JPH06220188A - Aromatic copolyeter amide - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer moldable in a molten state at a relatively low temperature, providing a molded article having excellent heat resistance, having a specific structure. CONSTITUTION:The objective polymer comprises units of formula I to formula V (-NH in the unit V is p-position or m-position based on -CO) and a unit of the formula -O-Ar-O-(Ar is bifunctional aromatic group) and has the molar ratio of the unit I/the whole constituent units of 0-85/100, the molar ratio of the unit IV/(the units II+III+IV) of 5/100-1, the molar ratio of the unit V/the units (I+V) of 0-20/100 and the molar ratio of the units (II+III+IV)/the units -O-Ar-O of equimolar ratio. The polymer, for example, is obtained by subjecting pacetoxybenzoic acid to give the unit I, 3,3'-dimethylbiphenyl-4,4'-dicarboxylic acid to give the unit II, 3,4'-dimethylbiphenyl-4,3'-dicarboxylic acid to give the unit III, terephthalic acid to give the unit IV, a p-aminobenzoic acid to give the unit V and 4,4'-dihydroxybiphenyl to give the unit -O-Ar-O- to polycondensation by deacetylating method.

Description

Detailed Description of the Invention

[0001]

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

[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 polyester amides having an amide group in the polymer chain are also known. For example, Po
lym.J., 21 (5), 409 (1989) contains 4,4'-dicarboxyl.
-1,10-diphenoxydecane, p-aminophenol, copolyesteramide consisting of hydroquinone, and 4,4'-
A copolyesteramide composed of dicarboxy-1,10-diphenoxydecane, p-aminophenol, p-phenylenediamine and hydroquinone is described in Polymer, 24 , 1611 (1983).
A copolyester amide consisting of 4,4'-dicarboxy-α, ω-diphenoxyalkane and p-aminophenol was reported in the Journal of Polymer Science, 47 (6), 499 (1990). ,
A copolyesteramide consisting of 4'-dicarboxy-1,10-diphenoxydecane, biphenol, p-aminobenzoic acid is described. Further, JP-A-3-172323 discloses that
In a copolyester consisting of saturated aliphatic α, ω-dicarboxylic acid, 4,4'-dihydroxybiphenyl and p-hydroxybenzoic acid, part of the unit is replaced with a unit derived from p-aminophenol or p-aminobenzoic acid Disclosed copolyesteramides are disclosed. However, the heat resistance of these copolyesteramides is not described at all.

Also, J. Polym. Sci .; Polymer Chemistr
y Edition, 19 , 3285 (1981) describes a copolyesteramide obtained from m-aminophenol and terephthalic acid, but it cannot be said to have sufficient heat resistance.

[0006]

An object of the present invention is to provide a novel copolyesteramide capable of being melt-molded at a temperature of 400 ° C. or lower and giving a molded article 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 amino group in the structural unit F exists in the para position or the meta position with respect to the carboxyl group.) A / [A + B + C
+ D + E + F] molar ratio is greater than 0 and less than 85/100, D
/ [B + C + D] molar ratio is 5/100 or more and less than 1, F /
The molar ratio of [A + F] is more than 0 and less than 20/100,
[B + C + D] and E relate to an aromatic copolyesteramide in which they are substantially equimolar.

The repeating unit A forming the aromatic copolyesteramide 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 are, for example, JP-A-2-115143 and JP-A-3-77843. Can be synthesized by the oxidative coupling reaction of alkyl orthotoluylate disclosed in.

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.

The repeating unit F is derived from p-aminobenzoic acid, pN-acetylaminobenzoic acid, m-aminobenzoic acid, mN-acetylaminobenzoic acid and the like. Among them, those derived from p-aminobenzoic acid, pN-acetylaminobenzoic acid and the like are preferable.

In the aromatic copolyesteramide of the present invention, the molar ratio of A / [A + B + C + D + E + F] is 0
Greater than 85/100. More preferably, it is more than 0 and 75/100 or less. When this molar ratio exceeds 85/100, the melting temperature of the aromatic copolyesteramide increases,
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 20/100 or more, the melt viscosity increases, and molding processability becomes difficult. [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 capable of forming 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 repeating 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 copolyesteramide relatively low.
It is preferably 0 mol% or less. Substitution rate is 10 mol%
If it exceeds, the melting temperature of the aromatic copolyesteramide is generally high, depending on the type of the repeating repeating unit, making molding difficult and maintaining the melting temperature at a relatively low temperature, but lowering the liquid crystallinity. Therefore, there arises a defect such as an increase in melt viscosity.

The method for producing the aromatic copolyesteramide 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 a dicarboxylic acid component to carry out polycondensation is used to produce a homogeneous polymer. be able to. In this method, polycondensation is carried out 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 resulting polymer. 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 copolyesteramide 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.

[0026]

Industrial Applicability The aromatic copolyesteramide 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.

[0027]

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.

Example 1 A glass container (100 ml) was equipped with an upper part of a glass separable three-necked flask, and a stirrer, a nitrogen introducing tube and a Claisen were attached. In this container, 4,4'-diacetoxybiphenyl (BP-Ac) 8.27 g (30.6 mmol), p-acetoxybenzoic acid (PHBA-Ac) 15.67 g (87 mmol), pN-acetylaminobenzoic acid (PABA- 0.53 g (3 mmol) of Ac) and 30 mg of triphenyl phosphate were charged. After vacuum deaeration and nitrogen replacement were repeated 3 times, the mixture was heated in a tin-dissolved metal bath at 250 ° C. for 5 minutes, allowed to cool, decompressed, and returned to normal pressure with nitrogen.

To this precondensation mixture 1.43 g (5.25 mmol) 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. After vacuum deaeration and nitrogen substitution were repeated 3 times, the mixture was heated in a tin bath at 260 ° C for 30 minutes. 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 pressure reduction reaches 0.3 Torr or less,
The reaction was continued for another 90 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, 8.27 g (30.6 mmol) of BP-Ac,
PHBA-Ac 14.59 g (81 mmol), PABA-Ac 1.61 g (9 mmol) and triphenyl phosphate 30 mg were charged and the same operation as in Example 1 was performed. Next, PA 1.41g (5.25mmol), QA 1.41g
(5.25 mmol) and 3.23 g (19.5 mmol) of TPA were added, and the same operation as in Example 1 was performed. However, the final temperature is 325 ℃
Then, the reaction was stopped at a reduced pressure time of 40 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, 4.88'-diacetoxybiphenyl ether (DHDE-Ac) 7.88 g (27.54 mmol), PHBA-Ac 16.7
5 g (93 mmol), 0.53 g (3 mmol) of PABA-Ac and 30 mg of triphenyl phosphate were charged and the same operation as in Example 1 was performed.
Then, PA 0.60 g (2.25 mmol), QA 0.60 g (2.25 mmol) and
3.73 g (22.5 mmol) of TPA was added and the same operation as in Example 1 was performed. However, the final temperature was 320 ° C., and the reaction was stopped at a reduced pressure time of 55 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.

[0033]

[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 amino group in the structural unit F exists in the para position or the meta position with respect to the carboxyl group.) A / [A + B + C
+ D + E + F] molar ratio is greater than 0 and less than 85/100, D
/ [B + C + D] molar ratio is 5/100 or more and less than 1, F /
The molar ratio of [A + F] is more than 0 and less than 20/100,
An aromatic copolyesteramide in which [B + C + D] and E are substantially equimolar.