar in formula V is a divalent arom, group; and the hydroxyl group derived from aminophenol in formula VI is at the p- or m-position to the imide group) in such molar amts. that the molar ratio of formula I (formulae I+II+III+IV+V+VI) is 0-0.85, that of formula IV /(formulae II+III+IV) is 0.05-1, that of formula VI/(formulae I+VI) is 0-0.2, and that of (formulae II+III+IV)/formula V is practically 1. The copolyesterimide is meltable at a relatively low temp., e.g. 400 deg.C, and can be molded into a bulk molding, film, fiber, etc., by a usual molding method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel copolyesterimide which can be melt-molded at a relatively low temperature.

[0002]

2. Description of the Related Art In recent years, various engineering plastics have been developed. In particular, a thermotropic liquid crystal polymer, which exhibits optical anisotropy when melted, has a highly molecularly oriented structure, has improved mechanical properties, and is excellent in molding processability, is drawing attention.

As these liquid crystal polymers, polyester obtained from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, polyester obtained from 4,4'-dihydroxybiphenyl, terephthalic acid and p-hydroxybenzoic acid, polyethylene Polyester obtained from terephthalate and p-hydroxybenzoic acid are known.

Liquid crystal polyesterimides having an imide group in the polymer chain are also known. For example, Macrom
olecules, 21 , 1929 (1988), N, N'-bis (ω-carboxyalkyl) benzophenone-3,3 ', 4,4'-tetracarboxylic acid diimide, hydroquinone, biphenol,
Homopolymers with various diols such as 2,6-naphthalene diol have been described. Also, Makromol. Chem., 1
84 , 1223 (1983) describes a self-condensation product of trimellitic anhydride and an imidized product of p-aminophenol. Also, J. Polym. Sci .: Part A: Polymer Chemistr
y, 27 , 431 (1989) includes N- (ω-carboxyalkylene)
-Trimellitimide and biphenol or N- (ω-
Copolyesterimides consisting of carboxyalkylene) -trimelliticimide, hydroquinone and p-hydroxybenzoic acid are described. However, these copolyesterimides have insufficient heat resistance.

Eur. Polym. J., 28 , 261 (1992), N-
Copolymers of (4-carboxyphenyl) -trimellitic imide with various diols such as biphenol, 2,6-naphthalene diol, 4,4'-dihydroxybiphenyl ether are described. However, this copolyesterimide has a high melting point, making it virtually impossible to melt process it without degrading the polymer.

[0006]

An object of the present invention is to provide a novel copolyesterimide which can be melt-molded at a temperature of 400 ° C. or lower and can give a molded product having excellent heat resistance.

[0007]

The present invention comprises repeating units A, B, C, D, E and F of the following formula:

[Chemical 2] (However, Ar in the structural unit E represents a divalent aromatic group, and the hydroxyl group derived from the aminophenol in the structural unit F exists in the para position or the meta position with respect to the imide group.) A / The molar ratio of [A + B + C + D + E + F] is greater than 0 and 85/100 or less, the molar ratio of D / [B + C + D] is 5/100 or more and less than 1, and the molar ratio of F / [A + F] is greater than 0 and 20/1.
Less than 00, and [B + C + D] and E are substantially equimolar with respect to the aromatic copolyesterimide.

The repeating unit A forming the aromatic copolyesterimide of the present invention is derived from p-hydroxybenzoic acid, its carboxylic acid ester, carboxylic acid halide, p-acetoxybenzoic acid and the like. .

Repeating unit B is 3,3'-dimethylbiphenyl
-4,4'-dicarboxylic acid, its dicarboxylic acid ester, dicarboxylic acid halide and the like.

Repeating unit C is 3,4'-dimethylbiphenyl
-4,3'-dicarboxylic acid, its dicarboxylic acid ester, dicarboxylic acid halide and the like.
The above 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid and 3,4′-dimethylbiphenyl-4,3′-dicarboxylic acid can be synthesized, for example, by an oxidative coupling reaction of alkyl orthotoluate. Available (Japanese Patent Application Sho 63-267202)
And Japanese Patent Application No. 1-211334).

The repeating unit D is derived from terephthalic acid, its dicarboxylic acid ester, dicarboxylic acid halide or the like.

The repeating unit E is 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, hydroquinone, resorcin, 1,5-dihydroxynaphthalene,
2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone and their diacetoxy compounds, etc. It was derived from. Among them, 4,4'-dihydroxybiphenyl, 4,4'-diacetoxybiphenyl, 4,4'-
Those derived from dihydroxybiphenyl ether, 4,4'-diacetoxy biphenyl ether and the like are preferable.

Repeating unit F is N- (4-hydroxyphenyl) -trimelliticimide, N- (4-acetoxyphenyl)-
It is derived from trimellitimide, N- (3-hydroxyphenyl) -trimellitimide, N- (3-acetoxyphenyl) -trimellitimide and the like.

The method for producing the above imides is not particularly limited, but for example, N- (4-acetoxyphenyl) -trimellitic imide can be produced by the following method.

Trimellitic anhydride and p-aminophenol are heated to 100 to 200 ° C. in a solvent such as N-methylpyrrolidone, dimethylformamide or dimethylacetamide, and the produced water is azeotropically distilled with toluene. It can be obtained by reacting for 1 to 7 hours while removing it to the outside, separating the produced N- (4-hydroxyphenyl) -trimeritimide, washing and drying. This imide can be converted to the corresponding acetoxy form by acetylation with acetic anhydride.

In the aromatic copolyesterimide of the present invention, the molar ratio of A / [A + B + C + D + E + F] is 0
Greater than 85/100. If this ratio exceeds 85/100, the melting temperature of the aromatic copolyesterimide will increase,
Molding is difficult.

The molar ratio D / [B + C + D] is 5/100 or more and less than 1, preferably 10/100 or more and less than 1.
If this molar ratio is less than 5/100, the melting point and heat resistance tend to decrease.

The molar ratio of F / [A + F] is larger than 0.
It is less than 20/100, preferably more than 0 and less than 15/100. If this molar ratio is greater than 20/100, the melt viscosity will increase, causing a problem in moldability. [B + C + D] and E
And are substantially equimolar.

In addition to the repeating units A, B, C, D and E described above, A, B, C, D and E are formed by repeating units derived from small amounts of monomers which can form other ester bonds.
May be replaced.

Specific examples of the repeating unit capable of forming other ester bond include isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′- Diphenyl dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl ketone-
4,4'-dicarboxylic acid, dicarboxy unit such as derived from 2,2-diphenylpropane-4,4'-dicarboxylic acid, and m-hydroxybenzoic acid, 4-hydroxy-4'-carboxydiphenyl ether, Examples thereof include oxycarboxy units derived from 1-hydroxy-4-naphthoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxybiphenyl-4′-carboxylic acid and the like.

The substitution ratio of these substituted repeating units is 1 relative to the repeating units [A + B + C + D + E + F] in order to make the melting point of the aromatic copolyesterimide relatively low.
It is preferably 0 mol% or less. Substitution rate is 10 mol%
If it exceeds, the melting temperature of the aromatic copolyesterimide is generally high, depending on the type of the repeating repeating unit, and the molding process is difficult, and the melting temperature is maintained at a relatively low temperature, but the liquid crystallinity is deteriorated. Therefore, there arises a defect such as an increase in melt viscosity.

The method for producing the aromatic copolyesterimide of the present invention is not particularly limited, and it can be produced by a known ester polycondensation reaction. Specific examples of the production method include (1) dicarboxylic acid dichloride and diol
Polycondensation in the presence of a primary amine, (2) polycondensation of diphenyl ester of dicarboxylic acid and diol by dephenol method, (3) polycondensation of diacetyl derivative of dicarboxylic acid and diol by deacetic acid method There is a method. A particularly preferred method is a deacetic acid polymerization method.

In the case of the deacetic acid polymerization method, the reaction may be started after all the comonomer components are added to the reaction tank, or the comonomer may be added stepwise.

In this polycondensation reaction, a method of acetylating and / or precondensing the monomers of the components A, E and F and then adding the dicarboxylic acid component to carry out polycondensation produces a homogeneous polymer. be able to. In this method, polycondensation is performed at 230 to 350 ° C., the temperature is raised stepwise to remove acetic acid, and then the pressure is reduced (about 0.1 Torr) to complete the reaction. The reaction time is preferably 1 to 10 hours.

The polycondensation reaction can be carried out in the presence or absence of a catalyst. Specific examples of the catalyst include stannous acetate, ferrous acetate, sodium acetate, antimony trioxide, magnesium, acetylacetone iron (III), titanium tetrabutoxide, sodium hypophosphite, potassium phosphate and other metals or metals. Compounds may be included, but are not limited to. The addition amount is 0.001 to 0.5% based on the weight of the produced polymer. The time of addition may be at the start of precondensation or at the start of polycondensation reaction.

The polycondensation reaction is carried out in the presence of a stabilizer for the purpose of preventing coloration due to heat deterioration during polymerization and improving the thermal stability of the polymer produced, in the range that does not significantly affect the physical properties of the polymer obtained. You can Specific examples of the stabilizer include phosphorous compounds such as phosphoric acid, phosphorous acid, sodium hypophosphite, triphenyl phosphate, triphenyl phosphite, and hindered phenols. It is not limited. The addition amount is 0.001 to 0.5% based on the weight of the produced polymer. The time of addition may be at the start of precondensation or at the start of polycondensation reaction.

The aromatic copolyesterimide of the present invention is
It has a logarithmic viscosity (η _inh ) of 1.0 or more at a concentration of 0.2 g / dl in pentafluorophenol at 60 ° C, and exhibits optical anisotropy (liquid crystallinity) in a molten state under a polarizing microscope observation.

[0028]

Industrial Applicability The aromatic copolyesterimide of the present invention forms a molten state at a relatively low temperature, for example, a temperature of 400 ° C. or lower, and by various commonly known molding methods,
It can be a bulk molding, a film, a fiber or the like. Further, since it dissolves in an organic polar solvent such as pentafluorophenol or p-chlorophenol, it is possible to obtain a molded product by a dissolution processing method. These molded products can be widely used for electric, electronic and automobile materials.
As a remarkable property, since it has liquid crystallinity in a molten state, it is possible to obtain a molded product having a highly molecular orientation. Therefore, a polymer material having excellent mechanical strength can be manufactured.

[0029]

EXAMPLES Examples of the present invention will be described below. (Measurement method) Each physical property value shown in the examples of the present invention was measured by the following methods. (1) Optical anisotropy: The sample was placed on a polarizing microscope, and using a TH600RMS type heating device manufactured by Rincom Co., the temperature was raised at 10 ° C./min under a nitrogen stream to be visually observed (liquid crystal starting temperature). (2) Thermal decomposition start temperature; SSC / 5200 T manufactured by Seiko Denshi Kogyo Co., Ltd.
Using a GA device, the temperature of the sample was raised in nitrogen at 20 ° C / min and the change in weight with time was observed. (3) Melting point: Using an SSC / 5200 DSC apparatus manufactured by Seiko Denshi Kogyo Co., Ltd., the sample was heated in nitrogen at 10 ° C./min, and an endothermic peak was observed. (4) Logarithmic viscosity; in pentafluorophenol at 60 ℃,
The sample was dissolved at a concentration of 0.2 g / dl and measured using an Ubbelohde viscometer. η _inh was calculated according to the following equation. η _inh = ln (t / t ₀ ) / c where t ₀ is the drop time of pentafluorophenol, t is the drop time of the sample solution, and c is the sample concentration.

Synthesis Example 1 Synthesis of N- (4-hydroxyphenyl) -trimellitic imide (4-PTMI) 19.64 g (0.18 mol) of p-aminophenol was added to a 500 ml flask equipped with a stirrer and a fractionating tube. After vacuum degassing and nitrogen replacement, 200 ml of N-methylpyrrolidone was added to make a uniform solution at 50 ° C., and 34.58 g of trimellitic anhydride (0.1
8 mol) was added. After heating at 110 ° C for 20 minutes, toluene
50 ml was added, and the mixture was heated at 160 ° C. for 4 hours while distilling off the produced water. After completion of the reaction, it was cooled, the reaction solution was poured into water, filtered and washed with methanol, and 48.83 g (95.8% yield) of N- (4-
Hydroxyphenyl) -trimellitic imide was obtained.

Synthesis Example 2 Synthesis of N- (4-acetoxyphenyl) -trimelliticimide (4-PTMI-Ac) N- (4-
Hydroxyphenyl) -trimellitic imide 48.83 g (0.172
mol), vacuum degassing and nitrogen substitution, then adding pyridine 300
ml was added, and a uniform solution was prepared at 50 ° C. After adding 35.2 g of acetic anhydride, the mixture was refluxed at 140 ° C. for 14 hours. After the reaction was completed, it was cooled with ice, filtered and dried to obtain 46.88 g (83.8% yield) of N-.
(4-acetoxyphenyl) -trimeritimide was obtained.
The elemental analysis and CI-MS spectrum of this compound are as follows. (Elemental analysis) (Theoretical value) C: 62.77, H: 3.38, N: 4.31 (Actual value) C: 63.1, H: 3.4, N: 4.4 (CI-MS spectrum) M / Z 326 (M + 1)

Synthesis Example 3 Synthesis of N- (3-hydroxyphenyl) -trimeritimide (3-PTMI) 27.29 g (0.25 mol) of m-aminophenol was added to a 500 ml flask equipped with a stirrer and a fractionating tube. After vacuum degassing and nitrogen replacement, 200 ml of N-methylpyrrolidone was added and made into a uniform solution at 50 ° C., then 48.03 g of trimellitic anhydride (0.2
5 mol) was added. After heating at 110 ℃ for 30 minutes, toluene
50 ml was added, and the mixture was heated at 160 ° C. for 4 hours while distilling off the produced water. After completion of the reaction, the reaction solution was cooled, poured into water, filtered and washed with methanol, and 68.57 g (96.8% yield) of N- (3-
Hydroxyphenyl) -trimellitic imide was obtained.

Synthesis Example 4 Synthesis of N- (3-acetoxyphenyl) -trimellitic imide (3-PTMI-Ac) N- (3− in a 500 ml flask equipped with a stirrer and cooling tube.
Hydroxyphenyl) -trimellitimide 68.57g (0.24m
ol), vacuum degassing and nitrogen substitution were performed, and then pyridine 400
ml was added to make a uniform solution at 80 ° C. Acetic anhydride 49.41g
After adding dropwise, the mixture was refluxed at 140 ° C. for 7 hours. After the reaction was completed, it was cooled with ice, filtered and dried to obtain 57.33 g (72.8% yield) of N-.
(3-acetoxyphenyl) -trimeritimide was obtained.
The elemental analysis and CI-MS spectrum of this compound are as follows. (Elemental analysis) (Theoretical value) C: 62.77, H: 3.38, N: 4.31 (Actual value) C: 63.0, H: 3.3, N: 4.4 (CI-MS spectrum) M / Z 326 (M + 1)

Example 1 An upper part of a glass separable three-necked flask was used in a stainless steel container (100 ml), and a stirrer, a nitrogen introducing tube and a Claisen were attached. In this container, 4,4'-diacetoxybiphenyl (BP-Ac) 8.27 g (30.60 mmol), N- (4-acetoxyphenyl) -trimeritimide (4-PTMI-Ac) 0.97
g (3 mmol), p-acetoxybenzoic acid (PHBA-Ac) 15.67 g (87 mm)
ol) and 30 mg of triphenyl phosphate were charged. After degassing in vacuum and repeating nitrogen replacement three times, the mixture was heated in a metal bath containing tin at 250 ° C. for 5 minutes, allowed to cool, decompressed, and then returned to normal pressure with nitrogen.

To this precondensation mixture, 1.43 g (5.25 mmol) of 3,3'-dimethylbiphenyl-4,4'-dicarboxylic acid (PA), 3,
4'-Dimethylbiphenyl-4,3'-dicarboxylic acid (QA) 1.41g
(5.25 mmol) and 3.23 g (19.5 mmol) of terephthalic acid (TPA) were added. The mixture was degassed in vacuum and replaced with nitrogen three times, and then heated in a tin bath at 260 ° C. for 1 hour. The temperature was raised to 320 ° C. over 1 hour and the temperature was maintained at 320 ° C. for 1 hour, and the acetic acid produced was distilled off together with flowing nitrogen. The degree of vacuum was gradually increased while maintaining the temperature at 320 ° C. After the degree of reduced pressure reached 0.3 Torr or less, the reaction was continued for another 55 minutes.

After completion of the reaction, the temperature was returned to room temperature and atmospheric pressure while introducing nitrogen. The obtained polymer was crushed and taken out of the container. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy occurs (liquid crystal onset temperature), and thermal decomposition onset temperature of the obtained polymer.

Example 2 In the same container as in Example 1, 4,8'-diacetobiphenyl ether (DHDE-Ac) 7.88 g (27.54 mmol), 4-PTMI-Ac 0.9
7 g (3 mmol), PHBA-Ac 16.75 g (93 mmol) and triphenyl phosphate 30 mg were charged and prepolymerized in the same manner as in Example 1, and further PA 0.60 g (2.25 mmol), QA 0.60 g (2.25 mmol) and TP.
A 3.73 g (22.5 mmol) of A was added and the reaction was carried out in the same manner as in Example 1. However, the final temperature was 320 ° C., and the reaction was stopped after a depressurization time of 45 minutes. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy occurs (liquid crystal onset temperature), and thermal decomposition onset temperature of the obtained polymer.

Example 3 In a container similar to that of Example 1, 8.27 g (30.60 mmol) of BP-Ac,
N- (3-acetoxyphenyl) -trimellitic imide (3-PTM
I-Ac) 0.97 g (3 mmol), PHBA-Ac 15.67 g (87 mmol) and triphenyl phosphate 30 mg were charged and prepolymerized in the same manner as in Example 1, and further PA 2.02 g (7.5 mmol) and QA 2.02 g ( 7.5mmo
l) and 2.49 g (15 mmol) of TPA were added and the reaction was carried out in the same manner as in Example 1. However, the final temperature was 315 ° C, and the reaction was stopped after a depressurization time of 60 minutes. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy occurs (liquid crystal onset temperature), and thermal decomposition onset temperature of the obtained polymer.

Example 4 In the same container as in Example 1, 8.27 g (30.60 mmol) of BP-Ac,
3-PTMI-Ac 0.97 g (3 mmol), PHBA-Ac 15.67 g (87 mmol) and triphenyl phosphate 30 mg were charged and prepolymerized in the same manner as in Example 1, and further PA 1.41 g (5.25 mmol) and QA 1.41 g (5.2
5 mmol) and 3.23 g (19.5 mmol) of TPA were added and the reaction was carried out in the same manner as in Example 1. However, the final temperature was 320 ° C., and the reaction was stopped when the pressure was reduced for 65 minutes. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy occurs (liquid crystal onset temperature), and thermal decomposition onset temperature of the obtained polymer.

[0040]

[Table 1]

Claims (1)

[Claims] 1. Comprised of repeating units A, B, C, D, E and F of the formula: (However, Ar in the structural unit E represents a divalent aromatic group, and the hydroxyl group derived from the aminophenol in the structural unit F exists in the para position or the meta position with respect to the imide group.) A / The molar ratio of [A + B + C + D + E + F] is greater than 0 and 85/100 or less, the molar ratio of D / [B + C + D] is 5/100 or more and less than 1, and the molar ratio of F / [A + F] is greater than 0 and 20/1.
An aromatic copolyester imide which is less than 00 and [B + C + D] and E are substantially equimolar.