JP2932570B2 - Copolyesteramide and method for producing the same - Google Patents

Description

The present invention relates to a novel copolymerized polyester amide having a high elastic modulus, a high strength, a high elongation, excellent heat resistance, excellent adhesiveness and a low water absorption, and a novel copolymerized polyester amide. The present invention relates to a production method, which relates to a copolymerized polyesteramide which forms a thermotropic liquid crystal at the time of molding and thus has excellent moldability and can be used as a product such as a molding material, a film or a fiber.

Further, according to the production method of the present invention, not only has the advantage that it can be produced with a conventional production apparatus, but also because it produces a flexible component in the reaction system, it has an excellent balance between heat resistance and mechanical performance. A copolymerized polyesteramide can be obtained.

[Conventional technology and problems]

In recent years, there has been an increasing demand for materials having excellent rigidity, strength, elongation, and heat resistance, regardless of any of fibers, films, and molded products. Polyester has been widely accepted for use in general molded products, but many polyesters have poor flexural modulus and flexural strength, so they were not suitable for applications requiring high modulus and high strength. .

In recent years, liquid crystalline polyesters have attracted attention as polyesters suitable for applications requiring high elastic modulus and high strength. Of particular interest has been the publication of Journal of Polymer Science Polymer Chemistry Edition Vol. 14 (1976), p. 2043, and Japanese Patent Publication No. Since the announcement of a thermo-liquid crystal polymer consisting of Jackson reports that this liquid crystal polymer exhibits more than five times the rigidity, more than four times the strength, and more than 25 times the impact strength of polyethylene terephthalate, demonstrating new possibilities for highly functional resins. Indicated.

However, the polymer by Jackson et al.
The heat distortion temperature (HDT) was low, heat resistance was poor, and there was a drawback that it was brittle. Therefore, Jackson et al., As components of the polymer, components (1) and (2) described below, By adding ingredients to polyester amide, HD
T and Rockwell hardness were improved.

However, this not only resulted in a higher melt viscosity and lower fluidity than a polymer composed of only the components (1) and (2), but also an HDT of at most 100 ° C. or less. (USP 4182842: Journal of Applied Polymer Science, Vol. 25 (1980) 1685-1694) Also, Jackson et al. Added aliphatic dicarboxylic acid and (4) to the components (1) and (3). Has developed polyester amide, but HDT is still only 114 ° C,
And the liquidity deteriorated. (US Pat. No. 3,859,251) JP-A-64-33123 proposes a novel polyesteramide, but it needs to contain a residue of —O—Ar—O— (Ar: aromatic compound).

Other polyesteramides are described in JP-A-57-14.
5123, 57-172921, 57-177020, 58-29820, 5
8-172, 58-89618, 61-236826, 63-120729,
64-31829, 64-31830, 1-190728, 1-1975
There are 25 grades, all of which use special compounds or wholly aromatic polyesteramides.

The present inventors have previously found and applied for a polyester amide excellent in heat resistance and fluidity (Japanese Patent Application No. 63-163).
No. 210154), however, as a result of intensive studies on polyester amides having excellent heat resistance, fluidity and mechanical properties, low water absorption and good adhesion, it was very surprising that a copolymer polyester having the following components was obtained. Amides have been found to achieve the above object, and have reached the present invention.

That is, the gist of the present invention is: (1) (A) 5-35 mol% of an aromatic dicarboxylic acid residue represented by the formula (1), (B) 5 to 35 mol% of an ethylene glycol residue represented by the formula (2), —O—CH ₂ CH ₂ —O— (2) (c) 30 to 80 mol% of the formula (3) Aromatic oxycarboxylic acid residue, (D) 2 to 20 mol% of an aminophenol residue represented by the formula (4), (R: a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) (E) 1 to 15 mol% of an ether-containing oxycarboxylic acid residue represented by the formula (5), (Here, when the number of moles of (1), (2), (3), (4) and (5) is represented by [1], [2], [3], [4] and [5], % Is a value with respect to the sum of [1] to [5].
Note that [5] does not include [2] and [3]. A) a copolymerized polyester amide mainly consisting of: a copolymerized polyester amide having a melt viscosity at 290 ° C. and 1000 sec ⁻¹ of 10 poise or more, and a method for producing the same. 5 to 50 mol% of a polyester or oligomer ester comprising a repeating unit represented by the general formula (6) (the weight of the repeating unit is 192, which corresponds to 1 mol), and 30-90 mol% of hydroxybenzoic acid represented by the general formula (7) is reacted to form a copolymerized oligomer (first step),
Next, acylation is carried out by adding an acylating agent (second step), and polymerization is carried out under reduced pressure (third step). In the three-step reaction, before the completion of the second step, the compound represented by the general formula (8) (R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) 2 to 20 mol% of an aminophenol represented by the general formula (9) 2 to 20 mol% of terephthalic acid and / or isophthalic acid (where the number of moles of (6), (7), (8) and (9) is [6], [7], [8], [8] [9], the mol% is a value based on the sum of [6] to [9].) The present invention is directed to a method for producing a copolymerized polyesteramide, characterized by adding and reacting.

 Hereinafter, the present invention will be described in detail.

The copolymerized polyesteramide of the present invention exhibits optical anisotropy (liquid crystallinity) in a specific molten phase, and is characterized by high rigidity, high strength, high elongation at break, and excellent heat resistance. In addition to having water-absorbing properties, it has low water absorption and good adhesion to metals and the like. For example, it shows excellent adhesiveness to stainless steel, iron, aluminum, copper, phosphor bronze and the like.

Further, the copolymerized polyesteramide of the present invention exhibits excellent liquidity because it exhibits liquid crystallinity. (Although it is a polyesteramide, it has fluidity comparable to that of polyester.) The copolymerized polyesteramide of the present invention is represented by the above formulas (1), (2), (3), (4) and (5). It is mainly composed of constituent components, and it is essential that the components (1) to (5) are included. The inclusion of the component (5) is preferable in terms of mechanical properties such as elastic modulus, tensile strength, and elongation at break.

Examples of the aromatic dicarboxylic acid residue represented by the formula (1) include a terephthalic acid residue and / or an isophthalic acid residue. Terephthalic acid residues and isophthalic acid residues may be used alone or as a mixture to form a copolymer. When the copolymer is used, the amount of terephthalic acid residues is preferably larger than the amount of isophthalic acid residues, and it is most preferable to use terephthalic acid alone.

The content ratio of the dicarboxylic acid residue represented by the formula (1) is
It is 5 to 35 mol%, preferably 10 to the sum of [1] to [5] (hereinafter sometimes referred to as [A]).
-30 mol%, more preferably 15-25 mol%. If it is less than 5 mol%, the fluidity will be deteriorated, and if it exceeds 35 mol%, the heat resistance will be undesirably deteriorated.

The content ratio of the ethylene glycol residue represented by the formula (2) is 5 to 35 mol% with respect to [A], preferably 10 to 35 mol%.
-30 mol%, more preferably 12-20 mol%. If it is less than 5 mol%, the fluidity will be deteriorated, and if it exceeds 35 mol%, the heat resistance will be undesirably deteriorated.

Specific examples of the oxybenzoic acid residue represented by the formula (3) include p-hydroxybenzoic acid and m-hydroxybenzoic acid.

Each of these residues may be used alone or as a copolymer. When a p-hydroxybenzoic acid residue and an m-hydroxybenzoic acid residue are used as a copolymer, it is preferable to increase the amount of the p-hydroxybenzoic acid residue. Most preferably, the p-hydroxybenzoic acid residue is used alone.

The content ratio of the oxybenzoic acid residue represented by the formula (3) is 30 to 80 mol%, preferably 40 to 80 mol%, based on [A].
~ 75 mol%, more preferably 45-70 mol%, most preferably 50-65 mol%.

If it is less than 30 mol%, the heat resistance decreases, and 80 mol%
If it exceeds, the fluidity decreases, which is not preferable.

Specific examples of the aminophenol residue represented by the formula (4) include, for example, p-aminophenol, m-aminophenol, pN-methylaminophenol, mN-methylaminophenol, p-N-phenylamino Residues such as phenol may be mentioned, and these may be used alone or in combination of two or more.

Of these, p-aminophenol and m-aminophenol residues are preferred.

The content ratio of the aminophenol residue represented by the formula (4) is 2 to 20% by mole, preferably 3 to 10% by mole, more preferably 3 to 7% by mole based on [A].

If it is less than 2 mol%, the mechanical properties and heat resistance are reduced, and the adhesion is undesirably reduced. If it exceeds 20 mol%, it is not preferable because the drawability is poor, the fluidity is deteriorated, and the water absorption is deteriorated.

The presence of the above components and the ether-containing oxycarboxylic acid represented by the formula (5) gives more excellent properties.

Specific examples of the ether-containing oxycarboxylic acid residue represented by the formula (5) include 4-β-hydroxyethoxybenzoic acid and 3-β-hydroxybenzoic acid.
Residues of hydroxybenzoic acid can be mentioned.

 One or more of these residues may be present.

In particular, it preferably contains a 4-β-hydroxyethoxybenzoic acid residue.

The content ratio of the ether-containing oxycarboxylic acid residue represented by the formula (5) is preferably 1 to 15 mol% with respect to [A].
In this range, mechanical properties and fluidity are particularly improved. If it is contained even at 1 mol%, the elastic modulus, strength and elongation are improved, but if it exceeds 15 mol%, heat resistance is undesirably lowered. It is preferably 1 to 12 mol%, more preferably 2 to 10 mol%, particularly preferably 2 to 7 mol%.

From the viewpoint of increasing the degree of polymerization, 0.85 [1] /
([2] + [4]) 1.15 is preferred, especially 0.90
[1] / ([2] + [4]) 1.10.

The inclusion of a small amount (approximately 2 equivalent% or less) of components other than the components listed here may be no problem.

Surprisingly, by containing these constituents, the polymer obtained in the present invention exhibits optical anisotropy (has liquid crystallinity) in the molten phase, and therefore has excellent moldability.

The polyesteramides of the present invention are not inferior in fluidity, elastic modulus and strength at all, but rather excellent in comparison with the corresponding polyesters, and are also greatly improved in heat resistance.

In addition, despite the presence of amide bonds, the water absorption is low and the adhesiveness is excellent.

According to the production method of the present invention, this ether-containing oxycarboxylic acid residue (5) can be synthesized in a reaction system (resulting from the reaction of (6) and (7)), and thus corresponds to the component (5). In addition to the advantage that it is not necessary to use the compound as a starting material, the addition of the component (5) has the characteristic that the balance between heat resistance and mechanical properties can be improved.

Further, the copolymer polyesteramide of the present invention can be produced by a usual polyester production apparatus (320 ° C. or lower). In addition, that it can be manufactured means that it can flow without solidifying in the polymerization tank, and can be extracted from the polymerization tank (has good extraction property).

 Next, the manufacturing method will be described.

The copolyesteramide of the present invention can be produced by various production methods. For example, there may be a melt polymerization method, a solution polymerization method, an interfacial polymerization method, etc., but the melt polymerization method is preferred from the viewpoint of simplicity of the process.

In the melt polymerization method, it can be produced by various methods. For example, the aforementioned Journal of Polymer Science Polymer Chemistry Edition
14 (1976), p. 2043 and JP-B-56-18016, that is, a method using various acetates as a starting material, or using a hydroxylated compound as a starting material and adding an acylating agent from the beginning. Although the method may be used, it is more preferable to produce according to the methods described in JP-A-60-186525 and JP-A-62-41220.

In order to explain the production method in more detail, polyethylene terephthalate or oligoethylene terephthalate is preferred as the polyester or oligoester comprising a repeating unit represented by the general formula (6). Particularly, oligoethylene terephthalate is preferred.

As the hydroxycarboxylic acid represented by the general formula (7), p-hydroxybenzoic acid and / or m-hydroxybenzoic acid are used.

As a reaction method, the raw material polyester or oligoester and hydroxybenzoic acid are brought into contact with each other under normal pressure to 200 to 320.
A first step of forming a copolymerized oligomer by heating at
It comprises a second step of performing acylation by adding an acylating agent, and a third step of polymerizing at 250 to 340 ° C. under reduced pressure. In this case, it is preferable to use acetic anhydride as the acylating agent in the second step.

The first reaction may be carried out at any temperature in the range of 210 to 300 ° C, but particularly preferably at 220 to 260 ° C, and the reaction is carried out for 20 minutes to 5 hours.

 During this reaction, the component (5) is generated.

Further, an ether-containing oxycarboxylic acid represented by the following formula (9) corresponding to the residue represented by the formula (5) May be added from the beginning.

As the ether-containing oxycarboxylic acid, 4-β-
Hydroxyethoxybenzoic acid, and 3-β-hydroxyethoxybenzoic acid can be mentioned.

The reaction can be carried out without a catalyst, but if necessary, a catalyst may be added.

The amount of the acylating agent in the second step is preferably about the same amount to about 1.5 times as much as the number of moles constituting the components (3) and (4) among the raw materials added by the end of the second step. .

When acetic anhydride is used as the acylating agent, the acylation reaction is preferably performed at 100 to 180 ° C.

The reaction time is usually in the range of 10 minutes to 10 hours.

The aminophenol represented by the general formula (8) and tereic and / or isophthalic acid may be added at any time before the completion of the second step, but is particularly preferably added after the completion of the first step reaction. It is also possible to add the above-mentioned aminophenol from the beginning to participate in the first-stage reaction. Examples of the aminophenol include m-aminophenol, p-aminophenol, pN-methylaminophenol, mN-methylaminophenol, and pN-phenylaminophenol. Further, two or more of these may be contained.

The third stage polymerization is carried out at 250 to 340 ° C.
It is preferably carried out at 0 to 320 ° C. Also, 760mmHg to 1mmHg
The time required for gradually reducing the pressure until 30 minutes or more, preferably 60 minutes or more, is carried out, especially from 30 mmHg to 1 m
It is important to gradually reduce the pressure to mHg.

In the first to third stages, the reaction can be carried out without a catalyst, but the reaction is carried out in the presence of a catalyst if necessary.

As the catalyst used in the first, second and third steps, a transesterification catalyst, a polycondensation catalyst, an acylation catalyst and a decarboxylic acid catalyst are used, and these may be used in combination. Preferred catalysts include Ti (OB
u) ₄ , BuSnOOH, Sn (OAc) ₂ , Zn (OAc) ₂ , Co (OA
c) ₂ , NaOAc, KOAc and the like. The amount used is 5 to 50,000 ppm, preferably 50 to 5,000 ppm, based on the polymer.

The melt viscosity of the final product is 10 poise or more, preferably 30 poise to 5000 poise, more preferably 50 poise to 2000 poise, as measured at 290 ° C. and 1000 sec ⁻¹ . Most preferably, it is 70 poise to 1200 poise.

The number of moles of the compound represented by the above (6), (7), (8) and (9) was changed to [6], [7], [8] and [9], respectively.
Then, the amount of the polyester or oligoester used is 5 to 50 mol% based on the sum of [6] to [8],
Preferably 10-35 mol%, more preferably 12-30 mol%
It is.

The content of hydroxybenzoic acid is 30 to 90 mol%, preferably 40 to 80 mol%, and more preferably 50 to 80 mol%. Moreover, about aminophenol, it is 2-20 mol%, Preferably it is 3-15 mol%, More preferably, it is 3-10 mol%.

For terephthalic acid and / or isophthalic acid,
It is 2 to 20 mol%, preferably 3 to 15 mol%, more preferably 3 to 10 mol%.

In the production of polyesteramide by this production method, there is also an advantage that the polymerization time can be shortened because the polymerization rate is high.

Since the copolymerized polyesteramide of the present invention can show an optically anisotropic phase in the molten phase, it has a very good fluidity, and therefore has good moldability and can be used for general melt molding such as extrusion molding, injection molding, and compression molding. It can be processed into molded articles, films, fibers and the like.

In particular, because of its high fluidity, it is suitable for precision molded products, thin-wall molded products, and the like. For example, it can be used for parts for automobiles, parts for information materials such as compact disks and floppy disks, parts for electronic materials such as connectors and IC sockets, and speaker cones utilizing the magnitude of internal loss.

In addition, it exhibits liquid crystallinity even at a temperature of 350 ° C. or less, and has a feature that it can be molded at a temperature of 350 ° C. or less, particularly 335 ° C. or less due to low fluidity. Further, it has a feature that the mechanical properties are improved as compared with the case where the molding is performed at a temperature exceeding 350 ° C. In particular, it can be molded at a low temperature of 230 ° C to 300 ° C.

Further, at the time of molding, the copolymerized polyesteramide of the present invention, glass fibers, fibers such as carbon fibers, talc, mica, fillers such as calcium carbonate, nucleating agents, pigments, antioxidants, lubricants, other stabilizers, It is also possible to add a filler or an additive such as a flame retardant, a thermoplastic resin or the like to impart desired characteristics to the molded article. In particular, it is preferable to add fibers and fillers because heat resistance is improved and anisotropy is reduced.

It is also possible to create a composition having both the characteristics of the other polymer and the advantages of the copolymerized polyesteramide of the present invention by blending or alloying with another polymer.

〔Example〕

Now, the present invention will be described in further detail with reference to Examples.
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 flow tester (manufactured by Shimadzu Corporation) at a temperature of 290 ° C., a shear rate (γ) of 1000 sec ⁻¹ , and a cylinder nozzle length / diameter = 10.
It was used.

¹ H-NMR was measured as a test sample by dissolving the polymer in trifluoroacetic acid, hexafluoroisopropanol, pentafluorophenol, or the like, using AM-500 manufactured by BRUKER.

Molded pieces for measuring the heat distortion temperature (HDT) were prepared using a Toshiba Machine 2.5 oz injection molding machine.

 The heat distortion temperature was measured according to ASTM-D-648.

The internal loss was measured with Vibron. Vibron uses Toyo Baldwin's Leo Vibron, a molded piece made using a 0.1oz injection molding machine made by Nippon Steel Corporation, 110Hz
Used below.

The tensile properties (tensile modulus, tensile strength, elongation at break) were measured using Toyo Baldwin's TENSILON / UTM-III L
Measurements were made on molded pieces prepared using a 0.1 oz injection molding machine. Also, Tg (glass transition temperature) is a measure of heat resistance.
Was obtained from Vibron's E ″.

The optical anisotropy (liquid crystal properties) was observed using a polarizing microscope equipped with a hot stage.

 The water absorption was measured according to ASTM D-570.

 Adhesion was determined by adhering to a metal surface.

In addition, it was also evaluated whether the obtained polymer could be extracted from the polymerization tank (extraction property).

Example 1 77.3 g (0.56 mol) of p-hydroxybenzoic acid and 30.7 g (0.16 dl / g) of oligoethylene terephthalate (η _inh = 0.12 dl / g) were placed in a glass polymerization tube provided with a stirring blade, a nitrogen inlet, and a vacuum port.
Mol), vacuum-nitrogen substitution was repeated three times, finally filled with nitrogen, and placed under a nitrogen stream at a flow rate of 0.5 / min. After the polymerization tube was heated to 220 ° C., transesterification was performed for 2 hours to produce a copolymerized oligomer.

Then, the temperature was lowered to 140 ° C in about 30 minutes, and terephthalic acid 6.6 g
(0.04 mol), 4.4 g (0.04 mol) of p-aminophenol
Then, 81.6 g (0.80 mol) of acetic anhydride was added dropwise over 30 minutes, and the mixture was further stirred for 1 hour to effect acylation. Thereafter, the temperature of the oil bath was raised to 290 ° C. over one and a half hours, 0.065 g of zinc acetate dihydrate was added, and the pressure was gradually applied to carry out polymerization for 2 hours. The final degree of vacuum was 6 mmHg. The product could flow under its own weight and be withdrawn from the bottom of the reactor. After chipping, 120 ° C
In vacuum overnight. The resulting polymer was milky white and opaque.

The melt viscosity of this polymer is 460 at 290 ° C. and 1000 sec ⁻¹ .
Poise. At this time, the polymer exhibited liquid crystallinity.

In addition, the tensile properties of molded pieces produced by a 0.1 oz injection molding machine are as follows: tensile elastic modulus 73,000 kg / cm ² , tensile strength 1,330 kg / cm ² ,
The elongation at break was 3.7%. In general, a breaking elongation of less than 3% is fragile, while a breaking elongation of more than 3.5% can be said to be a very tenacious resin.

The Tg was 96 ° C. and the internal loss was 0.06. HDT 131
° C, the water absorption was as low as 0.04%, and the adhesion to metal was good.

The ¹ H-NMR chart of this polymer is shown in FIG.

In the NMR chart, the above-mentioned components (1) to (5) can be quantified from the following chemical shifts.

(1) 8.0 to 8.8 ppm (2) 4.7 to 5.2 ppm (3) 7.0 to 7.7 ppm, 8.0 to 8.8 ppm (4) 7.8 ppm (5) 4.6 ppm Mol% (2) 16.6 mol% (3) 56.7 mol% (4) 4.1 mol% (5) 2.8 mol%, which corresponded to the charged amount.

The results of elemental analysis were as follows: C: 67.47% (67.88%) H: 3.50% (3.64%) N: 0.60% (0.52%) (Calculated values in parentheses) Example 2 In the same reactor as in Example 1, 66.2 g (0.48 mol) of p-hydroxybenzoic acid and 30.7 g (0.16 mol) of oligoethylene terephthalate (η _inh = 0.12 dl / g) And vacuum-nitrogen substitution was repeated three times.
It was placed under a nitrogen stream at a flow rate of / min. After the polymerization tube was heated to 220 ° C., transesterification was performed for 2 hours to produce a copolymerized oligomer.

Thereafter, the temperature was lowered to 140 ° C in about 30 minutes, and terephthalic acid 13.3 g
(0.08 mol), p-aminophenol 8.7 g (0.08 mol)
Then, 81.6 g (0.80 mol) of acetic anhydride was added dropwise over 30 minutes, and the mixture was further stirred for 1 hour to effect acylation. Thereafter, the temperature of the oil bath was raised to 290 ° C. over one and a half hours, 0.065 g of zinc acetate dihydrate was added, and the pressure was gradually applied to carry out polymerization for one and a half hours. The final degree of vacuum was 6 mmHg. The product flowed under its own weight and could be withdrawn from the bottom of the reactor. After chipping, 12
Vacuum dried at 0 ° C. overnight. The resulting polymer was milky white and opaque.

The melt viscosity of this polymer is 860 at 290 ° C and 1000 sec ^-1 .
Poise. At this time, the polymer exhibited liquid crystallinity.

In addition, the tensile properties of molded pieces produced by a 0.1 oz injection molding machine are as follows: tensile modulus 65,000 kg / cm ² , tensile strength 1,210 kg / cm ² ,
The elongation at break was 3.1%. HDT is 136 ℃ and water absorption is 0.0
5%. In addition, the adhesion to metal was good.

When each component of this polymer was quantified by NMR in the same manner as in Example 1, it was (1) 24.6 mol%, (2) 5.8 mol%, (3) 48.9 mol%, (4) 8.0 mol%, (5) 3.5 mol%. It corresponded to the charged amount.

The results of elemental analysis were as follows: C: 67.57% (67.91%) H: 3.60% (3.67%) N: 1.05% (1.04%) (Calculated values in parentheses) Example 3 In the same reactor as in Example 1, 77.3 g (0.56 mol) of p-hydroxybenzoic acid and 30.7 g (0.16 mol) of oligoethylene terephthalate (η _inh = 0.12 dl / g) And vacuum-nitrogen substitution was repeated three times.
It was placed under a nitrogen stream at a flow rate of / min. The polymerization tube was heated to 220 ° C., and transesterification was performed for 2 hours to produce a copolymerized oligomer.

Then, the temperature was lowered to 140 ° C in about 30 minutes, and terephthalic acid 6.6
g (0.04 mol) and m-aminophenol 4.4 g (0.04 mol) were added, and then 81.6 g (0.80 mol) of acetic anhydride was added dropwise over 30 minutes, and the mixture was further stirred for 1 hour for acylation. Was. Thereafter, the temperature of the oil bath was raised to 290 ° C. over one and a half hours, 0.065 g of zinc acetate dihydrate was added, and the pressure was gradually applied to carry out polymerization for one hour. The final degree of vacuum was 9 mmHg. The product could flow under its own weight and be withdrawn from the bottom of the reactor. After chipping,
Vacuum dried overnight at 120 ° C. The resulting polymer was milky white and opaque.

The melt viscosity of this polymer is 480 at 290 ° C. and 1000 sec ⁻¹
Poise. At this time, the polymer exhibited liquid crystallinity.

The tensile properties of the molded piece prepared in 0.1oz injection molding machine, tensile modulus 76,000kg / cm ^2, tensile strength 1,360kg / cm ^2,
The breaking elongation was 3.6%. Tg is 110 ℃, internal loss is
0.04. The water absorption was 0.03%. In addition, the adhesion to metal was good.

When the respective components of this polymer were quantified by NMR in the same manner as in Example 1, (1) 20.0 mol% (2) 16.8 mol% (3) 55.9 mol% (4) 4.1 mol% (5) 3.2 mol% It corresponded to the charged amount.

The results of elemental analysis were as follows: C: 67.68% (67.88%) H: 3.61% (3.64%) N: 0.52% (0.52%) (Calculated values in parentheses) Example 4 In the same reactor as in Example 1, 77.3 g (0.56 mol) of p-hydroxybenzoic acid and 30.7 g (0.16 mol) of polyethylene terephthalate ([η] = 0.62 dl / g) , Terephthalic acid 6.64 g (0.04 mol), p-aminophenol 4.36 g (0.
04 mol), vacuum-nitrogen substitution was repeated three times, and finally a nitrogen seal was formed. 81.6 g (0.80 mol) of acetic anhydride was added, stirred, immersed in an oil bath at 145 ° C., and acylated for 1 hour. Then raise the oil bath temperature to 275 ℃
The temperature was raised over time, and transesterification was performed at 275 ° C. for 30 minutes. The temperature is raised to 290 ° C in 30 minutes and gradually
Vacuum was applied for a minute. The product did not flow under its own weight and could not be withdrawn from the bottom of the reactor. After chipping,
Vacuum dried overnight at 120 ° C. The resulting polymer was milky white and opaque.

The melt viscosity of this polymer is 1300 at 290 ° C. and 1000 sec ⁻¹
Poise. At this time, the polymer exhibited liquid crystallinity.

The tensile properties of the molded piece prepared in 0.1oz injection molding machine, tensile modulus 55,000kg / cm ^2, tensile strength 1,020kg / cm ^2,
The breaking strength was 2.7%. HDT is 126 ℃ and water absorption is
0.04%. In addition, the adhesion to metal was good.

FIG. 2 shows the ¹ H-NMR chart of this polymer.

When each component of this polymer was quantified by NMR in the same manner as in Example 1, (1) 19.1% (2) 18.4% (3) 58.5% (4) 4.0%, which corresponded to the charged amount.

No peak was observed for the component (5). The results of elemental analysis were as follows: C: 67.50% (67.88%) H: 3.52% (3.64%) N: 0.55% (0.52%) (Calculated values in parentheses) Comparative Example 1 86.4 g (0.48 mol) of p-acetoxybenzoic acid and 30.7 g (0.16 mol) of polyethylene terephthalate ([η] = 0.62 dl / g) were prepared in the same reactor as in Example 1. , And vacuum-nitrogen substitution was repeated three times.
It was placed under a nitrogen stream at a flow rate of 5 / min. The polymerization tube was immersed in an oil bath, the temperature was raised to 275 ° C over 1 hour, and transesterification was performed for 1 hour while maintaining the temperature at 275 ° C. Further, the temperature was raised to 290 ° C in about one hour, and the pressure was gradually applied as it was,
Polymerization was performed for 4 hours. The final degree of vacuum was 0.3 mmHg. The product could be withdrawn from the bottom of the reactor but was difficult. Also, the yield was low. After napping, it was dried at 120 ° C. overnight. The resulting polymer was milky white and opaque.

The tensile properties of molded pieces made from this polymer using a 0.1 oz injection molding machine were as follows: tensile modulus 48,000 kg / cm ² , tensile strength
860 kg / cm ² and elongation at break were 2.6%. HDT was 103 ° C. and adhesion to metal was not good. The water absorption is
0.04%.

When each component of this polymer was quantified by NMR in the same manner as in Example 1, it was (1) 20.2 mol%, (2) 19.9 mol%, (3) 59.8 mol%, which corresponded to the charged amount.

Comparative Example 2 A reaction apparatus similar to that of Example 1 was charged with 93.8 g (0.68 mol) of p-hydroxybenzoic acid and 26.9 g (0.14 mol) of oligoethylene terephthalate (η _inh = 0.12 dl / g), followed by vacuum-replacement with nitrogen. Is repeated three times, and finally filled with nitrogen,
It was placed under a nitrogen stream at a flow rate of / min. After the polymerization tube was heated to 220 ° C., transesterification was performed for 2 hours to produce a copolymerized oligomer.

Then, the temperature was lowered to 140 ° C in about 30 minutes, and 86.7 g of acetic anhydride was used.
(0.85 mol) was added dropwise over 30 minutes, and stirring was continued for another 1 hour to effect acylation. Thereafter, the temperature of the oil bath was raised to 290 ° C. over one and a half hours, 0.065 g of acetic acid dihydrate was added, and the pressure was gradually applied to carry out polymerization for 3 hours. The final degree of vacuum was 3 mmHg. The product could flow under its own weight and be withdrawn from the bottom of the reactor. After forming the chip, it was vacuum-dried at 120 ° C. overnight. The resulting polymer was milky white and opaque.

The adhesion of this polymer to metal was not good.
The breaking elongation was 2.3% and the water absorption was 0.03%. Further, when each component was quantified by NMR in the same manner as in Example 1, it was (1) 15.3 mol% (2) 14.2 mol% (3) 66.7 mol% (5) 3.8 mol%, which corresponds to the charged amount. there were.

Comparative Example 3 A reaction apparatus similar to that of Example 1 was charged with 49.7 g (0.36 mol) of p-hydroxybenzoic acid and 23.0 g (0.12 mol) of oligoethylene terephthalate (η _inh = 0.12 dl / g), followed by vacuum-replacement with nitrogen. Is repeated three times, and finally filled with nitrogen,
It was placed under a nitrogen stream at a flow rate of / min. After the polymerization tube was heated to 220 ° C., transesterification was performed for 2 hours to produce a copolymerized oligomer.

Thereafter, the temperature was lowered to 140 ° C. in about 30 minutes, and terephthalic acid 26.
6 g (0.16 mol) and 17.4 g (0.16 mol) of p-aminophenol were added, and then 86.7 g (0.85 mol) of acetic anhydride was added dropwise over 30 minutes, and stirring was continued for another hour to effect acylation. Was. Thereafter, the temperature of the oil bath was raised to 290 ° C. over 1 hour, 0.065 g of zinc acetate dihydrate was added, and the pressure was gradually applied to carry out polymerization for 1 hour. The final degree of vacuum was 9 mmHg. The product did not flow under its own weight and was difficult to withdraw from the bottom of the reactor. After chipping,
Dry at 120 ° C. overnight. The resulting polymer was milky white and opaque.

The melt viscosity of this polymer is 3,000 at 290 ° C, 1000 sec ^-1
It was more than Poise. Its water absorption was 0.32%.

When each component of this polymer was quantified by NMR in the same manner as in Example 1, (1) 30.2 mol% (2) 8.0 mol% (3) 36.5 mol% (4) 21.0 mol% (5) 4.3 mol% It corresponded to the charged amount.

〔The invention's effect〕

The copolymerized polyesteramide of the present invention exhibits optical anisotropy when melted, exhibits high rigidity, high strength, and high elongation at break, and is excellent in heat resistance, low water absorption, and adhesion. In addition, the fluidity is excellent, and the moldability is good. Such copolymerized polyester amides, various molded articles,
It is useful as a material for films, fibers, and the like, and is particularly suitably used for precision molded products, thin molded products, and the like.

[Brief description of the drawings]

Figure 1 is a polymer obtained in Example 1 of the present invention ¹ H-
It is an NMR chart figure. FIG. 2, the polymer obtained in Example 4 of the present invention ¹ H-
It is an NMR chart figure.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 69/00-69/50 C08G 63/00-63/91 CA (STN)

Claims (2)

(57) [Claims] (1) 5 to 35 mol% of an aromatic dicarboxylic acid residue represented by the formula (1): (B) 5 to 35 mol% of an ethylene glycol residue represented by the formula (2), —O—CH ₂ CH ₂ —O— (2) (c) 30 to 80 mol% of the formula (3) Aromatic oxycarboxylic acid residue, (D) 2 to 20 mol% of an aminophenol residue represented by the formula (4), (R: a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) (E) 1 to 15 mol% of an ether-containing oxycarboxylic acid residue represented by the formula (5), (Here, when the number of moles of (1), (2), (3), (4) and (5) is represented by [1], [2], [3], [4] and [5], % Is a value with respect to the sum of [1] to [5].
Note that [5] does not include [2] and [3]. A) a copolymerized polyesteramide mainly comprising: and having a melt viscosity at 290 ° C. and 1000 sec ⁻¹ of 10 poise or more. 2. As a starting material A polyester or oligoester comprising a repeating unit represented by the general formula (6), 5 to 50 mol% (a weight of the above repeating unit of 192 corresponds to 1 mol), and 30-90 mol% of hydroxybenzoic acid represented by the general formula (7) is reacted to form a copolymerized oligomer (first step),
Next, acylation is performed by adding an acylating agent (second stage),
Further, in a three-stage reaction in which the polymerization is carried out under reduced pressure (third stage), before the end of the second stage, general formula (8) (R: a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) 2 to 20 mol% of an aminophenol represented by the following formula (9): 2 to 20 mol% of terephthalic acid and / or isophthalic acid (where the number of moles of (6), (7), (8) and (9) is [6], [7], [8], [9 ], The mol% is a value based on the sum of [6] to [9].) A process for producing a copolymerized polyesteramide, characterized by adding and reacting.