JPH0565340A - Liquid crystalline polyesteramide - Google Patents

Abstract

PURPOSE:To obtain the subject polyesteramide which has a high heat resistance, high tensile, bending, and impact strengths, etc., by incorporating dicarboxylic acid residues, diol residues, p-hydroxybenzoic acid residues, and aminophenol residues into the polyesteramide in specified molar ratios. CONSTITUTION:The objective polyesteramide comprises dicarboxylic acid residues of formula I (wherein R is a 6-18C divalent arom. hydrocarbon group), diol residues of formula II, p-hydroxybenzoic acid residues of formula III, and aminophenol residues of formula IV and satisfies the following requirements: equations V, VI, and VII hold true provided that the number of moles of residues of formulas I, II, III, and IV are [1], [2], [3], and [4], respectively; the value (r) calculated by equation IX satisfies 0<=r<=0.88 provided that [3-1] is the number of moles of p-hydroxybenzoic acid residues directly bonded to the diol residues; and the melt viscosity under a shear rate of 1,000sec<-1> at 310 deg.C is at least 50P.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystalline polyesteramide having a more alternately controlled sequence. The present invention has a high elastic modulus, high tensile strength, bending strength, impact strength, and the like, and has high toughness due to its high elongation, and at the same composition and the same composition ratio, mechanical properties as compared with conventional ones. The present invention relates to a liquid crystalline polyesteramide having excellent heat resistance as well.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for materials having excellent rigidity, strength, elongation and heat resistance regardless of whether they are fibers, films or molded products. Polyester has come to be widely used for general molded products, but many polyerters have poor flexural modulus and flexural strength.
It was not suitable for applications requiring high strength.

In recent years, liquid crystalline polyester has been attracting attention as a polyester suitable for applications requiring high elastic modulus and high strength. The Journal of Polymer Science
Polymer Chemistry Edition Volume 14 (197
6 years) 2043 pages, USP3,778,410, USP
3,804,805 and Japanese Patent Publication No. 56-18016. J. Only after Jackson et al. Announced a thermal liquid crystal polymer composed of polyethylene terephthalate and acetoxybenzoic acid. Among them, Jackson et al. Found that this liquid crystal polymer has a rigidity of 5 times or more that of polyethylene terephthalate.
It was reported that it exhibits more than double the strength and more than 25 times the impact strength, and shows a new possibility for high performance resin.

However, the polymer of Jackson et al. Has the drawback of being very brittle and having low strength and elongation. It is considered that this is mainly because the chain ratio of the p-oxybenzoic acid residues represented by the following formula is very large.

[0005]

[Chemical 3]

Further, it is considered that the melting point, the softening point and the like vary depending on the ratio of the chain of p-oxybenzoic acid residues.
A high proportion of this linkage means that the sequence and its distribution, as well as the composition distribution, are widely distributed, that is to say have a high degree of heterogeneity.

[0007]

The present applicant has previously disclosed a polyesteramide having excellent heat resistance and fluidity (Japanese Patent Application No. 2-41817). However, Japanese Patent Application No. 2
In the production method of No. -41817, only a random copolymer having a chain of p-oxybenzoic acid residues in the meaning described below was obtained, and the strength and elongation were slightly inferior.

[0008]

Therefore, the present inventors have proposed a liquid crystalline polyesteramide comprising structural units represented by the following chemical formulas (1), (2), (3) and (4), and further having tensile strength and bending. The present invention has been achieved as a result of studying a system having high strength, impact strength, and the like and excellent heat resistance, and paying attention to controlling the sequence and composition distribution, that is, making the sequence alternating, as a result.

[0009]

[Chemical 4]

(R in the above chemical formula (1) has 6 to 1 carbon atoms.
8 shows a divalent aromatic hydrocarbon group of 8. ) That is, the present invention comprises the above formulas (1) to (4) and satisfies the following condition (a) to
A liquid crystalline polyesteramide satisfying the condition (c).

(A) The above chemical formulas (1), (2),
The molar numbers of (3) and (4) are [1], [2],
When [3] and [4] are set,

[0012]

[Equation 3]

[0013] (B) A p-oxybenzoic acid residue represented by the above formula (3), which is directly linked to the diol residue represented by the formula (2), is designated as (3-1), and (3-1) Where r is the number of moles of [3-1], r obtained from the following formula (I)
Is 0 ≦ r ≦ 0.88.

[0014]

[Chemical 5]

(The unit corresponding to the underlined portion is the (3-1) unit.)

[0016]

[Equation 4]

(C) The melt viscosity (at a shear rate of 1000 sec ^-1 ) measured at 300 ° C is 50 poises or more. Hereinafter, the present invention will be described in more detail. A first feature of the present invention is to reduce the number of constitutional units of the following formula (3-2), which is a chain of the formula (3), and increase the number of constitutional units of the above (3-1).

[0018]

[Chemical 6]

For this purpose, the parameter r (sequence generation ratio) defined by the above formula (I) is 0 ≦ r ≦ 0.
88 must be met. The lower limit of r is preferably ([3] -2 × [2]) / [3] or more, more preferably {([3] -2 × [2]) / [3]} + 0.2 ×
More than {[2] / [3]}, more preferably {([3]
-2 × [2]) / [3]} + 0.4 × {[2] /
[3]} and above. Most preferably {([3] -2
× [2]) / [3]} + 0.6 × {[2] / [3]} or more.

The upper limit of r is preferably 0.85 or less, more preferably 0.83 or less, still more preferably 0.80.
Hereafter, it is most preferably 0.78 or less. In addition, when calculating [3-1] in the above formula (I), it should be noted that the unit of the following formula has two units of (3-1).

[0021]

[Chemical 7]

When [3] exceeds twice [2], [3]-[3-1]> 0 is inevitably satisfied. Therefore, r cannot be 0. In this case, the lower limit value of r (r ≧ 0) should be read as ([3] −2 × [2]) / [3]. However, it is preferable that {([3] −2 × [2]) / [3]} − 0.03 ≦ r in consideration of calculation error and the like.

Next, the meaning of the above equation will be described. In the derivation of the formula (I), B. Volmert edited by Polymer Chemistry; Springe
r-Verlag: NY 1973 pages 117 to 123, Japanese Patent Application No. 3-73366 and the like were referred to.

Considering the sequence of p-oxybenzoic acid represented by the formula (3), the above (3-1) and (3-2) are considered.
The following four types (3-3-a) and (3-3-b) are possible.

[0025]

[Chemical 8]

However, hereinafter, (3-3-a) and (3-3
-B) is put together and described as (3-3). Here, the molar numbers of (3), (3-1), (3-2), and (3-3) are [3], [3-1], [3-2], and [3-], respectively.
[3], the influence of other chains such as unterminated groups and acid anhydride bonds is sufficiently small, so that the following formula is obtained.

[3] ≈ [3-1] + [3-2] + [3-3] ... (II)

Now, in general, there is a concept of monomer reactivity ratio at the time of producing a high molecular weight copolymer. The probability W that there are three types of monomers M ₁ , M ₂ , and M ₃ and M ₁ or M ₂ enters next to the active species to M ₁ * is represented by the following formula.

[0029]

[Equation 5]

[0030] Here, k ₁₁ is the reaction rate constant M ₁ enters the next ~M ₁ *, k ₁₂ is the reaction rate constant k ₁₃ where M ₂ enters the next ~M ₁ * is next to ~M ₁ * The reaction rate constants in which M ₃ enters are R ₁ = k _{11 /} k _{13 and} R ₂ = k ₁₂ / k ₁₃ . After all R ₁
Is a reaction rate ratio in which M ₁ and M ₃ enter next to ˜M ₁ *, that is, a ratio of easiness of formation of M ₁ -M ₁ chain and M ₁ -M ₃ chain.

On the other hand, since the system of the present invention is a sequential reaction and side reactions such as transesterification are also considered, the above monomer reactivity ratio does not immediately determine the composition and sequence of the polymer, but the same concept You can That is, when the proportion of the structural unit M ₁ or the structural unit M ₂ next to the structural unit M ₁ and is W, considered as of formula (III).

[0032]

[Equation 6]

Hereinafter, r is referred to as a sequence productivity ratio.
M ₁ as a structural unit (3) and M ₂ as a structural unit (4), M
Considering that ₃ is a structural unit (2) and (2) and (4) can form a bond at both ends, formula (IV) is obtained.

[0034]

[Equation 7]

On the other hand, W is a ratio of (3) or (4) next to (3), that is, W = ([3-2] + [3-3]) / [3]. Since it is [3] and [3-1] that can be measured by analysis, W = ([3]-[3-1]) / [3] by substituting the relationship of the formula (II), the above formula ( I) is derived.

Next, the meaning of the sequence generation ratio r will be described. When r> 1, it means that the ratio of (3) or C = O side is (3) or (4) is larger than the ratio of (2). That is, when r> 1, it means that the ratio of (3-1) generated is low. As r becomes larger, (3) is more likely to form a chain with (3) or (4), and (3-1) is less likely to be produced. This case is expressed as a block.

When r≈1, it means that the ratio of (2) on the C = O side of (3) is equal to the ratio of (3) or (4).

That is, when r≈1, [3-1] / [3] and ([3] + [4]) / ([3] + [4] + [2]) are equivalent. This case is expressed as random. When r <1, it means that the ratio of (2) near the C = O side of (3) is high. The smaller r is, the higher the generation ratio of (3-1) is. This case is expressed as alternate.

When r = 0, the left side of the equation (I) = 0, so that [3] = [3-1]. That is, all of (3) on the C = O side means (2). However, as described above, r = 0 when [3] exceeds twice [2].
However, r is substantially ([3] -2 × [2]) /
[3] ≦ r and r = ([3] −2 × [2]) /
In the case of [3], it can be said in a sense as an ideal alternating copolymer. From another point of view, when r> 1, it means that the sequence fraction of the following formula (1-1), which is a chain of (1) and (2), is large.

[0040]

[Chemical 9]

When r≈1, it means that the sequence of (1-1) exists in a continuous random fraction, and when r <1, it means that the sequence of (1-1) decreases. To do. That is, the polyesteramide of the present invention is (1-
In other words, the sequence of 1) is few.

Next, the structural units (1) to (4) will be described. R of the dicarboxylic acid unit represented by the structural unit (1)
Is a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and specifically, Ph (1,4-phenylene), Ph '
(1,3-phenylene), 2,6-naphthyl, Ph-P
h, Ph'-Ph ', Ph-X-Ph, Ph-X-P
h '(wherein X is _{O, S, SO 2, CH} 2, C (CH 2) _can be _2, etc. is improved), and the like. From now on, they may be used alone or may be mixed to form a copolymer. Of these, Ph, Ph'2,6-naphthyl, P
h-Ph and Ph'-Ph 'are preferable. When used alone, Ph, 2,6-naphthyl and Ph-Ph are preferred.
Ph, 2,6-naphthyl is particularly preferable. Even when they are used as a mixture, at least one unit is preferably selected from one of Ph, 2,6-naphthyl and Ph-Ph, and the sum of these is 50% or more, more preferably 66 in terms of the molar ratio of R. It should be at least%.

Examples of preferred mixed systems include Ph and P
h ', Ph and 2,6-naphthyl, Ph and Ph-Ph, P
Examples thereof include h'and Ph-Ph, Ph-Ph and 2,6 naphthyl. Of course, three or more kinds may be used from now on, but up to two kinds are preferable. The aminophenol unit represented by the structural unit (4) is a paraaminophenol residue (4-p) and / or a metaaminophenol residue (4
-M). The ratio of (4-p) and (4-m) is such that the ratio of para-aminophenol residues is preferably more than 50%, more preferably 80% or more, and particularly preferably 90% or more.

The ratio of the molar numbers [1] and [3] of the structural unit (1) to the structural unit (3) satisfies 0.65 ≦ [3] / ([1] + [3]) ≦ 0.88. There is a need. If 0.65> [3] /
When it is ([1] + [3]), the heat resistance decreases, which is not preferable. From the viewpoint of heat resistance, 0.68 ≦
[3] / ([1] + [3]) More preferably, 0.70
≦ [3] / ([1] + [3]). On the other hand, the upper limit is [3] / ([1] + [3]) ≦ 0.88. If the amount of [3] is larger than this, the absolute amount of (3-2), which is the chain of (3), increases, which is not preferable. 0.68 of this
≦ [3] / ([1] + [3]) ≦ 0.86 is preferable,
Furthermore, 0.70 ≦ [3] / ([1] + [3]) ≦ 0.85
Is particularly preferable and 0.75 ≦ [3] / ([1] +
[3]) ≦ 0.85 is most preferable.

When the number of moles of (2) is [2], [1]
The ratio of [2] and [2] is 0.8 to increase the polymerization degree.
0 ≦ [1] / [2] ≦ 1.2, preferably 0.85 ≦
[1] / [2] ≦ 1.15 More preferably 0.90 ≦
[1] / [2] ≦ 1.10.

In order to improve the hydrolysis resistance,
0.80 ≦ [1] / [2] ≦ 1.0 is preferable, and when capping the terminal group, conversely 1.0 ≦ [1] / [2]
≦ 1.2 is preferable.

Regarding the ratio of (4), 0.02 ≦ [4]
/([3]+[4])≦0.30. If the ratio of [4] is less than the lower limit, the heat resistance is lowered and the strength is lowered, which is not preferable. If the content exceeds the upper limit, the melting temperature becomes high, and the molding temperature becomes high, which is not preferable.

A more preferable range is [4] / ([3] +
[4]) = A is preferably 0.03 ≦ A ≦ 0.2
0, and more preferably 0.04 ≦ A ≦ 0.15.
In terms of mechanical properties, R in (1) is 1.4-phenylene,
When [1] / [3] = 20/80, the liquid crystalline polyesteramide of the present invention has a breaking elongation and a strength (tensileness, bending) of about 20% as compared with the conventional liquid crystalline polyesteramide.
The above is improved and the heat resistance is also improved. Since the sequence is alternated, the structure (especially higher-order structure) does not remain after melting, so the melt viscosity is low and it can be formed at low temperature.
Further, since it has a uniform structure, it is easily dissolved in a solvent, and the crystallinity is improved when compared with the same composition ratio.

Next, a method of obtaining r will be described. The polymers of the invention cannot simply be determined from NMR.
Therefore, the inventors of the present invention have made earnest studies and found a method for obtaining r. That is, when the liquid crystalline polyesteramide of the present invention is reacted with a primary amine, the ester bond of (3-1) remains without being selectively cleaved and other ester bond (for example, the ester bond of (3-2)) is left. ) Is disconnected. By utilizing this, the sequence of the liquid crystalline polyesteramide of the present invention can be analyzed.

The present measuring method will be described in more detail. For example, the liquid crystalline polyesteramide of the present invention is pulverized, and a large excess of n-propylamine is added to the pulverized sample at 40 ° C. for 90 minutes.
The component material of (3-1) is measured by treating for ¹ minute and then measuring the obtained decomposition product by ¹ H-NMR. (1), (2), (3), determined by methanol decomposition
R can be calculated from the ratio of (4) and the component amount of (3-1). According to this method, the C = O of the compound of (3)
Information on the side sequence will be obtained.

Regarding the melt viscosity, the polyesteramide of the present invention generally exhibits a low melt viscosity because it exhibits liquid crystallinity. For example 275 ° C., 10 ³ sec melt viscosity at ^-1 5000 poise, preferably 30 to 3000 poise, more preferably 100 to 2500 poise. Most preferably, it is 200 to 2000 poise. Further, the liquid crystalline polyesteramide of the present invention has 275 ° C. and 295 ° C.
One of the characteristics is that the value of the melt viscosity ratio in is small.

The melt viscosity is a value measured at 30 ° C. by dissolving p-chlorophenol / o-dichlorobenzene (1/1) as a solvent at room temperature to a concentration of 0.5 g / dl. Next, the liquid crystalline polyesteramide of the present invention will be described. The sequence controlled liquid crystalline polyesteramide of the present invention may be produced by any method. For example, an interfacial polycondensation method, a solution polycondensation method, a melt polycondensation method, etc. can be considered.

As the interfacial polycondensation method, for example, there is a method using acid chloride. As the solution polycondensation method, the method of Higashi et al., That is, the direct polycondensation method can be considered. As the melt polycondensation method, an acetate method, a phenyl ester method and the like can be considered. In this report, it was produced by the melt polycondensation method by taking advantage of the fact that the transesterification of the structural unit (2) is unexpectedly unlikely to occur at high temperatures. That is, as a method for producing a polyester in which r satisfies the above range, the present inventors have made it possible to easily form the chain of (3-1), from the beginning, that is, at the time of the raw material, the structural unit of (3-1) Keep a lot. That is, compounds represented by the following chemical formulas (5) and (6) are used as raw materials.

[0054]

[Chemical 10]

(Here, Z ₁ , Z ₂ and Z ₃ are each a hydrogen atom and / or an acetyl group.) An example of the production method will be further described. The compound (5) and HOOCRCO are described below.
OH (7) In addition, further, Z ₄ X-Ph-COOH
(8) is added (Z ₄ is synonymous with Z ₁ and Ph is 1.4
-Fenlene divalent residue is shown), and acetic anhydride is added if necessary, and acetylation is performed at 100 to 170 ° C. This is 5 minutes to 3 hours, preferably 20 minutes to 1.5 hours. The amount of acetic anhydride is preferably about the same as the hydroxyl group and amino group of the raw material and about 1.5 times the amount. It is preferably 1.1 to 1.4 times the amount of hydroxyl groups and amino groups.

The ratio of (5) to (7) is 0.85 ≦
[7] / [5] ≦ 1.15 is preferable, and particularly 0.9 ≦
[7] / [5] ≦ 1.1 is preferable. Alternatively, it is also possible to start from compound (6) above. _{That, Z 3 O-Ph-COOCH} 2 CH 2 OH (6) HOOCRCOOH (7) Z 4 O-PhCOOH (8)

Acetic anhydride is added to and acetylation is carried out at 100 to 170 ° C. This is 5 minutes to 3 hours, preferably 20 minutes to 1.5 hours. The amount of acetic anhydride is (6-1) when Z ₃ = H in (6), (8-1) when Z = H in (8) and acetic anhydride (9), and the number of moles of each is To [7
−1] and [6-1] [9] 1.0 ≦ [9] / ([6-1] + [8-1]) ≦ 1.5 Particularly preferably 1.1 ≦ [9] / ([6-1) + [8
−1]) ≦ 1.4.

Before the acetylation, (6), (7) and (8) may be reacted in advance, and (6),
(8) may be reacted in advance. In that case, it is preferable to carry out in the range of 1.0 ≦ [8] / [6] ≦ 4.0, particularly 1.0 ≦ [8] /
[6] ≦ 2.0 is preferable.

This reaction may be carried out using a solvent, but it is preferably carried out without a solvent in consideration of subsequent removal.
In the case of reacting (6) with (8) and / or (7), it is preferable to melt (8) and / or (7) where (6) is molten. The temperature is 145-2
It is preferably carried out at 20 ° C. From the viewpoint of the degree of polymerization, the ratio of (6) and (7) is preferably 0.8 ≦ [6] / [7] ≦ 1.2, and further 0.9 ≦ [6] / [7] ≦ 1.1. More preferable.

As a total charging ratio, the ratio of [6] and [8] is 1 ≦ [8] / [6] ≦ 5, preferably 1
≦ [8] / [6] ≦ 3.5. All / or a part of (7), (8-2) (when Z _{4 of} (8) is an acetyl group is (8-2)), all / or a part thereof is being acetylated, and You may add after conversion. The reaction can be carried out without a catalyst, and a catalyst may be added if necessary.

Thereafter, the temperature is raised to start polymerization. 220 polymerization
Polymerization is carried out at ˜340 ° C., preferably at 260˜320 ° C. It is particularly preferable to carry out at 265 to 300 ° C. Most preferably, it is 265 to 290 ° C. It also has the advantage that it can be polymerized at low temperature in spite of its heat resistance. The time required for gradually reducing the pressure from 760 mmHg to 1 mmHg is 30 minutes or more, preferably 6 minutes.
It is carried out for more than 0 minutes, especially from 30mmHg to 1m
It is important to gradually reduce the pressure to mHg.

It is possible to carry out without polymerization at the time of polymerization, but if necessary, it is carried out in the presence of a catalyst. As the catalyst to be used, an ester exchange catalyst, a polycondensation catalyst, an acylation catalyst and a decarboxylic acid catalyst are used, and they may be mixed and used from now on. Preferred catalysts are Ti (OBu) ₄ ,
BuSnOOH, Sn (OAc) ₂ , Sb ₂ O ₃ , Fe
(Acac) ₃ , Zn (OAc) ₂ , Co (OAc) ₂ ,
NaOAc, KOAc, etc. are mentioned. The amount used is 5 to 50,000 ppm, preferably 50, based on the polymer.
~ 5,000 ppm.

The polymerization time may be 10 hours or less, preferably 7 hours or less. Most preferably, it is performed within 1 to 4 hours. Although this polymerization has the advantage that it can be carried out at a low temperature, it has the advantage that it can be easily extracted even if it is carried out at a low temperature, and no trouble occurs during the extraction. This may also be due to the fact that the sequence is controlled more alternately.

[0064]

EFFECTS OF THE INVENTION The characteristics of the liquid crystalline polyesteramide in which the sequence of the present invention is controlled alternately are: 1. It has high tensile strength and bending strength. 2. Has high impact strength. 3. Has a high elongation at break. 4. High heat resistance with the same composition and composition ratio. 5. Good fluidity with the same composition and composition ratio. Etc. The physical properties of the polymer of the present invention are far superior to the conventional ones in terms of balance between mechanical properties and heat resistance, and individual physical properties may be inferior. Further, since the heat resistance is high, the fluidity is good, so that the polymerization temperature and the molding temperature can be lowered, which means that a polymer having good heat resistance can be produced by a conventional production apparatus.

Therefore, it is very useful as a product such as a molding material, a film and a fiber having a high degree of characteristics. In particular, it has become possible to apply it to fields that were previously unavailable. Furthermore, as the sequences etc. become more alternating,
It can be expected that the crystallinity is improved in the case of the same composition ratio (that is, by becoming more uniform). This is D
The degree can be grasped from SC and X-ray scattering.

[0066]

The present invention will be described in more detail below.
The present invention is not limited to the following examples unless it exceeds the gist. The melt viscosity in the examples was measured using a Shimadzu flow tester, and the shear rate (r) was used.
1000sec ^-1 , cylinder nozzle length 1 diameter = 2
0 was used. The optical anisotropy (liquid crystallinity) was observed using a polarization microscope with a hot stage.

The molding was performed using a 0.1 oz injection molding machine manufactured by Nippon Steel Co., Ltd. Tensile properties (tensile modulus, tensile strength, elongation at break) were measured for the 0.1 oz molded product using TENSILON / UTMIIIL manufactured by Toyo Baldwin. As the measurement of heat resistance, the Vicat softening temperature was measured. Vicat softening temperature is Toyo Seiki's automatic HDT
Using the equipment, the sample was
It is the temperature at which the needle penetrated 1 mm at a temperature rising rate of 0 ° C./hr. ¹ H-NMR is AM-5 manufactured by BRUKER
00 was used and measurement was performed at 500 MHz.

Example 1 48.6 of a diol compound represented by the following chemical formula (11) was placed in a glass polymerization tube equipped with a stirring blade, a nitrogen inlet and a pressure reducing port.
g (0.161 mol), terephthalic acid 33.4 g (0.
201 g), 33.4 g of p-hydroxybenzoic acid (0.
242 mol) and 4.4 g of p-aminophenol
(0.040 mol) was charged, and after replacing with N _{2 under} reduced pressure, 82.1 g (0.81) of acetic anhydride was further added, and the system was heated to 140 ° C. with stirring and kept at 140 ° C. for 1 hour.

[0069]

[Chemical 11]

Thereafter, the temperature was raised to 275 ° C. over 1.5 hours, and when the temperature reached 275 ° C., depressurization was started. The pressure was reduced to 10 mmHg in the first hour and then to 0.3 mmHg for 1.5 hours. The torque was sufficiently increased 4 hours after the start of the pressure reduction, and the polymerization was terminated. Then, the mixture was left standing and pressure was restored to extract the polymer from the polymerization tube. The extraction was very good.

After being made into chips, it was dried at 120 ° C. overnight. The melt viscosity of this polymer is 275 ° C. 1000 sec.
^{At -1} , it was 650 poise. Further, this polymer, which was confirmed to be a liquid crystal by a polarization microscope, had r = 0.75. Incidentally, FIG. 1 shows an NMR chart after amine decomposition used for obtaining r = 0.75.

The tensile property of this polymer is that the elongation at break is 4.
The tensile strength was 2%, the tensile strength was 2,350 kg / cm ² , and the tensile elastic modulus was 9.0 × 10 ⁴ kg / cm ² . The Vicat softening temperature was 215 ° C. Also, this polymer was dissolved in a mixed solvent of p-chlorophenol / o-dichlorobenzene and found to be uniform.

After decomposition with methanol, the composition ratio of each polymer obtained by gas chromatography was [1] = 20.8 mol%, [2] = 16.7 mol%,
[3] = 58.3 mol% and [4] = 4.1 mol%. It should be noted that, in detail, how to obtain r is 4.57 ppm d derived from (3-1) in FIG.
45-4.25 ppm c and 3.95-3.80 p
Based on the integral value of the name signal of b of pm and the integral value of f of 7.70 ppm derived from (3-2), [3
−1] / [3] was calculated. [3] = [3-1] +
[3-2] is set.

[0074]

[Equation 8]

The r value was calculated by substituting the quantitative values of [1], [2], [3], and [4] above and [3-1] / [3] above into the formula (I).

Example 2 29.3 g (0.161 g) of a diol compound represented by the following chemical formula (12) was placed in a glass tube equipped with a stirring blade, a nitrogen inlet and a pressure reducing port.
, P-acetyloxybenzoic acid 72.5 g (0.
(403 mol) was charged, the pressure was replaced with nitrogen under reduced pressure, and the system was heated with stirring with a nitrogen flow.

[0077]

[Chemical formula 12]

After becoming transparent at 200 ° C., the mixture was kept for 2 hours for reaction. Next, terephthalic acid 33.4 g (0.201
Mol), 4.4 g (0.040 mol) of p-aminophenol, and 30.7 g (0.301 mol) of acetic anhydride were added, and the mixture was held for 1 hour at 140 ° while stirring. Then, the temperature was raised to 275 ° C. over 1.5 hours and depressurization was started. Three hours after the depressurization was started, the torque was sufficient, so that the polymerization was terminated. Then, the mixture was allowed to stand still and the pressure was restored to extract the polymer from the bottom of the polymerization tube. The extractability was very good.

After being made into chips, it was dried at 120 ° C. overnight. The melt viscosity of this polymer is 275 ° C. 1000 sec.
^{At -1} , it was 530 poise. Moreover, it confirmed that it was a liquid crystal with a polarization microscope. The tensile properties of this polymer are: elongation at break 4.8%, tensile strength 2,630 kg / cm.
² Tensile elastic modulus was 9.5 × 10 ⁴ kg / cm ² . The bigat softening temperature was 210 ° C. Further, this polymer was dissolved in a p-chlorophenol / o-dichlorobenzene mixed solvent and found to be uniform.

Comparative Example 1 Oligoethylene terephthalate, p-hydroxybenzoic acid terephthalic acid and p-aminophenol were used as raw materials, and the composition ratio was made to be the same as that of the example based on the method described in Japanese Patent Application No. 2-041817. Manufactured. The melt viscosity of the obtained polymer is 2500 at 275 ° C. and 1000 sec ⁻¹ .
It was a poise. The r value of this polymer was 0.98. The tensile properties are as follows: elongation at break 3.7%, tensile strength 1,
330 kg / cm ² , tensile elastic modulus 7.3 × 10 ⁴ kg / c
It was m ² . The Vicat softening temperature was 145 ° C.

Comparative Example 2 Polyethylene terephthalate, p-acetoxybenzoic acid, terephthalic acid and p-aminophenol diacetate were used as raw materials, and the composition ratio was the same as in Example 1 by the method described in JP-B-59-13531. Was manufactured. (In Japanese Examined Patent Publication, for example, p-aminophenol diacetate is replaced by hydroquinone diacetate.) The melt viscosity of the obtained polymer is 275 ° C. 1000.
It was 3200 poise at sec ^-1 . R of this polymer
The value was 1.33, and the tensile properties were elongation at break 3.1.
%, And the tensile strength was 1,220 kg / cm ² .

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of an amine decomposition product of a liquid crystalline polyesteramide obtained in Example 1.

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[Procedure amendment]

[Submission date] December 1, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The upper limit of r is preferably 0.85 or less, more preferably 0.83 or less, still more preferably 0.80.
Hereafter, it is most preferably 0.75 or less. In addition, when calculating [3-1] in the above formula (I), it should be noted that the unit of the following formula has two units of (3-1).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

After being made into chips, it was dried at 120 ° C. overnight. The melt viscosity of this polymer is 275 ° C. 1000 sec.
^{At -1} , it was 530 poise. Moreover, it confirmed that it was a liquid crystal with a polarization microscope. This polymer has r = 0.7
It was 0. The tensile properties of this polymer are: elongation at break 4.
8%, tensile strength 2,630 kg / cm ² tensile elastic modulus 9.
It was 5 × 10 ⁴ kg / cm ² . The bigat softening temperature was 210 ° C. Further, this polymer was dissolved in a p-chlorophenol / o-dichlorobenzene mixed solvent and found to be uniform.

Continuation of the front page (72) Inventor Ikuyuki Sakata 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (2)

[Claims] 1. A dicarboxylic acid residue represented by the following chemical formula (1), a diol residue represented by the following chemical formula (2),
A liquid crystalline polyesteramide comprising a p-oxybenzoic acid residue represented by the chemical formula (3) and an aminophenol residue represented by the chemical formula (4) and satisfying the following conditions (a), (b) and (c). [Chemical 1] (In the above formula (1), R represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms) (a) The above chemical formulas (1), (2),
The molar numbers of (3) and (4) are [1], [2],
When [3] and [4] are set, Is. (B) The p-oxybenzoic acid residue represented by the above formula (3), which is directly linked to the diol residue represented by the formula (2), is designated as (3-1), and (3-1) When the number of moles of) is [3-1], r obtained from the following formula (I)
Is 0 ≦ r ≦ 0.88. [Chemical 2] (The unit corresponding to the underlined part is (3-1).) (C) Melt viscosity measured at 300 ° C (shear rate 100
(At ⁰ sec ⁻¹ ) is 50 poise or more. 2. A unit of chemical formula (1) and a chemical formula (3)
2. The liquid crystalline polyesteramide according to claim 1, wherein the molar ratio of the units is 0.7 ≦ [3] / ([1] + [3]) ≦ 0.85.