JP3185414B2 - Aromatic copolyesterimide - 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 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 has excellent moldability, has attracted attention.

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

[0004] Liquid crystalline polyesterimides having an imide group in the polymer chain are also known. For example, Macrom
olecules, 21 , 1929 (1988) include N, N'-bis (ω-carboxyalkyl) benzophenone-3,3 ', 4,4'-tetracarboxylic 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-condensate of an imidized product of trimellitic anhydride and p-aminophenol. Also, J. Polym. Sci .: Part A: Polymer Chemistr
y, 27 , 431 (1989): N- (ω-carboxyalkylene)
-Trimellitimide and biphenol or N- (ω-
Copolyesterimides consisting of (carboxyalkylene) -trimellitic imide, hydroquinone and p-hydroxybenzoic acid are described. However, these copolyesterimides have insufficient heat resistance.

In Eur. Polym. J., 28 , 261 (1992), N-
Copolymers of (p-carboxyphenyl) -trimellitimide with various diols such as biphenol, 2,6-naphthalenediol, 4,4'-dihydroxybiphenyl ether are described. However, since this copolyesterimide has a high melting point, it has been virtually impossible to melt-process without decomposing 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 less and can give a molded article having excellent heat resistance.

[0007]

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

Embedded image (However, Ar in the formula represents a divalent aromatic group, and R is

Embedded image A / [A + B + C + D + E +
F] is greater than 0 and not more than 85/100, D / [B + C
+ D] is greater than or equal to 5/100 and less than 1, the molar ratio of F / [E + F] is greater than 0 and less than 40/100, and [B + C +
D] and [E + F] relate to aromatic copolyesterimides that are substantially equimolar.

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. .

The repeating unit B is 3,3'-dimethylbiphenyl
It is derived from -4,4'-dicarboxylic acid, its dicarboxylic acid ester, dicarboxylic acid halide and the like.

The repeating unit C is 3,4'-dimethylbiphenyl
It is derived from -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. Yes (Japanese Patent Application No. 63-267202)
No., and Japanese Patent Application No. 1-211334).

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

The repeating unit E includes 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether, hydroquinone, resorcinol, 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 diacetyls Is derived from Among them, those derived from 4,4'-dihydroxybiphenyl, 4,4'-diacetoxybiphenyl, 4,4'-dihydroxybiphenyl ether, 4,4'-diacetoxybiphenyl ether and the like are preferable.

The repeating unit F is N, N'-bis (p-hydroxyphenyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide, N, N'-bis (p-acetoxyphenyl) biphenyl -3,3 ', 4,4'-tetracarboxylic diimide, N, N'-bis
(2-Hydroxyethyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide, N, N'-bis (2-acetoxyethyl) biphenyl-3,3', 4,4'-tetracarboxylic acid It is derived from diimide and the like.

The method for producing the above diimides is not particularly limited. For example, N, N'-bis (p-hydroxyphenyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide is as follows: The method can be used.

The biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride and p-aminophenol are heated to 100 to 200 ° C. in a solvent such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like. The resulting N, N'-bis (p-hydroxyphenyl) biphenyl-3,3 ', 4,4'- was reacted for 1 to 7 hours while removing the generated water azeotropically with toluene while removing it from the system. The tetracarboxylic diimide can be obtained by separating, washing and drying. This diimide can be converted to the corresponding acetyl form by acetylation using acetic anhydride. The above reaction can be performed continuously, and a diacetoxy derivative can be synthesized in high yield.

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. When this ratio exceeds 85/100, the melting temperature of the aromatic copolyesterimide increases,
It is difficult to form.

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

The molar ratio of F / [E + F] is greater than 0
It is less than 40/100, preferably greater than 0 and less than 30/100. If the molar ratio is greater than 40/100, the melt viscosity will increase, and the molding processability will be difficult. [B + C + D] and [E + F] are substantially equimolar.

The above repeating units A, B, C, D, E and F
Alternatively, A, B, C, D, E and F may be replaced by repeating units derived from small amounts of monomers capable of forming other ester and imide bonds.

Specific examples of the repeating unit capable of forming another 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 units such as derived from 2,2-diphenylpropane-4,4′-dicarboxylic acid, and m-hydroxybenzoic acid, 4-hydroxy-4′-carboxydiphenyl ether, Oxycarboxy units derived from 1-hydroxy-4-naphthoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxybiphenyl-4′-carboxylic acid and the like can be mentioned.

Specific examples of the repeating unit constituting another imide bond include N, N′-bis (m-hydroxyphenyl) biphenyl-3,3 ′, 4,4′-tetracarboxylic diimide, N, N '-
Bis (4-hydroxybutyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide, N, N'-bis (6-hydroxyhexyl) biphenyl-3,3', 4,4'-tetracarboxylic Acid diimide and the like can be mentioned.

In order to make the melting point of the aromatic copolyesterimide relatively low, the substitution ratio of these substituted repeating units is 1 relative to the repeating unit [A + B + C + D + E + F].
It is preferably at most 0 mol%. Substitution ratio is 10 mol%
Above, the melting temperature of the aromatic copolyesterimide generally increases, depending on the type of the substituted repeating unit, and the molding process is difficult.Although the melting temperature is kept relatively low, the liquid crystallinity decreases. As a result, disadvantages such as an increase in melt viscosity occur.

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 secondary amine, (2) polycondensation from diphenyl ester of dicarboxylic acid and diol by phenol removal method, (3) polycondensation from diacetyl derivative of dicarboxylic acid and diol by deacetic acid method 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 have been added to the reaction vessel, or the comonomer may be added stepwise.

In this polycondensation reaction, if a method is used in which the monomers of the A, E and F components are acetylated and / or pre-condensed and then a dicarboxylic acid component is added for polycondensation, a homogeneous polymer is produced. be able to. In this method, the polycondensation is carried out at 230 to 350 ° C., the temperature is increased stepwise to remove acetic acid, and the reaction is completed under reduced pressure (about 0.1 Torr). 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, iron (III) acetylacetone, titanium tetrabutoxide, sodium hypophosphite, potassium phosphate and other metals or metals. Compounds can be mentioned, but are not limited thereto. The amount of addition is 0.001 to 0.5% based on the weight of the produced polymer. The timing of addition may be at the start of the precondensation or at the start of the polycondensation reaction.

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

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

[0029]

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

[0030]

Embodiments 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 method. (1) Optical anisotropy: The sample was placed on a polarizing microscope, and heated at a rate of 10 ° C./min under a nitrogen stream using a TH600RMS type heating device manufactured by Linkham Inc. and visually observed (liquid crystal onset temperature). (2) Thermal decomposition onset temperature; SSC / 5200 T manufactured by Seiko Denshi Kogyo
Using a GA device, the sample was heated in nitrogen at a rate of 20 ° C./min, and the time-dependent change in weight was observed. (3) Melting point: Using an SSC / 5200 DSC device manufactured by Seiko Instruments Inc., the sample was heated in nitrogen at 10 ° C./min, and an endothermic peak was observed. (4) Logarithmic viscosity; in pentafluorophenol at 60 ° C,
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 falling time of pentafluorophenol, t is the falling time of the sample solution, and c is the concentration of the sample.

Synthesis Example 1 (Synthesis of N, N'-bis (p-acetoxyphenyl) biphenyl-3,3 ', 4,4'-tetracarboxylic acid diimide (BPTD-Ac)) After that, p-aminophenol 10.91 g (0.1 mol) and N-methylpyrrolidone 100
After preparing a homogeneous solution at 40 ° C.,
14.71 g (0.05 mol) of 3,3 ', 4,4'-tetracarboxylic dianhydride
Was added. After a homogeneous solution was obtained by heating, 30 ml of toluene was added, and the mixture was heated at 160 ° C. for 2 hours while distilling off generated water. Thereafter, 20.4 g (0.2 mol) of acetic anhydride was added dropwise. After a few minutes, a yellow precipitate precipitated. In addition, 4 hours 1
Heated at 60 ° C. After cooling, filtration, washing with methanol,
27.48 g (98% yield) of N, N'-bis (p-acetoxyphenyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide was obtained. Elemental analysis and FD-MS spectrum of the obtained diimide compound were as follows. (Elemental analysis) (Theoretical value) C: 68.57, H: 3.60, N: 5.00 (Measured value) C: 68.67, H: 3.54, N: 5.04 (FD-MS spectrum) M / Z 560 (M ⁺ )

Synthesis Example 2 (N, N'-bis (2-acetoxyethyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide
(Synthesis of (EBTD-Ac)) After degassing in vacuum and purging with nitrogen, put 6.15 g (0.1 mol) of 2-aminoethanol and 100 mol of N-methylpyrrolidone in a 500 ml flask.
Then, 14.71 g (0.05 mol) of biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride was added. After a homogeneous solution was obtained by heating, 30 ml of toluene was added, and the mixture was heated at 160 ° C. for 2 hours while distilling off generated water. Then acetic anhydride
20.4 g (0.2 mol) was added dropwise, and the mixture was further heated at 160 ° C. for 4 hours. After cooling, filter, wash with methanol, 20.59 g (89%
Yield) N, N'-bis (2-acetoxyethyl) biphenyl
-3,3 ', 4,4'-tetracarboxylic diimide was obtained. Elemental analysis and FD-MS spectrum of the obtained diimide compound were as follows. (Elemental analysis) (Theoretical value) C: 62.07, H: 4.34, N: 6.03 (Measured value) C: 62.30, H: 4.32, N: 6.05 (FD-MS spectrum) M / Z 464 (M ⁺ )

Example 1 A stainless steel container (100 ml) was equipped with a stirrer, a nitrogen inlet tube and Claisen using the upper part of a glass separable three-necked flask. In this container, 4.85′-diacetoxybiphenyl (BP-Ac) 7.85 g (29.07 mmol), N, N′-bis
(p-acetoxyphenyl) biphenyl-3,3 ', 4,4'-tetracarboxylic diimide (BPTD-Ac) 0.84 g (1.5 mmol), p-
16.21 g (90 mmol) of acetoxybenzoic acid (PHBA-Ac) and 30 mg of triphenyl phosphate were charged. After degassing in vacuum and repeating nitrogen replacement three times, 250 ° C in a metal bath with tin dissolved
After heating for 5 minutes, the mixture was allowed to cool, reduced in pressure, and then returned to normal pressure with nitrogen.

To this precondensation mixture, 2.02 g (7.5 mmol) of 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid (PA),
4'-dimethylbiphenyl-4,3'-dicarboxylic acid (QA) 2.02g
(7.5 mmol) and 2.49 g (15 mmol) of terephthalic acid (TPA) were added. After degassing under vacuum and repeating nitrogen substitution three times, the mixture was heated in a tin bath at 260 ° C. for 1 hour. The temperature was raised to 315 ° C. over 1 hour and maintained at 315 ° C. for 1 hour, and the acetic acid produced was distilled off together with flowing nitrogen. While maintaining the temperature at 315 ° C., the degree of vacuum was gradually increased. After the degree of decompression reaches 0.3 Torr or less,
The reaction was continued for another 60 minutes.

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

Example 2 In a container similar to that of Example 1, 7.85 g (29.07 mmol) of BP-Ac,
0.84 g (1.5 mmol) of BPTD-Ac, 16.21 g (90 mmol) of PHBA-Ac and 30 mg of triphenyl phosphate were charged and prepolymerized in the same manner as in Example 1, and further, 1.62 g (6 mmol) of PA and 1.62 g (6 mm
ol) and 2.99 g (18 mmol) of TPA, 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 60 minutes of reduced pressure. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the results of the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy (liquid crystal onset temperature) and thermal decomposition onset temperature of the obtained polymer were obtained.

Example 3 In a container similar to that of Example 1, 6.61 g (24.48 mmol) of BP-Ac,
3.36 g (6 mmol) of BPTD-Ac, 16.21 g (90 mmol) of PHBA-Ac and 30 mg of triphenyl phosphate were charged and prepolymerized in the same manner as in Example 1; further, 2.02 g of PA (7.5 mmol) and 2.02 g of QA (7.5 mm
ol) and 2.49 g (15 mmol) of TPA, 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 50 minutes of reduced pressure. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the results of the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy (liquid crystal onset temperature) and thermal decomposition onset temperature of the obtained polymer were obtained.

Example 4 5.78 g (21.42 mmol) of BP-Ac was placed in the same container as in Example 1.
0.84 g (1.5 mmol) of BPTD-Ac, 18.91 g (105 mmol) of PHBA-Ac and 30 mg of triphenyl phosphate 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
(7.5 mmol) and 1.24 g (7.5 mmol) of TPA were added.
The reaction was carried out in the same manner as described above. However, the final temperature is 320 ℃,
The reaction was stopped at a reduced pressure time of 40 minutes. The resulting polymer is
It was pale yellow and opaque, and the fluidity was good. Table 1 shows the results of the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy (liquid crystal onset temperature) and thermal decomposition onset temperature of the obtained polymer were obtained.

Example 5 In a container similar to that in Example 1, 7.85 g (29.07 mmol) of BP-Ac,
N, N'-bis (2-acetoxyethyl) biphenyl-3,3 ', 4,
4'-tetracarboxylic diimide (EBTD-Ac) 0.69 g (1.5 mmo
l), PHBA-Ac 16.21 g (90 mmol) and triphenyl phosphate 3
0 mg was charged and prepolymerized in the same manner as in Example 1.
1.62 g (6 mmol), QA 1.62 g (6 mmol) and TPA 2.99 g (18 mm
ol) 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 75 minutes of reduced pressure. The obtained polymer was pale yellow and opaque and had good fluidity. Yield of the obtained polymer, logarithmic viscosity,
Table 1 shows the results of the melting point, the temperature showing the optical anisotropy (liquid crystal onset temperature), and the thermal decomposition onset temperature.

Example 6 In the same container as in Example 1, 7.44 g (26.01 mmol) of 4,4'-diacetoxybiphenyl ether (DHDE-Ac) and BPTD-Ac
84 g (1.5 mmol), PHBA-Ac 17.29 g (96 mmol) and triphenyl phosphate 30 mg were charged and prepolymerized in the same manner as in Example 1,
Furthermore, 0.60 g (2.25 mmol) of PA, 0.60 g (2.25 mmol) of QA and
The reaction was carried out in the same manner as in Example 1 except that 3.73 g (22.5 mmol) of TPA was added. However, the final temperature was 320 ° C., and the reaction was stopped at a reduced pressure time of 45 minutes. The obtained polymer was pale yellow and opaque and had good fluidity. Table 1 shows the results of the yield, logarithmic viscosity, melting point, temperature at which optical anisotropy (liquid crystal onset temperature) and thermal decomposition onset temperature of the obtained polymer were obtained.

[0041]

[Table 1]

Claims (1)

(57) [Claims] 1. It is composed of repeating units A, B, C, D, E and F of the following formula: (However, Ar in the formula represents a divalent aromatic group, and R represents A / [A + B + C + D + E +
F] is greater than 0 and not more than 85/100, D / [B + C
+ D] is greater than or equal to 5/100 and less than 1, the molar ratio of F / [E + F] is greater than 0 and less than 40/100, and [B + C +
Aromatic copolyesterimide wherein D] and [E + F] are substantially equimolar.