JP3284631B2 - Method for producing copolyester and copolyesteramide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystalline polyester (amide) in which the sequence is more alternately controlled.
And a method for producing the same.

According to the production method of the present invention, the polymerization rate is high,
In addition to low sublimation, the liquid crystalline polyester (amide) obtained by the production method of the present invention has a high modulus of elasticity, high tensile strength, bending strength, impact strength, and the like. With the same composition and the same composition ratio, not only the mechanical properties but also the heat resistance are superior to the conventional one.

The liquid crystalline polyester (amide) of the present invention
However, these characteristics can be exhibited because a thermotropic liquid crystal is formed during molding and the sequence is more alternately controlled. Therefore, it is very useful as a product such as a molding material, a film, or a fiber.

[0004] In particular, the molding material is suitable for automobile parts, electric and electronic parts, thin molded articles, and precision molded articles.

[0005] Further, since the difference between the solid heat resistance temperature and the temperature at which sufficient melting is possible is small, there is an advantage in polymerization that polymerization can be performed at a low temperature in spite of high heat resistance.

[0006]

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. Polyesters have been widely accepted for use as general molded articles, but many polyesters are inferior in flexural modulus and flexural strength, and thus are not suitable for applications requiring high elastic modulus and high strength.

In recent years, liquid crystalline polyester has attracted attention as a polyester suitable for applications requiring high elastic modulus and high strength. Of particular interest was the Journal of Polymer Science.
Polymer Chemistry Edition, Volume 14 (197
6 years) page 2043, USP 3,778,410, USP
No. 3,804,805 and JP-B-56-18016. J. Jackson et al. Published a thermo-liquid crystalline polymer composed of polyethylene terephthalate and acetoxybenzoic acid. Among them, Jackson et al. Reported that this liquid crystal polymer had a rigidity of at least five times that of polyethylene terephthalate,
It has been reported that it exhibits more than twice the strength and more than 25 times the impact strength, demonstrating new possibilities for high-performance resins.

However, the polymer of Jackson et al. Has the drawbacks of being very brittle and having low strength and low elongation. This is considered to be mainly due to the fact that the ratio of the chain of the p-oxybenzoic acid residue represented by the following formula (7) is extremely large, that is, the block is statistically block-like.

[0009]

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It is considered that this is because the sequence and its distribution and the composition distribution are distributed over a wide range, that is, the heterogeneity is large.

The present applicants have previously discovered a copolyester developed by Jackson et al. That improves the elongation at break of polyester (Japanese Patent Application Laid-Open No. 60-186527).
The idea there is to reduce the above (7), which is a chain of p-oxybenzoic acid units, and this is the cause of trying to reduce (7).

However, Japanese Patent Application Laid-Open No. 60-186527
According to the production method described in JP-A No. 60-186525 or JP-A-60-186525, only a random polymer can be formed even though the method is devised so that p-oxybenzoic acid does not chain at the beginning as much as possible. Low, and
2 and JP-A-2-45524 have been proposed, but even if these methods are used, the chain of (7) is often statistically random, and physical properties such as strength and elongation at break are poor. Not very good.

Further, Japanese Patent Application Laid-Open Nos. Hei 3-56527 and Hei 3-
59024 and Japanese Patent Application No. 2-91640 (Japanese Patent Application No. 3-733).
66)

[0014]

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[0015] A method of performing polycondensation using such as is described.

[0016]

However, when polycondensation is carried out by a usual method, self-condensation of (3) tends to occur in (7), which leaves fragility and lowers heat resistance. Needed. In addition, there is a lot of sublimation in the polymerization, which causes clogging of pipes and slows down the polymerization speed.

The present invention provides a novel copolymer which is capable of suppressing sublimation in the polymerization process under such circumstances, and in which the obtained copolymerized polyester (amide) is excellent in mechanical strength and heat resistance. An object of the present invention is to provide a method for producing a polyester (amide).

[0018]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the gist of the present invention is represented by the following formulas (1) and (2).
And (3),

[0019]

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{Circle around (1)} in the above formulas (1) to (3), M ¹ , M ² , M ³
Represents H or a CH ₃ CO— group, and R ¹ represents 6 to 18 carbon atoms.
Represents a divalent aromatic hydrocarbon group of the formula (1), and optionally (4) and / or (5) and / or (6),

[0021]

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Wherein M ⁴ , M ⁵ , M ⁶ and M ⁷ are H or C
It indicates H ₃ CO- group, R ² represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms excluding the 1,4-phenylene, R ^3,
R ⁴ represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, Y is -OM ⁸ and / or -NHM ⁹ and / or -
A COOH group (M ⁸ and M ⁹ represent HH or CH ₃ CO—). ｝ After further adding acetic anhydride and reacting at a temperature of 170 ° C. or less, the temperature is raised to 260-320 ° C.
Wherein the polycondensation is carried out at a pressure of 10 mm or less in the temperature range described above, wherein the system is depressurized at least once by 260 ° C. to a range of 20 to 700 mmHg in the temperature raising process, the method comprising the steps of: It is in.

Hereinafter, the present invention will be described in detail. In the present invention, as a raw material,

[0024]

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In a system in which is used as an essential component, the temperature is raised after reacting with acetic anhydride.
It is characterized in that the pressure is reduced to not more than g.

Conventionally, generally, the reaction is carried out at normal pressure after the reaction using acetic anhydride. During this heating process, the product produced from (3) or (3) is produced.

[0027]

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[0028]

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The self-condensation of (7) and the like generally makes (7) easy to produce.

By the way, during this heating, 20 mmHg-70
By setting the pressure to 0 mmHg, (7) is surprisingly less likely to be produced than in the conventional method, and the system is more controlled, probably because the self-condensate (7) of (3) is reduced. It was found that both the mechanical properties and the heat resistance were further improved. In addition, sublimation is greatly reduced by the progress of oligomerization of the system.

When the pressure is reduced to less than 20 mmHg, a large amount of sublimate is generated, which causes blockage of piping and the like, which is not preferable. If it exceeds 700 mmHg, the ratio of (7) increases as in the ordinary method, and the physical properties deteriorate, which is not preferable.

The pressure reduction during the temperature raising process may be started any number of times after the reaction with acetic anhydride, but it is preferable to start the pressure reduction at a temperature of 200 ° C. or higher, more preferably 215 ° C.
Above, more preferably 230 ° C. or higher. This greatly reduces sublimation.

The degree of pressure reduction is not less than 20 mmHg and not more than 700 mmHg. In particular, the pressure is preferably reduced to 50 mmHg or more, more preferably 150 mmHg.
Or more, more preferably 300 mmHg or more and 600 mm or more
Hg or less.

In the production method of the present invention, finally, 2
Perform polycondensation at 60 to 320 ° C. at 10 mmHg or less,
Further, by adding a transition metal compound selected from Groups V to VIII of the periodic table before the pressure becomes 10 mmHg or less, the polymerization rate is improved, and the sublimate is greatly reduced. In addition, since these transition metal compounds suppress transesterification, the degree of (7) is further reduced, and the mechanical properties and heat resistance are further improved.

In particular, as the transition metal species, V, Nb,
Ta, Group VI Cr, Mo, W, Group VII Mn, Group VIII Ni, Co, Fe, etc., particularly preferably Group VIII Ni and Fe, and most preferably Fe.

These may be in the form of salts, for example, acetates, oxides,
Used as acetylacetonate salt, chloride and the like.

Of these, acetate and acetylacetonate are preferred. Specific examples of preferred compounds include F
e (acac) ₃ , Fe (oAc) ₃ , FeCl _{3 and the} like. Particularly, Fe (acac) ₃ is preferable. These may be used as a mixture. The amount used is 20 to 5000 ppm as a metal compound to the polymer, preferably 30 to 1000 ppm, more preferably 50 to 1000 ppm.
It is 500 ppm, more preferably 70 to 300 ppm.

The addition time of these compounds is 10 mmH
g or less before polycondensation. Although it may be added from the beginning, it is preferable to add it after reacting with acetic anhydride because the degree of transesterification increases or the catalyst is easily deactivated when it is added from the beginning, and at a temperature lower than 260 ° C. It is preferred to add.

When added at 260 ° C. or higher, there are many sublimates, which tend to be undesirable. When the pressure is reduced at the time of raising the temperature, it is preferable to add the pressure before reducing the pressure of the system. The compound is
It may be added in portions.

In the present invention, after the reaction with acetic anhydride, a transition metal compound of Group V to Group VIII is used in a temperature range of up to 260 ° C. to produce from (1).

[0041]

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The degree of improvement in reactivity of (1-1) results from (3).

[0043]

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By surpassing the degree of improvement in reactivity of (3-1),
Therefore, it is considered that (7) is unlikely to occur. That is, it is considered that (3-1) relatively easily reacts to (1-1). In particular, it is considered that the effect becomes remarkable when the Fe compound is used, and that the transesterification is suppressed. That is,

[0045]

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It is considered that the use of such a production method resulted in an increase in the mechanical properties and heat resistance because more of the structure was present in the system. When a group I or II compound is used, it is not preferable because of high sublimation and a low polymerization rate. The use of group II Zn or group III or group IV Ti is not preferred because of the frequent transesterification and the like, resulting in poor mechanical properties and heat resistance.

The molar ratio of the compounds (1) to (6) used in the present invention is represented by {1} to {6}, respectively.
As the compound of (1),

[0048]

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And the like. Among them, (1)
-1) is preferred. The ratio of {1} is {1} + (2} +
10 to 45 for {3} + {4} + {5} + {6}
Mol%, preferably 12 to 35 mol%, more preferably 15 to 30 mol%.

The R of the dicarboxylic acid unit represented by the formula (2)
¹ represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and specifically,

[0051]

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[0052] (- X- is -O -, - S -, - SO 2 -,
—CH ₂ —, —C (CH ₂ ) ₂ — and the like can be mentioned). These may be used alone or may be mixed to form a copolymer. Of these

[0053]

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Is preferred. When used alone

[0055]

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Is preferred. (In particular

[0057]

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When mixed and used, at least one unit is

[0059]

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It is preferable to be selected from one of the following:
The total of these is preferably at least 50%, more preferably at least 66%, by mole ratio of R ¹ .

As a preferred mixed system,

[0062]

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And the like. Of course, three or more of these may be used, but up to two are preferred. The ratio of {2} is 15 to 45 mol%, preferably 15 to 40 mol%, more preferably 18 to 35 mol%. As the compound of the formula (3),

[0064]

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The following can be mentioned. It is preferable to use (3-1). The ratio of {3} is 10 to 70 mol%, preferably 20 to 65 mol%, more preferably 30 to 6 mol%.
5 mol%. As R _{2 in the} formula (4),

[0066]

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And the like. (X represents alkyl, phenyl, halogen, etc.)

[0068]

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Is preferred. The ratio of {4} is 0 to 20 mol%, preferably 0 to 15 mol%. More preferably, it is 0 to 10 mol%. As R _{3 in the} formula (5),

[0070]

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(-X- is -O-, -S-, -SO _3- ,
—CH ₂ —, —C (CH ₃ ) ₂ — and the like can be mentioned). These may be used alone or as a mixture. The ratio of {5} is 0
It is 20 mol%, preferably 0 to 15 mol%. As R ₄ of the compound represented by the formula (6),

[0072]

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And the like. Specific examples of (6) include:

[0074]

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And its acetates. The ratio of {6} is 0 to 20 mol%, preferably 0
１５15 mol%. The molar ratios used from (1) to (6) increase the degree of polymerization.

[0076]

(Equation 1)

Is preferable, and

[0078]

(Equation 2)

Are preferable, and in particular,

[0080]

(Equation 3)

Is preferred.

[0082]

(Equation 4)

In this case, the polymerization rate is particularly high, and the number of heterogeneous bonds in the main chain is small, which is preferable. Incidentally, {M ⁱ O-} is, M ⁱ
Represents the number of moles of O-group. Here, Mi is ^calculated by the above equation (1).
M ¹ in the ^{~ (6), M 2,} M 3, M 4, showing the M ^5, M ⁶ or M ^8. {M ^j HN-} represents the number of moles of the M ^j HN- group. Here, M ^j represents M ⁷ or M ⁹ in the above formula.

The timing of adding acetic anhydride is as follows:
It may be added simultaneously with the compound of (6) or may be added later. Moreover, the compounds when M ⁱ is CH ₃ CO- group may be added after reaction with acetic anhydride.

The amount of acetic anhydride to be added is OH group + NH of the whole system.
The equivalent is preferably 1.0 to 2.0 times, and more preferably 1.1 to 1.5 times the equivalent number of the _two groups. Further, the ratio is preferably 1.3 to 1.4 times. If it is less than 1.0 times, the polymerization rate is slow and sublimation is increased, which is not preferable. 2.0
If it exceeds twice, coloring becomes intense and physical properties are deteriorated, which is not preferable. Even when there is no OH group in the system, C
Preferably added 0.1-0.4 equivalents relative to the number of equivalents of H ₃ CO- group.

The reaction with acetic anhydride is carried out at 170 ° C. or lower.
Preferably, it is performed at 120 to 160 ° C. The reaction time is 10 minutes to 3 hours, preferably 30 minutes to 2 hours. Thereafter, the temperature is raised, and finally, the temperature is raised to 260 to 320 ° C. and 10 mmH.
Although the polycondensation is carried out at a pressure of not more than g, the conventional method is usually carried out at normal pressure in this heating step.

In the present invention, as described above, at least once during this heating step, the system is heated to 20 to 700 mmH.
It is important to reduce the pressure to g.

By taking this operation, the self-condensate (7) of (3) is reduced, or the strength of the produced polymer is improved, the heat resistance is improved, and the oligomerization of the system proceeds. Sublimation is also greatly reduced. After the temperature is raised, the polymerization process starts. The polymerization is preferably carried out at 260-320 ° C, more preferably at 265-300 ° C, and most preferably at 265-280 ° C. If the temperature is lower than 260 ° C., the polymerization rate is extremely slow, and if it exceeds 320 ° C., the physical properties of the produced polymer deteriorate, which is not preferable. It is preferable that the polymerization temperature be lower since the transesterification reaction does not easily occur.

The temperature may be kept constant during the polymerization process,
It is good to raise the temperature gradually. The time required for gradually reducing the pressure to 1 mmHg in the initial stage of the polymerization is 30 minutes or more, preferably 60 minutes or more, and particularly from 30 mmHg to 1 mmHg.
It is important to gradually reduce the pressure to mmHg.

The copolymerized polyester (amide) produced according to the present invention has a high strength and is suitable for a thin-walled molded product or film. In addition, since it has a high fluidity, it is suitable for precision molded products and the like. For example, parts for automobiles, parts for information materials such as compact disks and floppy disks, connectors,
It can be used for parts of electronic materials such as IC sockets.

At the time of molding, the copolymerized polyester obtained by the production method of the present invention is mixed with fibers such as glass fibers and carbon fibers, fillers such as talc, mica and calcium carbonate;
It is also possible to add a nucleating agent, a pigment, an antioxidant, a lubricant, other stabilizers, a filler such as a flame retardant or an additive, a thermoplastic resin or the like to impart desired properties to the molded article.

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

[0093]

Next, the present invention will be described in more detail.
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 at a shear rate of 1000 sec.
c ⁻¹ , length / diameter of cylinder nozzle = 20 was used.

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

Molding was performed using a 0.1 oz injection molding machine manufactured by Nippon Steel Corporation to produce molded pieces. Tensile properties (tensile modulus, tensile strength, elongation at break) of the above-mentioned 0.1 oz molded product are TENSILON / UT manufactured by Toyo Baldwin.
It was measured using M-IIIL.

Incidentally, the elongation at break of the tensile properties was set at 0.1.
The 1 oz molded piece (dumbbell piece) has a lower elongation and a considerably lower strength than the ASTM molded piece. Therefore, if the elongation of this molded piece is 3.2% or more, it can be said that the polymer is considerably tough. If it is less than 3.0%, it can be said that the polymer is quite brittle.

As an index of heat resistance, HDT determined as follows was used. That is, HDT is 0.1 oz
The Vicat softening temperature is obtained from the molded piece obtained by the injection molding machine, and the HDT is obtained from the molded piece molded using a 2.5 oz Toshiba Machine's injection molding machine with a conventionally manufactured liquid crystal polyester or a commercially available liquid crystal polyester. Is a value obtained based on the fact that there is a good correlation between the two.

The Vicat softening temperature was measured using Toyo Seiki's automatic HD.
Using a T-measuring device, the sample was at a temperature at which the needle penetrated 1 mm at a heating rate of 50 ° C./hr using the runner portion of the above-mentioned 0.1 oz molded piece.

Reference Example 1

[0101]

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Synthesis of (1,2-ethylene-bis-4-hydroxybenzoate) In xylene, p-hydroxybenzoic acid and ethylene glycol were converted to p-hydroxybenzoic acid / ethylene glycol =
2/1 (molar ratio), and p-
Toluenesulfonic acid was charged.

This was heated to the reflux temperature of xylene and reacted. After completion of the reaction, the unreacted portion was removed by washing with water to obtain 1,2-ethylene-bis-4-hydroxybenzoate of high purity. The structure was confirmed by H-NMR.

Example 1 41.4 g (0.137 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and 21% of terephthalic acid were placed in a glass polymerization tube provided with a stirrer made of Hastelloy, a nitrogen inlet and a decompression port. 9.9 g (0.132 mol) and 56.7 g (0.411 mol) of p-hydroxybenzoic acid were charged.
_{After 2-} substitution under reduced pressure, 97.8 g (0.9%) of acetic anhydride was further added.
6 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. After that, over 2.0 hours 27
The temperature was raised to 5 ° C., and the pressure was increased from 140 ° C. to 230 ° C. under normal pressure (under an N ₂ atmosphere). Thereafter, the pressure was reduced to 400 mmHg, and the temperature was raised to 275 ° C. while maintaining 400 mmHg. After reaching 275 ° C, 400mmHg to 5mmHg over 1 hour
When the polymerization was performed at 5 mmHg for 30 minutes, the torque was sufficiently increased, and the polymerization was terminated. Sublimation was hardly observed, and the pull-out property was good.

The polymer had a melt viscosity of 145 at 275 ° C.
0 poise, tensile elasticity 10.5 GPa, tensile strength 1
970 kg / cm ² , HDT 208 ° C.

Example 2 41.4 g (0.137 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and terephthalic acid 21 were added to a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. 9.9 g (0.132 mol) and 56.7 g (0.411 mol) of p-hydroxybenzoic acid were charged.
_{After 2-} substitution under reduced pressure, 97.8 g (0.9%) of acetic anhydride was further added.
6 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. After that, over 2.0 hours 27
The temperature is raised to 5 ° C., and the pressure is increased from 140 ° C. to 230 ° C. under normal pressure (under N ₂ atmosphere).
c) 0.076 g of ₃ was added, and then the pressure was reduced to 400 mmHg, and the temperature was raised to 275 ° C while maintaining 400 mmHg. 27
After reaching 5 ° C, it takes 5 hours from 400mmHg for 1 hour
Although the pressure was adjusted to mHg, when the pressure reached 5 mmHg, the torque was sufficiently increased, and thus the polymerization was terminated. The polymerization rate was further improved than in Example 1. No sublimation was observed, and the pull-out property was good.

The polymer had a melt viscosity of 138 at 275 ° C.
0 poise, tensile elasticity 11.0 GPa, tensile strength 2
190 kg / cm ² , HDT 216 ° C.

Comparative Example 1 41.4 g (0.137 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and terephthalic acid 21 were placed in a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. 9.9 g (0.132 mol) and 56.7 g (0.411 mol) of p-hydroxybenzoic acid were charged.
_{After 2-} substitution under reduced pressure, 97.8 g (0.9%) of acetic anhydride was further added.
6 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. Thereafter, the temperature was raised to 275 ° C. under normal pressure (under N ₂ atmosphere) over 2.0 hours. After the pressure reached 275 ° C., the pressure was reduced, the temperature was changed from 760 mmHg to 5 mmHg over 1 hour, polymerization was performed at 5 mmHg for 30 minutes, and then polymerization was performed at 1 mmHg or less for 30 minutes.
The polymerization was terminated because the torque was sufficiently increased. Extractability was difficult. The polymer had a melt viscosity of 14 at 275 ° C.
30 poise, tensile modulus 9.0 GPa, tensile strength 1
680 kg / cm ² , HDT 202 ° C.

Example 3 41.4 g (0.137 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and terephthalic acid 21 were placed in a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. 2.9 g (0.132 mol), 52.9 g (0.383 mol) of p-hydroxybenzoic acid and 3.8 g (0.028 mol) of m-hydroxybenzoic acid were charged.
_{After 2-} substitution under reduced pressure, 97.8 g (0.9%) of acetic anhydride was further added.
6 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. After that, over 2.0 hours 27
The temperature is raised to 5 ° C., and the pressure is increased from 140 ° C. to 230 ° C. under normal pressure (under N ₂ atmosphere).
c) 0.076 g of ₃ was added, and then the pressure was reduced to 300 mmHg, and the temperature was raised to 275 ° C with 300 mmHg. 27
After reaching 5 ° C, it takes 5 hours from 300mmHg over 1 hour.
When the polymerization was carried out at 5 mmHg for 10 minutes at a pressure of mHg, the torque was sufficiently increased and the polymerization was terminated. Sublimation was hardly observed, and the pull-out property was good.

The polymer had a melt viscosity of 740 at 275 ° C.
Poise, tensile modulus 11.5 GPa, tensile strength 23
20 kg / cm ² , HDT 188 ° C.

Example 4 32.5 g (0.108 mol) of 1,2-ethylene-bis-4-hydroxybenzoate was added to a glass polymerization tube provided with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. '
-13.3 g (0.072 mol) of dihydroxybiphenyl, 29.0 g (0.175 mol) of terephthalic acid and 44.5 g (0.323 mol) of p-hydroxybenzoic acid were charged, and after N ₂ -replacement under reduced pressure, Acetic anhydride 9
7.3 g (0.953 mol) was added, and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. Thereafter, the temperature is raised to 300 ° C. over 2.0 hours, and the pressure is increased from 140 ° C. to 230 ° C. under normal pressure (under N ₂ atmosphere).
At this time, 0.076 g of Fe (acac) ₃ was added, and then the pressure was reduced to 400 mmHg, and the pressure was reduced to 400 mmHg.
The temperature was raised to 0 ° C. After reaching 300 ° C, take 4 hours
From 00 mmHg to 5 mmHg, when the torque reached 5 mmHg, the torque was sufficiently increased and the polymerization was terminated.
Sublimation was hardly observed, and the pull-out property was good.

The polymer had a melt viscosity of 860 at 300 ° C.
Poise, tensile strength 1960 kg / cm ² , HDT22
6 ° C.

Comparative Example 2 32.5 g (0.108 mol) of 1,2-ethylene-bis-4-hydroxybenzoate, 4,4,4 were added to a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. '
-13.3 g (0.072 mol) of dihydroxybiphenyl, 29.0 g (0.175 mol) of terephthalic acid and 44.5 g (0.323 mol) of p-hydroxybenzoic acid were charged, and after N ₂ -replacement under reduced pressure, Acetic anhydride 9
7.3 g (0.953 mol) was added, and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. Thereafter, the temperature was raised to 300 ° C. under normal pressure (under N ₂ atmosphere) over 2.0 hours. After the temperature reached 300 ° C., the pressure reduction was started, the pressure was reduced from 760 mmHg to 0.5 mmHg over 1 hour, and the polymerization was further performed for 2.5 hours. Sublimation occurred considerably, and extraction was difficult.

The polymer had a melt viscosity of 960 at 300 ° C.
Poise, tensile strength 1750kg / cm ² , HDT21
0 ° C., lower than that of Example 4.

Example 5 49.1 g (0.163 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and p-amino were placed in a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. Phenol 4.4 g (0.04 mol), terephthalic acid 32.8 g (0.198 mol) and p-hydroxybenzoic acid 33.7 g (0.244 mol) were charged, and N ₂ −
After the replacement under reduced pressure, 92.8 g (0.91 mol) of acetic anhydride was further added, and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. 275 ° C over 2.0 hours
The temperature is raised from 140 ° C. to 230 ° C. at normal pressure (under N ₂ atmosphere). At 230 ° C., Fe (acac) ₃
After adding 0.076 g, the pressure was reduced to 400 mmHg, and the temperature was raised to 275 ° C. while maintaining 400 mmHg. 275
After reaching ℃, 400mmHg to 5mm over 1 hour
Hg, hold at 5mmHg for 30 minutes, then 0.3mm
When the polymerization was performed at 0.3 mmHg for 1 hour, the torque was sufficiently increased, and the polymerization was terminated. Sublimation was hardly observed.

The polymer had a melt viscosity of 200 at 275 ° C.
0 poise, tensile modulus 11 GPa, tensile strength 259
It was 0 kg / cm ² and HDT197 ° C.

Example 6 49.1 g (0.163 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and terephthalic acid 26 were added to a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. .0g (0.157 mol), p- hydroxybenzoic acid 33.7 g (0.244 mol) and p- charged amino acid 11.1 g (0.081 mol), N ₂
-After the replacement under reduced pressure, 92.9 g (0.91 g) of acetic anhydride was further added.
1 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. After that, over 2.0 hours 27
The temperature is raised to 5 ° C., and the pressure is increased from 140 ° C. to 230 ° C. under normal pressure (under N ₂ atmosphere).
c) ₃ 0.11 g was added, and then the pressure was reduced to 400 mmHg, and the temperature was raised to 275 ° C. while maintaining 400 mmHg. 27
After reaching 5 ° C, it takes 5 hours from 400mmHg for 1 hour
mHg, hold at 5 mmHg for 30 minutes, then 0.3 m
When the polymerization was performed at 0.3 mmHg for 1 hour, the torque was sufficiently increased, and the polymerization was terminated. Sublimation was hardly observed.

The polymer had a melt viscosity of 250 at 275 ° C.
0 poise, tensile elasticity 11.5 GPa, tensile strength 2
600 kg / cm ² , HDT 210 ° C.

Example 7 41.4 g (0.137 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and 21% of terephthalic acid were placed in a glass polymerization tube provided with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. 9.9 g (0.132 mol) and 56.7 g (0.411 mol) of p-hydroxybenzoic acid were charged.
_{After 2-} substitution under reduced pressure, 97.8 g (0.9%) of acetic anhydride was further added.
6 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. After that, over 2.0 hours 27
The temperature is raised to 5 ° C., but at 140 ° C. to 230 ° C. under normal pressure (under N ₂ atmosphere), and at 230 ° C., Ni (OA
c) ₂ · 4H ₂ O was added 0.053 g, then 400m
The pressure was reduced to mHg, and the temperature was raised to 275 ° C. while maintaining 400 mmHg. After reaching 275 ° C, 400mmH over 1 hour
g was changed to 5 mmHg, and polymerization was performed at 5 mmHg for 30 minutes. No sublimation was observed at all, and the withdrawability was good.

The polymer had a melt viscosity of 132 at 275 ° C.
0 poise, tensile elasticity 11.5 GPa, tensile strength 2
050 kg / cm ² , HDT 215 ° C. Example 7 41.4 g (0.137 mol) of 1,2-ethylene-bis-4-hydroxybenzoate and 21.9 g of terephthalic acid were added to a glass polymerization tube equipped with a Hastelloy stirring blade, a nitrogen inlet, and a vacuum port. 0.132 mol) and 56.7 g (0.411 mol) of p-hydroxybenzoic acid were charged.
_{After 2-} substitution under reduced pressure, 97.8 g (0.9%) of acetic anhydride was further added.
6 mol), and the system was heated to 140 ° C. while stirring and kept at 140 ° C. for 1 hour. After that, over 2.0 hours 27
The temperature is raised to 5 ° C., and the pressure is increased from 140 ° C. to 230 ° C. under normal pressure (under N ₂ atmosphere).
c) ₂ · 4H ₂ O was added 0.053 g, then 400m
The pressure was reduced to mHg, and the temperature was raised to 275 ° C. while maintaining 400 mmHg. After reaching 275 ° C, 400mmH over 1 hour
g was changed to 5 mmHg, and polymerization was performed at 5 mmHg for 30 minutes. Sublimation was hardly observed, and the withdrawability was good.

The polymer had a melt viscosity of 145 at 275 ° C.
0 poise, tensile modulus 10.8 GPa, tensile strength 2
000 kg / cm ² , HDT 210 ° C.

[0122]

As described above, according to the present invention,
Sublimation during polymerization can be suppressed, and the resulting polymer is excellent in heat resistance and strength.

────────────────────────────────────────────────── (5) References JP-A-3-56527 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08G 69 / 44

Claims (3)

(57) [Claims] 1. Addition of the following formulas (1), (2) and (3): 中 In the above formulas (1) to (3), M ¹ , M ² and M ³ are H or C
R ₃ represents a H ₃ CO— group, and R ¹ represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. (4) and / or (5) and / or (6) may optionally be added, Formula 2 In the formula, M ⁴ , M ⁵ , M ⁶ , and M ⁷ represent H or a CH ₃ CO— group, and R ² has 6 to 1 carbon atoms excluding 1,4-phenylene.
8 represents a divalent aromatic hydrocarbon group, R ³ and R ⁴ represent a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and Y represents —OM.
⁸ and / or -NHM ⁹ and / or -COOH groups (M
^8, M ⁹ represents a represents H or CH ₃ CO- group). ｝ Further, after adding acetic anhydride and reacting at a temperature of 170 ° C. or less, the temperature is raised, and
In performing the polycondensation at a pressure of not more than mmHg, the system is at least once brought up to 260 ° C.
A method for producing a copolymerized polyester (amide), wherein the pressure is reduced to a range of mmHg. 2. The copolymerized polyester according to claim 1, wherein a transition metal compound selected from Groups V to VIII of the periodic table is added before the pressure becomes 10 mmHg or less. Amide). 3. The method for producing a copolymerized polyester (amide) according to claim 2, wherein the transition metal compound selected from Groups V to VIII of the periodic table is an iron compound.