JPH05156007A - Aromatic polyesteramide and its production - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyesteramide having a liquid crystal nature, high mechanical strength and high modulus, excellent in heat resistance, moldability, dimensional stability and chemical resistance, etc., by reacting each of specific monomer components using a conventional polyester production device. CONSTITUTION:A raw monomer mixture comprising (A) 1-30mol% of an aromatic aminophenol compound (reactive derivative) of formula I [R<1> is H or methyl; R<2> is 1-6C (oxygen-contg.)hydrocarbon group; (n) is an integer of 1-4], (B) 2-30mol% of 4,4'dihydroxydiphenyl of formula II, (C) 2-30mol% of 2,6 naphthalenedicarboxylic acid (reactive derivative) of formula III, (D) 0-30mol% of terephthalic acid (derivative) of formula IV, and (E) 40-75mol% of p- hydroxybenzoic acid (reactive derivative) of formula V is made to react in the presence of an acid anhydride at 100-400 deg.C while distilling off the acid anhydride and the acid component derived therefrom, thus obtaining the objective aromatic polyesteramide having >=10 poise melt viscosity and made up of constituents of respective formulas VI to X (where, formula IX is arbitrary one).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel aromatic polyesteramide and a method for producing the same. More specifically, the present invention has high elastic modulus, high strength, excellent heat resistance, exhibits liquid crystallinity (optical anisotropy) when melted, has extremely good moldability (fluidity), and has dimensional stability. chemical resistance,
The present invention relates to the aromatic polyester amide excellent in flame retardancy and an industrially advantageous production method thereof.

[0002]

2. Description of the Related Art In recent years, materials having excellent toughness and heat resistance have been demanded in all fields of fibers, films and molded products. By the way, recently, a polymer (liquid crystal polymer) which exhibits optical anisotropy when melted has been attracting attention as a polymer suitable for a use requiring a high elastic modulus and a high strength. For example, “Journal of Polymer Science Polymer Chemistry Edition”, 14th
Volume 2043, p. 2076 (1976)
No. 8016], a liquid crystal copolymerized polyester is proposed. However, although the above liquid crystal copolymerized polyester has higher toughness than conventional general polyesters, it is not always satisfactory in heat resistance.

Further, British Polymer Journal Vol. 13, No. 1, p. 5 (1981), JP-A-57-17
7021, 55-27391 and the like propose liquid crystalline polyesteramides. However,
The above-mentioned liquid crystalline polyesteramide has a drawback that it has a high softening point and cannot be produced by a usual polyester producing apparatus.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is excellent in toughness, heat resistance, fluidity and moldability, and is particularly suitable as engineering plastics. Moreover, it is an object of the present invention to provide an aromatic polyesteramide which can be efficiently produced using a conventional polyester production apparatus and a production method thereof.

[0005]

[Means for Solving the Problems] As a result of intensive research to achieve the above-mentioned object, the present inventors have surprisingly found that a specific structural unit, that is, an aromatic aminophenol unit having a substituent group. , 4,4'-dihydroxydiphenyl unit, 2,6-naphthalenedicarboxylic acid unit, P-
A liquid crystalline aromatic polyesteramide containing a hydroxybenzoic acid unit and an arbitrary terephthalic acid unit in a predetermined ratio and having a specific melt viscosity, and a raw material monomer forming each of the above structural units The present inventors have found that the above object can be easily achieved by a specific manufacturing method used in a predetermined ratio, and have completed the present invention.

That is, the present invention uses the aromatic polyesteramide as the first invention and the method for producing the same as the second invention, and the summary of each invention is as follows. The gist of the first invention is an aromatic polyesteramide having the structural units represented by (a) to (e) in the chemical formula [Chemical Formula 1] described in claim 1 in the following proportions. Yes (however, (d) is any structural unit), 1000 sec at 320 ° C
^The aromatic polyester amide has a melt viscosity of 10 poise or more measured under the condition of ^-1 . (A): 1 to 30 mol%, (b): 2 to 30 mol%,
(C): 2 to 30 mol%, (d): 0 to 30 mol%,
(E): 40 to 75 mol% (however, the sum of (a) to (e) is 100 mol%) The gist of the second invention is the chemical formula [Chemical Formula 2] described in claim 2. The raw material monomers represented by the formulas (a ') to (e') are used in the proportions described below (however, (d ') is an arbitrary raw material component), and in the presence of an acid anhydride, 100 to 400 The method for producing an aromatic polyester amide according to claim 1, wherein the raw material monomer is reacted while distilling off the acid anhydride and the acid component derived therefrom at a temperature of ° C. (A '): 1 to 30 mol%, (b'): 2 to 30 mol% (c '): 2 to 30 mol%, (d'): 0 to 30 mol% (e '): 40 to 75 Mol% (however, (a ') to (e')
Is 100 mol%)

The present invention will be described in detail below. The greatest feature of the aromatic polyester amide of the present invention is that the aromatic aminophenol structural unit having a substituent group exhibits epoch-making toughness, and in spite of containing a large amount of aromatic aminophenol unit. The point is that it can be extracted from the polymerization device.

The aromatic polyester amide of the present invention has, as an essential constituent unit, (a) to (a) in the above chemical formula [Chemical formula 1].
It contains the structural units represented by (c) and (e) and, as an optional component, the structural unit represented by (d) in the above chemical formula [Chemical Formula 1]. In the above, the structural unit (a) is a substituted aromatic aminophenol unit, (b) is 4,4′-dihydroxydiphenyl unit, and (c) is 2,
6-naphthalenedicarboxylic acid unit, (d) is an aromatic dicarboxylic acid unit, and (e) is an aromatic oxycarboxylic acid unit.

In the aromatic aminophenol unit (a), R ¹ is a hydrogen atom or a methyl group, and R ² has 1 to 1 carbon atoms.
A hydrocarbon group having 6 or an oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. Specific examples of R ² include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, and a phenoxy group. And the aromatic aminophenol unit (a) is
It is formed from an aromatic aminophenol compound represented by (a ′) in the chemical formula [Chemical Formula 2] or a reactive derivative thereof. In the aromatic aminophenol compound represented by the above (a ′), R ¹ , R ² and n have the same meaning as in the structural unit (a).

Specific examples of the aromatic aminophenol compound or the reactive derivative include 3-methyl-4-aminophenol, 2-methyl-4-aminophenol and 3-methyl-4-aminophenol.
Ethyl-5-N-methyl-aminophenol, 3-methoxy-4-N-methylaminophenol, 3-methoxy-4-aminophenol, 2-phenyl-4-aminophenol, 3-t-butyl-4-amino Phenol acetate, 3-cyclohexyl-5-aminophenol,
Examples thereof include 3,5-dimethyl-4-aminophenol and the like, but are not necessarily limited thereto.

Among the above specific examples, 3-methyl-4-
Aminophenol, 2-methyl-4-aminophenol and 3-methoxy-4-N-methylaminophenol are preferable, and especially 3-methyl-4-aminophenol,
2-Methyl-4-aminophenol is preferred. The aromatic aminophenol compound or reactive derivative may be used alone or in combination of two or more.

The 4,4'-dihydroxydiphenyl unit (b) is formed from 4,4'-dihydroxydiphenyl represented by (b ') in the chemical formula [Chemical Formula 2] or its reactive derivative. Specific examples of these are:
Examples thereof include, but are not limited to, 4'-dihydroxydiphenyl, 4,4'-diacetoxydiphenyl, and 4,4'-dibenzoyloxydiphenyl.
Among these specific examples, 4,4'-dihydroxydiphenyl is preferable.

The 2,6-naphthalenedicarboxylic acid unit (c) is formed from 2,6-naphthalenedicarboxylic acid represented by (c ') in the chemical formula [Chem. 2] or its reactive derivative. Specific examples of these include 2,6-
Examples thereof include, but are not limited to, naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, and diphenyl 2,6-naphthalenedicarboxylic acid. Among these specific examples, 2,6-naphthalenedicarboxylic acid is preferable.

The aromatic dicarboxylic acid unit (d) is formed from terephthalic acid represented by (d ') in the chemical formula [Chemical Formula 2] or a derivative thereof. Specific examples of these are:
Examples thereof include terephthalic acid, dimethyl terephthalate, diphenyl terephthalate, and dichloride terephthalate.
It is not limited to these.

The aromatic oxycarboxylic acid unit (e) is formed from p-hydroxybenzoic acid represented by (e ') in the chemical formula [Chemical Formula 2] or a reactive derivative thereof.
Specific examples of these include p-hydroxybenzoic acid, p
-Acetoxybenzoic acid, methyl p-hydroxybenzoate and the like can be mentioned, but the invention is not limited thereto.
Among these specific examples, p-hydroxybenzoic acid is preferred.

The proportion of the aromatic aminophenol unit (a) (the proportion to the total amount of the structural units (a) to (e); the same applies hereinafter) is 1 to 30 mol%, preferably 2 to 28 mol%, and more preferably Is 5 to 25 mol%. When the proportion of the aromatic aminophenol unit (a) is less than 1 mol%, the effect of improving the elastic modulus and strength is not sufficient.

The proportion of 4,4'-dihydroxydiphenyl units (b) is 2 to 30 mol%, preferably 3 to 25.
Mol%, more preferably 5 to 20 mol%. 4,
When the proportion of the 4'-dihydroxydiphenyl unit (b) is less than 2 mol%, the effect of enhancing the liquid crystallinity is not sufficiently exerted, and when it exceeds 30 mol%, the degree of polymerization is not sufficiently increased. Increasing the liquid crystallinity means improving the elastic modulus and the moldability (improving the fluidity, that is, decreasing the melt viscosity).

The proportion of the 2,6-naphthalenedicarboxylic acid unit (c) is 2 to 30 mol%, preferably 5 to 30.
Mol%, more preferably 10 to 30 mol%. Two
When the proportion of the 6-naphthalenedicarboxylic acid unit (c) is less than 2 mol%, the effect of enhancing the liquid crystallinity is not sufficiently exhibited, and when it exceeds 30 mol%, the degree of polymerization is not sufficiently increased.

The proportion of aromatic dicarboxylic acid units (d) is
It is 0 to 30 mol%, preferably 0 to 25 mol%, and more preferably 0 to 20 mol%. When the proportion of the aromatic dicarboxylic acid unit (d) exceeds 30 mol%, the degree of polymerization may not be sufficiently increased, and a normal polyester production apparatus (for polyester having a melting temperature of 320 ° C. or lower)
Then it becomes difficult to manufacture. That is, solidification occurs during polymerization,
It becomes difficult to extract the produced polymer from the polymerization tank.

The proportion of the aromatic oxycarboxylic acid unit (e) is 40 to 75 mol%, preferably 40 to 65 mol%,
More preferably, it is 40 to 60 mol%. When the proportion of the aromatic oxycarboxylic acid unit (e) exceeds 75 mol%, the fluidity is deteriorated and it becomes difficult to manufacture the polyester with a normal polyester manufacturing apparatus.

Regarding the above structural units (a) to (d), when the respective molar numbers are represented by the symbols [a] to [d], the following mathematical formula [Numerical formula 1], particularly mathematical formula [ It is preferable to satisfy the relationship represented by [Equation 2]. By satisfying such a relationship, the aromatic polyester amide of the present invention can have a higher degree of polymerization.

[0022]

## EQU1 ## 0.9 ≦ ([1] + [2] / [3] + [4]) ≦ 1.1

## EQU2 ## 0.95 ≦ ([1] + [2] / [3] + [4]) ≦ 1.05

The aromatic polyester amide of the present invention exhibits liquid crystallinity by containing the above-mentioned specific structural unit in a specific amount, and therefore has excellent moldability, and
It has remarkably high elastic modulus and strength, and further has excellent characteristics such as good fluidity. Moreover, the aromatic polyester amide of the present invention has a manufacturing advantage that it can be easily manufactured using a conventional polyester manufacturing apparatus (for example, a vertical polyethylene terephthalate manufacturing apparatus).

In the aromatic polyesteramide of the present invention, the structural units (a) and (c) improve the liquid crystallinity,
It exerts the effect of increasing the elastic modulus and fluidity, but in particular,
The structural unit (a) (the aminophenol unit having a substituent) does not raise the flow starting temperature so much, and therefore the elastic modulus and the strength can be increased without causing the problem that the production becomes difficult even if the content is increased. The effect of increasing
This is unexpected.

The aromatic polyesteramide of the present invention is required to have a melt viscosity of 10 poise or more measured at a temperature of 320 ° C. and a shear rate of 1000 sec ⁻¹ .
If it is less than 10 poise, sufficient strength cannot be obtained. A preferable melt viscosity under the measurement conditions is 50 poise or more,
A particularly preferable melt viscosity is in the range of 100 to 10,000 poise.

The aromatic polyester amide of the present invention uses each of the above-mentioned raw material monomers so that each structural unit has a predetermined ratio, and a known polymerization method such as a melt polymerization method, a solution polymerization method, It can be produced by polycondensation by an interfacial polymerization method or the like. In the case of the melt polymerization method, a part of the raw material monomer is usually used as an acylated product or ester, and the polymerization is carried out at a temperature of about 200 to 400 ° C., or an acylating agent is added to the raw material monomer. A method of polymerizing is adopted. Further, in the case of the solution polymerization method or the interfacial polymerization method, the raw material monomer is used by converting its carboxyl group into an acid halide (particularly, acid chloride). Further, in the case of the interfacial polymerization method, the raw material monomer is , The hydroxyl group is converted into a salt for use.

The melt polymerization method is advantageous for industrial production because it does not require post-treatment after the polymerization reaction, while the solution polymerization method and the interfacial polymerization method can perform the polymerization reaction at a relatively low temperature. There is an advantage that you can. In particular, according to the production method of the present invention described below, the aromatic polyester amide of the present invention can be produced extremely advantageously and efficiently in terms of production cost and workability.

The process for producing an aromatic polyester amide of the present invention is carried out in the presence of an acid anhydride at a temperature of 100 to 400 ° C. while distilling off the acid anhydride and the acid component derived therefrom to remove the raw material monomer. It is characterized by reacting. In the production method of the present invention, it is necessary to use the raw material monomers (a ′) to (e ′) represented by the chemical formula [Formula 2] in the proportions described below. (A '): 1 to 30 mol%, (b'): 2 to 30 mol% (c '): 2 to 30 mol%, (d'): 0 to 30 mol% (e '): 40 to 75 Mol% (however, (a ') to (e')
Is 100 mol%)

Examples of the above-mentioned acid anhydride include acetic anhydride, propionic anhydride, benzoic anhydride and the like. Among these, acetic anhydride is particularly preferable. The acid anhydrides are used alone or in combination of two or more. The ratio of its use is such that the acid anhydride, the raw material monomers (a '), (b') and (e ') are each expressed in moles [Anh], [a'], [b ']. And the symbols of [e '], it is preferable to satisfy the relationship expressed by the following mathematical formula [Equation 3], especially the mathematical formula [Equation 4].

[0030]

## EQU3 ## 0.8 ≦ [Anh] / {2 ([1 ′] + [2 ′]) + [5 ′]} ≦ 2.0

## EQU4 ## 1.0 ≦ [Anh] / {2 ([1 ′] + [2 ′]) + [5 ′]} ≦ 1.5

The above reaction can be carried out in the presence of a catalyst, if necessary. As such a catalyst, for example,
_{BuSnOOH, Bu 2 SnO, Ti (} O-i-Pr)
₄ , Zn (OAc) ₂ , Sn (OAc) ₂ , Sb
₂ O ₃ , Co (OAc) ₂ , KOAc and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The reaction temperature is not particularly limited as long as it is in the range of 100 to 400 ° C., but when acid anhydride is mainly added to perform acylation, a temperature of about 100 to 200 ° C. is preferable. .. After that, if condensation is mainly performed,
It is advantageous to raise the temperature and carry out at a temperature of 250 to 400 ° C.

In the production method of the present invention, the reaction is carried out while the above acid anhydride and the acid formed therefrom are distilled out of the system. In order to efficiently carry out this distillation, an inert gas such as nitrogen or argon can be circulated in the reaction system or reduced pressure can be applied. Further, when it is desired to further increase the degree of polymerization, it is also possible to apply a solid phase polymerization method.

The aromatic polyesteramide of the present invention obtained as described above can be subjected to general melt molding such as extrusion molding, injection molding and compression molding, and molded articles, films, fibers, etc. Can be easily processed. In particular, since it has high fluidity, high elastic modulus, and high strength, it is suitable for precision molded products, thin-walled molded products, and the like.

The aromatic polyesteramide of the present invention includes
For example, fibers such as glass fiber and carbon fiber, talc,
Addition of fillers such as mica and calcium carbonate, nucleating agents, pigments, antioxidants, lubricants, stabilizers, flame retardants and other fillers and additives, other thermoplastic resins, etc. It is also possible to impart the characteristics of. Also,
A composition having the advantages of the other polymer and the advantages of the aromatic polyester amide of the present invention can also be obtained by blending with another polymer or alloying. The aromatic polyester amide of the present invention is particularly characterized by being easily compatible with polyamide.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The raw material monomers used in each example, and the measuring methods of the respective physical properties and characteristics are as follows.

<Raw material monomers> (1) The following four raw material monomers were used for the aromatic aminophenol unit (a). The structural unit formed from these is represented by the following symbols in parentheses () in the tables below. 3-methyl-4-aminophenol ((a
1)) 3,5-Dimethyl-4-aminophenol (structural unit represented as (a2)) 2-phenyl-4-aminophenol (structural unit represented by (a
3)) 3-amino-4-methylphenol (structural unit (a
4)) p-aminophenol (structural unit is shown as (a5))

(2) 4,4'-Dihydroxydiphenyl was used as the 4,4'-dihydroxydiphenyl unit (b). (3) 2,6-naphthalenedicarboxylic acid unit (c) was 2,6-naphthalenedicarboxylic acid. (4) Terephthalic acid was used as the aromatic dicarboxylic acid unit (d). (5) p-Hydroxybenzoic acid was used as the aromatic oxycarboxylic acid unit (e).

<Measurement Method of Physical Properties and Properties> (1) Melt Viscosity Using a flow tester (manufactured by Shimadzu Corporation), temperature 320
The measurement was carried out under conditions of a temperature of 1000 ° C., a shear rate of 1000 sec ⁻¹ and a cylinder nozzle length / diameter ratio of 20. (2) IR analysis As an infrared spectrophotometer, 20D × manufactured by Nicolet
BFT-IR was used to measure a KBr disc as a test sample. (3) Tensile test A molded piece was pulled and measured with Tensilon. The molded piece was molded using a 0.1 oz injection molding machine manufactured by Nippon Steel Co., Ltd. to prepare a molded piece. (4) Optical anisotropy (liquid crystallinity) It was observed using a polarizing microscope with a hot stage.

Example 1 7.39 g (0.06 mol / 7.7 mol%) of 3-methyl-4-aminophenol was added to a polymerization tube equipped with a stirring blade, a pressure reducing port, and an N ₂ introducing port, 4,4. 22.35 g of'-dihydroxydiphenyl (0.12 mol / 15.3 mol%), 2,
19.46 g (0.09 mol / 11.5 mol%) of 6-naphthalenedicarboxylic acid, 14.95 g of terephthalic acid
(0.09 mol / 11.5 mol%), p-hydroxybenzoic acid 58.01 g (0.42 mol / 54.0 mol%)
Was charged, the atmosphere was replaced with N ₂ under reduced pressure, the reaction vessel was sealed with N ₂ , and 87.59 g (0.86 mol) of acetic anhydride was added. The polymerization tube was immersed in an oil bath at 145 ° C., reacted for 1 hour under stirring, and then heated to 320 ° C. over 1.5 hours. Then, a pressure was gradually applied to complete the polycondensation reaction to obtain a polymer.

The above polymer flowed by its own weight at 320 ° C. and could be withdrawn from the bottom of the polymerization tube. Also, the melt viscosity is 280 poise, and 2
It started to flow at 83 ° C. and exhibited optical anisotropy (liquid crystallinity). Further, the tensile elastic modulus was 95300 kg / cm ² , the tensile strength was 2230 kg / cm ² , and the elongation at break was 4.5%, showing extremely high toughness.

The IR chart of the above polymer is shown in FIG. The elemental analysis results are shown below (however, the values in parentheses are calculated values). C: 74.25% (73.33%) H: 3.55% (3.67%) N: 0.73% (0.78%)

Example 2 14.78 g of 3-methyl-4-aminophenol (0.12 mol / 15.3 mol%), 4, 4 were placed in a polymerization tube equipped with a stirring blade, a pressure reducing port, and an N ₂ introducing port. 11.17 g of'-dihydroxydiphenyl (0.06 mol / 7.7 mol%),
2,6-naphthalenedicarboxylic acid 19.46 g (0.0
9 mol / 11.5 mol%), terephthalic acid 14.95 g
(0.09 mol / 11.5 mol%), p-hydroxybenzoic acid 58.01 g (0.42 mol / 54.0 mol%)
Was charged, the atmosphere was replaced with N ₂ under reduced pressure, the reaction vessel was sealed with N ₂ , and 87.59 g (0.86 mol) of acetic anhydride was added. Then, polymerization was performed in the same manner as in Example 1 to obtain a polymer. This polymer also flowed by its own weight at 320 ° C. and could be withdrawn from the bottom of the polymerization tube. The melt viscosity is 2
00 poise and begins to flow at 290 ° C.
It exhibited optical anisotropy (liquid crystallinity). The tensile modulus is 102400 kg / cm ² , and the tensile strength is 2360 kg / cm ² .
cm ² , and the elongation at break was 4.0%, which was an extremely high value for toughness.

Comparative Example 1 13.10 g (0.12 mol / 1) of p-aminophenol
5.4 mol%), 4,4'-dihydroxydiphenyl 1
1.17 g (0.06 mol / 7.7 mol%), 2,6-
Naphthalene dicarboxylic acid 19.46 g (0.09 mol /
11.5 mol%), terephthalic acid 14.95 g (0.0
9 mol / 11.5 mol%), p-hydroxybenzoic acid 5
Polymerization was performed in the same manner as in Example 2 except that 8.01 g (0.42 mol / 53.9 mol%) was used to obtain a polymer. This polymer was difficult to flow at 320 ° C., and the yield of the polymer extracted from the bottom of the polymerization tube was low. The melt viscosity is 3500 poise and the tensile elastic modulus is 5610.
0 kg / cm ^2, tensile strength of 1250 kg / cm ^2, elongation at break was 1.7%.

Examples 3-6 and Comparative Examples 2-3 As shown in Table 1, aromatic aminophenol units (a)
And Example 1 except that the kind of raw material monomer and the charging ratio were changed in order to change the content ratio of each structural unit.
A polymer was obtained in the same manner as in. The above results are shown in Table 1. Table 1 also shows the results of Examples 1 and 2 and Comparative Example.
Shown in. In addition, (a1) to (a4) in Table 1 represent each structural unit in the following chemical formula [Chemical Formula 3], and (b) to (e)
Represents each structural unit in the chemical formula [Formula 1].

[0046]

[Chemical 3]

[0047]

[Table 1] Actual example ─────────────────────────── 1 2 3 4 5 ──────────── ───────────────────────── <Structural unit> a1 (7.7) a1 (15.3) a1 (22.9) a1 (23.6) a2 (10.0) b (15.3) b (7.7) b (5.7) b (5.0) b (15.0) c (11.5) c (11.5) c (28.6) c (14.3) c (15.0) d (11.5) d (11.5) − d ( 14.3) d (10.0) e (54.0) e (54.0) e (42.8) e (42.8) e (50.0) <Polymerization temperature> (℃) 320 320 320 320 320 <Withdrawability> ○ ○ ○ ○ ○ <Melt viscosity ＞ (Poise) 280 200 350 400 220 <Tensile modulus> (× 10 ⁴ ) 9.53 12.244 11.23 10.87 9.96 <Tensile strength> 2230 2360 2850 2420 2280 <Elongation at break> (%) 4.5 4.0 3.8 3.5 3.7 <Liquid crystallinity> ○ ○ ○ ○ ○ ─────────────────────────────────────

[0048]

[Table 2] Examples Comparative Examples ───── ────────────────── 6 1 2 3 3 ───────────── ─ ───────────────── <Structural unit> a2 (15.3) a5 (15.4) -a5 (7.7) b (7.7) b (7.7) b (23.0) b (15.3) c (11.5) c (11.5) c (11.5) -d (11.5) d (11.5) d (11.5) d (23.0) e (54.0) e (53.9) e (54.0) e (54.0) <polymerization temperature> ( ℃) 320 320 320 320 <Extractability> ○ × ○ × <Melt viscosity> (Poise) 290 3500 250 2800 <Tensile modulus> (× 10 ⁴ ) 11.45 5.61 6.29 8.85 <Tensile strength> 2620 1250 1580 750 <Elongation at break > (%) 3.4 1.7 2.5 1.3 <Liquid crystallinity> ○ ○ ○ − ───────────── ───────────────────

[0049]

As described above, according to the present invention, there is provided a liquid crystalline polyesteramide having high strength, high elastic modulus, and excellent fluidity and moldability. Further, the above-mentioned liquid crystalline aromatic polyesteramide can be produced without any trouble by using the conventional melt-type polyester production apparatus.

[Brief description of drawings]

1 is an IR chart of the polymer obtained in Example 1. FIG.

Claims (2)

[Claims] 1. (a) to (e) in the following chemical formula [Chemical formula 1]:
An aromatic polyester amide containing structural units represented by the following ratios (however, (d) is an arbitrary structural unit), the melt viscosity measured under the conditions of a temperature of 320 ° C. and a shear rate of 1000 sec ^−1. Is 10 poise or more, an aromatic polyesteramide. (A): 1 to 30 mol%, (b): 2 to 30 mol &,
(C): 2 to 30 mol%, (d): 0 to 30 mol%,
(E): 40 to 75 mol% (however, the total of (a) to (e) is 100 mol%) (In the above formula, in the structural unit (a), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 6 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 6 carbon atoms, and n is 1 ~ Represents an integer of 4) 2. The following chemical formula [Chemical formula 2] (a ′) to
The raw material monomer represented by (e ′) is used in the following proportions (provided that (d ′) is an arbitrary raw material component), and the acid is added in the presence of an acid anhydride at a temperature of 100 to 400 ° C. The method for producing an aromatic polyester amide according to claim 1, wherein the raw material monomer is reacted while distilling the anhydride and the acid component derived therefrom. (A '): 1 to 30 mol%, (b'): 2 to 30 mol% (c '): 2 to 30 mol%, (d'): 0 to 30 mol% (e '): 40 to 75 Mol% (however, (a ') to (e')
Is 100 mol%) (In the above formula, in the raw material monomer (a ′), R ¹ , R
² and n have the same meaning as in the structural unit (a) in the chemical formula [Chemical Formula 1].