JPH0446971B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of the Invention) This invention relates to six
-oxy-2-naphthoyl component, 4-oxy-
The present invention relates to a wholly aromatic polyester resin containing a 4'-carboxybiphenyl component and an oxybenzoyl component, which is derived from a polyester-forming reactant and is capable of forming an optically anisotropic melt phase. PRIOR ART Polyesters, poly(ester-amides) and poly(ester-carbonates) containing a 6-oxy-2-naphthoyl component and capable of forming anisotropic melts are described, for example, in U.S. Pat.
No. 4161470, No. 4219461, No. 4256624, No. 4279803
No. 4299756, No. 4318841, No. 4318842,
No. 4330457, No. 4337190, No. 4347349, No.
No. 4351917, No. 4351918, No. 4355133, No.
No. 4359569, No. 4362777, No. 4370466, and No.
Known in No. 4371660. can form optically anisotropic melt phases and can be easily melt-processed to produce high-quality fibers, films,
A new polyester has now been developed that can be formed into three-dimensional molded articles. According to this invention, the first order components (), () and (): [In the formula, the bond is in the meta configuration and/or para configuration] These components may be substituted on at least some hydrogen atoms of the aromatic ring, and this substitution When present, the substituent is selected from alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, and mixtures thereof, in which the wholly aromatic Component () is present in the polyester at a concentration of about 20-60 mol%, component () is present at a concentration of about 20-60 mol% and component () is present at a concentration of about 10-40 mol%. , However, the total molar concentration of component () and component () is approximately 50 ~
It is 90 mol%. Melt processable wholly aromatic polyesters are provided that are capable of forming an anisotropic melt phase at temperatures below 325°C. The melt-processable, wholly aromatic polyesters of this invention essentially comprise at least three circulating components which, when combined in the polyester, provide optically anisotropic melting at temperatures below about 325°C. It was found that a phase was formed. The melting temperature of the polymer was measured per minute using a differential scanning calorimeter.
This can be confirmed by observing the DSC melt transition peak at a heating rate of 20°C. The fully aromatic polyesters of this invention have melting points in the range of about 250-345°C as measured by differential scanning calorimetry. This polyester has the ability to exhibit anisotropy (i.e. liquid crystallinity) in the melt, so
In melt processing, it is easy to form products with highly ordered molecular structures. Preferred polyesters can be melt processed at temperatures ranging from about 250 to 380°C. The usual difficulties encountered when attempting to melt process many aromatic polyesters according to conventional methods are effectively eliminated.
The polyesters of this invention are referred to as "wholly" aromatic in the sense that each component present in the ester contributes to at least one aromatic ring in the polymer backbone. The first essential unit [i.e. component ()] of the polyester of this invention has the following formula: It is a 6-oxy-2-naphthoyl component represented by Although not specifically shown in the structural formula, at least some of the hydrogen atoms on the aromatic ring of component () may be substituted. Such optional substituents include C1-C4 alkyl groups, C1-C4 alkoxy groups, halogens (e.g. Cl, Br, I), phenyl,
or a mixture thereof. Representative ring-substituted compounds from which component () is derived include 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy- 2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, 6-hydroxy-4,7-dichloro-2-naphthoic acid,
Includes 6-hydroxy-5-phenyl-2-naphthoic acid and the like. The presence of ring substitution tends to change the physical properties of the resulting polymer to some extent (e.g., the polymer softens at lower temperatures, improves its impact strength, and increases the crystallinity of the solid polymer). ). In preferred embodiments where a polyester with optimal crystallinity in the solid state is required, no ring substitution is present. As will be clear to those skilled in the art, component () can be derived from unsubstituted 6-hydroxy-2-naphthoic acid and its derivatives. 6-
A convenient laboratory method for the preparation of hydroxy-2-naphthoic acid is described by K. Fries and K. Schimmelcshmidt.
Berichte, Vol. 58, 2835-45 (19250). This description is incorporated herein by reference. U.S. Pat. No. 1,593,816 discloses 6-naphthol by reaction of carbon dioxide with potassium salt of β-naphthol.
The present invention relates to a method for synthesizing hydroxy-2-naphthoic acid. Additionally, U.S. Patent Nos. 4,287,357 and 4,329,424
See No. 4,345,094, and No. 4,345,095. Ingredients () are approximately 20 to 60% of fully aromatic polyester
Present in a concentration of mol%. In particularly preferred embodiments, component () is about 35-65 mole % (e.g.
present at a concentration of approximately 40-60 mol%). The second essential unit of the polyester of this invention [i.e., the component () has the following structural formula, It is a 4-oxy-4'-carboxybiphenyl component represented by Although not specifically shown in the structural formula, at least some of the hydrogen atoms present on the aromatic ring of component () may be substituted. Such optional substituents may be those described for component (). In preferred embodiments requiring a polyester with optimal crystallinity in the solid state, no ring substitution is present. As is clear to those skilled in the art, the ingredients () are:
It can be derived from 4-hydroxy-4'-carboxybiphenyl (eg 4-hydroxybiphenyl-4'-carboxylic acid). 4-Hydroxy-4'-carboxybiphenyl can be produced according to known techniques. For example, 4-methoxy-4'-carboxybiphenyl is described by Johnson et al., J. American Chem. Soc., 68 ,
1649 (1946) method,
This compound was then described by Gray et al., J.
It can be demethylated and converted to 4-hydroxy-4'-carboxybiphenyl according to the method of Chem. Soc., 1418 (1955). Instead of the above method, Sehmidt, Savoy
and Ahernethy, J.Amer.Chem.
Soc., 1944, (66), pp. 491-494,
Direct iodination of 4-hydroxy-biphenyl acetate, benzoate or benzenesulfonate gives 4-hydroxy-biphenyl.
4'-iodobiphenyl can be synthesized, and this iodo compound can then be synthesized by Bach, Barclay, Kende and Cohen, J.Medical Chem., 1968, (11), 992
It can be converted to 4-hydroxy-4'-cyanobiphenyl by reacting it with cuprous cyanide according to the method of P. et al. Furthermore, this nitrile can be hydrolyzed to a hydroxy acid with strong aqueous alkali according to known techniques. Ingredients () are approximately 20~ of fully aromatic polyester
Consists of 60 mol%. In a preferred embodiment,
Component () is about 35-60 mol% (e.g. about 40-60
present in a concentration of mol %). The total molar concentration of components () and () in the wholly aromatic polyester of this invention is about 50-90 mole percent. The third essential component () of the present invention has the following structural formula, (wherein the indicated bonds are in the meta and/or para configuration). Component () can therefore be referred to as a m-oxybenzoyl component or a p-oxybenzoyl component. In a preferred embodiment, the bonding of component () is in the para configuration. Although not shown in the structural formula, at least some of the hydrogen atoms present on the aromatic ring of component () may be substituted in some cases. This optional substituent may be as described for component (). As is clear to those skilled in the art, the ingredients () are:
It can be derived from m-hydroxybenzoic acid and/or p-hydroxybenzoic acid. Representative examples of ring-substituted compounds from which component () can be derived include 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid,
2,3-dichloro-4-hydroxybenzoic acid,
3,5-dichloro-4-hydroxybenzoic acid,
2,5-dichloro-4-hydroxybenzoic acid, 3
-bromo-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-
4-hydroxybenzoic acid, 2,6-dimethyl-4
-Hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 2-phenyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, etc. . The presence of ring substitution in component () tends to change the physical properties of the resulting polymer to some extent, as described above for component (). In preferred embodiments where a polyester with optimal crystallinity in the solid state is required, no ring substitution is present. Component () is about 10 to 40 mol% (e.g. about 15 to 40% by mole)
40 mol%) into the fully aromatic polyester. Optionally, components () and () can be present with or without the concomitant presence of component (). The component () is the formula −
It is a dioxyaryl component represented by O-Ar-O-, where Ar is a divalent group comprising at least one aromatic ring. Component () is one in which the two valencies linking this component to other components in the polymer backbone are symmetrically arranged on one or more aromatic rings (e.g., in the para position with respect to each other). Preferably, it is symmetrical in the sense that it is present on the naphthalene ring, or diagonally arranged when present on the naphthalene ring. Preferred components serving as component () include the following formula: Contains the components shown in or a mixture thereof.
A particularly preferred dioxyaryl component that functions as component () is hydroquinone. component()
At least some of the hydrogen atoms present on the aromatic ring may be substituted. This optional substituent may be as described for component (). In preferred embodiments where a polyester with optimal crystallinity in the solid state is required, no ring substitution is present. component()
Typical examples of ring-substituted compounds that can be derived include methylhydroquinone, chlorohydroquinone, bromohydroquinone, phenylhydroquinone, and the like. Examples of asymmetric dioxyaryl components of component () include those derived from resorcinol. Ingredients () are approximately 0 to 25 of fully aromatic polyester
and when present, is preferably incorporated into the wholly aromatic polyester in a concentration of about 15 to 25 mole %. The component () is the formula

A dicarboxyaryl moiety of the formula: ##STR1## where Ar' is a divalent group comprising at least one aromatic ring. Component () is one in which the two valencies linking this component to other components in the polymer backbone are arranged symmetrically on one or more aromatic rings (e.g., in the para position with respect to each other). It is preferable to be symmetrical in the sense that the diagonal is arranged diagonally when present on the naphthalene ring. component()
Preferred ingredients that can function as
The following formula, Contains the components shown in or a mixture thereof.
A particularly preferred dicarboxyaryl component that functions as component () is a terephthaloyl component derived from terephthalic acid. At least some of the hydrogen atoms present on the aromatic ring may optionally be substituted. This optional substituent may be as described for component (). In preferred embodiments where a polyester with optimal crystallinity in the solid state is required, no ring substitution is present. component()
Examples of asymmetric dicarboxyaryl moieties include moieties derived from isophthalic acid. Ingredients () are about 0 to 100% of fully aromatic polyester.
constitutes 25 mol%, and when present approximately 15
It is introduced into the fully aromatic polyester at a concentration of ~25 mol%. If a phenyl substituent is present in any of the components (), (), (), (), or (),
This phenyl group may be a normal group,
For example, a group capable of substituting a hydrogen atom on an aromatic ring may be supported. For example, such substituents are C1-C4 alkyl groups, C1-C4 alkoxy groups, or halogens (eg, Cl, Br, I). In addition to the aryl hydroxy acids of components (), (), and (), the wholly aromatic polyester of this invention can contain low concentrations (eg, 10 mole % or less) of other aryl hydroxy acids. provided that these components do not raise the melting point of the resulting polymer above a specified temperature or otherwise inhibit the development of the desired anisotropy in the melt (described below). The fully aromatic polyesters of this invention generally depend on the choice of synthetic route.

[Formula] or

It has a terminal group of [Formula]. As will be clear to those skilled in the art, the terminal groups may optionally be capped. That is, the acidic end group may be capped with various alcohols,
The hydroxy end groups may then be capped with various organic acids. For example, in some cases
At the end of the polymer chain, the formula Phenyl ester and methyl ester represented by

[Formula] is included. Optionally, the polymer is placed in an oxygen-containing atmosphere (e.g. in air).
It is also possible to crosslink oxidatively in bulk form or as an already shaped product by heating for a short time (for example a few minutes) below the melting point. The polyesters of this invention are virtually insoluble in all common solvents, such as hexafluoroisopropanol and o-chlorophenol, and are therefore not suitable for solution processing. This polyester is
Surprisingly, it can be easily processed using common melt processing techniques, as discussed below. Most compositions are soluble in pentafluorophenol. Generally, the wholly aromatic polyester of this invention is
about 2000-200000, and preferably about 10000-
50,000, for example about 20,000 to 25,000. The molecular weight can be determined by standard methods that do not involve dissolution of the polymer, such as end group measurement of compression molded membranes by infrared spectroscopy. Instead of the above method, a light scattering method in a pentafluorophenol solution can also be used to measure the molecular weight. Fully aromatic polyesters, when dissolved in pentafluorophenol at a concentration of 0.1% by weight, generally exhibit an internal viscosity ( ) of 4 or higher (e.g., about 4-15) at 60 DEG C. before heat treatment. In some cases, the wholly aromatic polyester produced does not dissolve sufficiently in pentafluorophenol in the measurement of internal viscosity described above. The wholly aromatic polyesters of this invention are considered to be crystalline in the sense that the extruded fibers provide a diffraction pattern characteristic of polymerized crystalline materials in X-ray diffraction using Ni-per-CuKα irradiation and a flat plate camera. I can think. Despite the generally observed degree of crystallinity, the fully aromatic polyesters of this invention can be readily melt processed in all cases. Unlike the aromatic polyesters commonly found in many prior art applications, the fully aromatic polyesters of the present invention are easy to process, form anisotropic melt phases, and therefore exhibit very high regularity in the molten polymer. occurs. The wholly aromatic polyesters of this invention form liquid crystals in the melt phase and thus have a strong tendency for the polymer chains to align in the shear direction. Such anisotropy appears at temperatures at which melt processing can be carried out to produce molded articles. Such regularity in the melt can be confirmed by conventional polarization techniques using crossed polarizers. More specifically, the anisotropic melt phase is confirmed by observing the sample under a nitrogen atmosphere at 40x magnification using a Leitz polarizing microscope with the sample placed on a Leitz hot stage. The polymer melt is optically anisotropic. That is, it allows light to pass through when tested with orthogonal polarizers. The amount of light that passes through increases when the sample is sheared (ie when it flows), but it is still optically anisotropic even in the resting state. The fully aromatic polyesters of this invention can be prepared by a variety of ester formation techniques that involve reacting organic monomeric compounds with functional groups that upon condensation form the desired circulating components. For example, the functional groups of the organic monomer compounds include carboxylic acid groups, hydroxyl groups, ester groups, alkoxy groups, acid halides, and the like. Organic monomeric compounds can be reacted in the absence of a heat exchange fluid by melt acidolysis. Therefore, by first heating these, a sufficiently molten liquid of the reactants is prepared. In this case, certain reactants, such as terephthalic acid, are initially present as solids. The polymer product is suspended in the reaction liquid as solid polymer particles.
Vacuum can be applied to facilitate the removal of volatiles (eg acetic acid, or water) produced in the final condensation stage. "Melt Processable Thermotropic Wholly"
Aromatic Pulleyester Containing
Gordon W Calundan for a share entitled "Polyoxybenzoyl Uuits"
No. 4,067,852 describes another slurry polymerization process that can be used to make the polyesters of this invention, in which the solid product is suspended in a heat exchange medium. The disclosure of this patent is incorporated herein by reference. When using either the melt acidolysis method or the slurry method of U.S. Pat. No. 4,067,852, the organic monomeric reactants deriving components (), (), () and can be used in a modified form in which the hydroxyl group of is esterified (ie, becomes an acyl ester). Preferably, lower acyl groups having about 2 to about 4 carbon atoms are used. component(),
Preferably, acetic esters of organic compounds forming (), (), and () are used. That is,
Particularly preferred reactants for the condensation reaction are 6-acetoxy-2-naphthoic acid, 4-acetoxy-2-naphthoic acid,
4'-carboxybiphenyl, 4-acetoxybenzoic acid, and hydroquinone diacetate. Typical catalysts sometimes used in the process of U.S. Pat. No. 4,067,852 include dialkyltin oxides (e.g., dibutyltin oxide), diaryltin oxides, titanium dioxide, alkoxytitanium silicates, titanium alkoxides, etc. , alkali metal and alkaline earth metal salts of carboxylic acids, gaseous acid catalysts such as Lewis acids (eg, BF ₃ ), hydrogen halides (eg, HCl), and the like. The amount of catalyst used is typically about 0.001 to 1% by weight, and most commonly about 0.01 to 0.2% by weight, based on the total weight of monomers. The molecular weight of the polyester already formed can be further increased by solid-state polymerization, in which the particulate polymer is prepared under an inert atmosphere (for example under a nitrogen atmosphere) at a temperature of about 240°C.
Cook for 10-12 hours. The fully aromatic polyester of this invention has excellent color properties and is white or pale blue. Since this polyester tends to incorporate fewer ester units per unit weight, it is expected to have higher stability to high temperatures. By melt processing the wholly aromatic polyester of this invention, relatively thick products such as three-dimensional molded products, fibers, films, tapes, etc. can be manufactured. The polyester of this invention is suitable for molding applications;
It can then be molded by standard injection molding methods commonly used in the manufacture of molded articles. Unlike polyesters commonly found in the prior art, it is not necessarily necessary to use harsh injection molding conditions (eg, high temperatures), compression molding, impact molding, or plasma spraying. Fibers or membranes can be melt extruded. Molding materials can be prepared by incorporating about 1 to 60% by weight of solid fillers (eg talc) and/or reinforcing materials (eg glass fibers) into the fully aromatic polyesters of this invention. The fully aromatic polyesters of this invention can also be used as coating materials applied as powders or as liquid dispersions. When forming fibers or membranes, the extrusion orifice is selected from those commonly used for melt extrusion of such molded articles. For example, when forming a polymer film, a shaped injection orifice (ie, a slit die) with a rectangular slit shape is used. When forming fibrous products, a spinneret having one, and preferably multiple extrusion orifices, is used. For example, 1~
A standard conical spinneret with 2000 holes (e.g. 6-1500 holes), such as those having a diameter of about 1-70 mils (e.g. 5-40 mils) commonly used for melt spinning of polyethylene terephthalate. can be used. Generally, a thread of about 20 to 200 continuous filaments is formed. The melt spinnable polyester is heated at a temperature above its melting point, e.g.
Applies to extrusion orifices at 250°C to 380°C. The resulting filamentary material or film after extrusion through the shaping orifice is passed along its length through a solidification or quenching zone which converts the molten filamentary material or film into a solid filamentary material or film. . The resulting fibers are generally about 1 to 50 denier per filament;
And preferably about 1 to 20 denier. The filamentary material or membrane obtained is optionally subjected to a heat treatment, thereby further enhancing its physical properties. Such heat treatment can increase the strength of the fiber or membrane. More particularly, the fibers or membranes are grown under an inert atmosphere (e.g. nitrogen, argon, helium) or in a flowing oxygen-containing atmosphere (e.g. air), with or without reaction, at a temperature below the melting point of the polymer. heat treatment until the desired property enhancement is achieved. The heat treatment time generally ranges from several minutes to several days. As the fiber is heat treated, its melting point gradually increases. The temperature of the atmosphere may be increased stepwise or continuously during the heat treatment, or may be maintained at a constant level. For example, the fibers are heated at 250℃ for 8 hours, and
Heat at 280°C for 2 hours. Alternatively, the fibers can be heated for about 24 hours at a temperature of about 15-20°C below their melting point. Optimal heat treatment conditions will vary depending on the specific composition of the polyester and the processing history of the fiber. The as-spun fibers formed from the polyesters of this invention are well-aligned and exhibit satisfactory physical properties;
This fiber is suitable for use in high performance applications.
As-spun fibers generally have an average single filament tenacity of 5 g/d (denier) or more (e.g., about 5 to 15 g/d) and about 300 g/d or more (e.g., about
300 to 1000 g/d) and high temperature (e.g. about 150 to 200
℃) has very high dimensional stability. These properties make the fibers particularly advantageous for use as tire cords and in other industrial applications, such as conveyor belts, hoses, cables, resin reinforcements, etc. Films formed from the polyesters of this invention can be used as packing tapes, cable wraps, magnetic tapes, motor dielectric films, and the like. Fibers and membranes exhibit inherent resistance to burning. Next, examples will be described to further specifically explain the present invention. However, this does not limit the scope of the invention. Example 1 In a 300 ml three-necked round-bottomed flask equipped with a closed paddle stirrer, a gas inlet tube, and a distillation apparatus connected to a condenser, (a) 23.0 g (0.1 mol) of 6-acetoxy- 2-
Naphthoic acid, and (b) 25.6 g (0.1 mole) of 4-acetoxy-4'-carboxybiphenyl were added. The flask was thoroughly purged of oxygen by evacuating and filling with dry argon three times, and then heated on an oil bath with a slow stream of argon. The contents of the flask were heated to 280° C. with continued stirring. After heating at 280°C for 45 minutes, 7ml of acetic acid was collected and the temperature was increased to 300°C.
After continuing heating at 300°C for 45 minutes, the temperature was increased to 320°C and held for 10 minutes. The melt began to opalescent after 8.2 ml of acetic acid was collected. A viscous, opaque, pearl-like melt formed. The melt was then heated to 340°C for 45 minutes, 350°C for 25 minutes, and finally evacuated to 0.5 mm Hg at 360°C for 15 minutes. A total of 10 ml of acetic acid was recovered. The vacuum was relieved with dry argon and the contents of the flask were allowed to cool. The produced polymer is pale yellowish brown, and at 60℃
It was highly insoluble in pentafluorophenol at 300° C., exhibited a melting endotherm at 337° C. when subjected to differential scanning calorimetry (heating rate 20° C./min), and provided an anisotropic melt phase. Example 2 The method of Example 1 was substantially repeated. However, the molar concentration of component () was increased and the molar concentration of component () was decreased. More specifically: (a) 20.7 g (0.09 mol) of 6-acetoxy-2-
naphthoic acid, and (b) 15.36 g (0.06 mol) of 4-acetoxy-4'-
Carboxybiphenyl was added to Lalasco. The contents of the flask, 280
℃ for 45 minutes, 300℃ for 45 minutes, 320℃ for 45 minutes, 340℃ for 20 minutes, 350℃ for 30 minutes, and finally 360℃ for 40 minutes at 0.5 mmHg. .
The wholly aromatic polyester produced is highly insoluble in pentafluorophenol at 60°C, with a concentration of about 317
℃ and provided an anisotropic melt phase. Example 3 In a 300 ml three-necked round-bottomed flask equipped with a closed paddle stirrer, a gas inlet tube, and a distillation apparatus connected to a condenser, (a) 23.0 g (0.1 mol) of 6-acetoxy- 2-
Naphthoic acid, (b) 25.6 g (0.1 mole) of 4-acetoxy-4'-carboxybiphenyl, and (c) 18.0 g (0.1 mole) of 4-acetoxybenzoic acid were added. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow flow of argon. While continuing to stir, heat the contents of the flask to 250°C.
Heat to 250℃, hold at 250℃ for 45 minutes, heat to 280℃, hold at 280℃ for 45 minutes, heat to 300℃, hold at 300℃.
°C for 45 min, heat to 320 °C, hold at 320 °C for 30 min, heat to 340 °C, hold at 340 °C for 15 min, and finally vacuum the flask to 0.5 mmHg.
Heated at 340°C for 45 minutes. The total yield of acetic acid is
It was 13.8ml. The resulting molten polymer was creamy and opaque. When stirred, the polymer became opalescent. The polymer was cooled under argon, removed from the flask, and ground to a powder. The internal viscosity of the polymer () was measured at 60 °C in pentafluorophenol at a concentration of 0.1% by weight,
The following formula, = l _o (7rel)/c (where c is the concentration of the solution (0.1% by weight),
and rel is the relative viscosity. ), it was approximately 5.2. When the polymer was subjected to differential scanning calorimetry (heating rate 20°C/min), it exhibited a melting endotherm at 257°C. The polymer melt was optically anisotropic. The polymer was dried in a vacuum oven and extruded while molten at 307° C. through a single hole spinneret having a diameter of 0.007 inches at a rate of 0.42 g/min. The as-spun filament was quenched in ambient air (72°C, 65% relative humidity) and wound at a speed of 1460 m/min. The resulting as-spun polyester fiber pieces were 2.74 denier and had the following monofilament properties: Tensile strength 11.0 g/d Tensile modulus 690 g/d Elongation 2.4% As a comparative method, Example 3 was substantially repeated. However, component () (derived from 6-acetoxy-2-naphthoic acid) was omitted. moreover,
The final polymerization temperature was increased to 360°C instead of 340°C. A total of 9.3 ml of acetic acid was recovered during the polymerization reaction. The resulting polymer exhibited dual melting endotherms at 333°C and 400°C and was virtually insoluble in pentafluorophenol at 60°C. Unlike the polymer of Example 3, this comparative polymer, which is not within the scope of this invention, did not flow upon heating to 400°C;
Moreover, it could not be melt-spun into fibers and was difficult to process. Example 4 The method of Example 3 was substantially repeated. However, different molar concentrations of reactants were used. More specifically: (a) 27.6 g (0.12 mol) of 6-acetoxy-2-
naphthoic acid, (b) 30.7 g (0.12 mol) of 4-acetoxy-4'-
Carboxybiphenyl, and (c) 28.8 g (0.16 moles) of 4-acetoxybenzoic acid were added to the flask. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. While continuing to stir, heat the contents of the flask to 250°C.
Heat to 250℃, hold for 45 minutes, heat to 280℃, hold at 280℃ for 45 minutes, heat to 320℃, 320℃
℃ for 45 minutes. At this point, the yield of acetic acid is
It was 20.3ml. Finally, the contents of the flask were evacuated to 0.5 mm Hg with stirring and heated to 340 °C.
Heat for 30 minutes. The resulting polymer has an opaque cream color;
After extracting with acetone to remove low molecular impurities,
At 60°C, it had an internal viscosity of about 6.22 when measured at a concentration of 0.1% by weight in pentafluorophenol, and exhibited a sharp melting endotherm at 245°C. The molten polymer was anisotropic at temperatures above 250°C. The resulting polymer was melt spun at 287° C. through a spinneret having a diameter of 0.007 inches at a rate of 0.42 g/min and wound at a speed of 689 m/min. The resulting as-spun fiber fragments were 5.1 denier and had the following monofilament properties: Tensile strength 8.9 g/d Tensile modulus 560 g/d Elongation 2.3% Example 5 The method of Example 3 was substantially repeated. However, different molar concentrations of reactants were used. More specifically: (a) 27.6 g (0.12 mol) of 6-acetoxy-2-
naphthoic acid, (b) 40.1 g (0.16 mol) of 4-acetoxy-4'-
Carboxybiphenyl, and (c) 21.6 g (0.12 moles) of 4-acetoxybenzoic acid were placed in a flask. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. While continuing to stir, heat the contents of the flask to 250°C.
Heat to 250℃, hold for 40 minutes, heat to 300℃, hold at 300℃ for 30 minutes, heat to 320℃, 320℃
℃ for 45 minutes. At this point, the yield of acetic acid is
It was 22.0ml. Finally, the contents of the flask were evacuated to 0.6 mm Hg while stirring in the molten state and heated at 340°C to 360°C for 60 minutes. The resulting polymer is yellow-brown and opaque, presents an anisotropic melt phase, has an internal viscosity of approximately 12.5 when measured in a 0.1% strength by weight solution in pentafluorophenol at 60°C, and 270°C. showed a sharp melting endotherm. The resulting polymer was melt spun at 285° C. through a spinneret having a diameter of 0.007 inches at a rate of 0.14 g/min and wound at a speed of 312 m/min. The as-spun fiber obtained was 5.0 denier and had the following monofilament properties: Tensile strength 7.2 g/d Tensile modulus 532 g/d Elongation 1.8% Example 6 The method of Example 3 was substantially repeated. However, different concentrations of reactants were used. More specifically: (a) 41.4 g (0.18 mol) of 6-acetoxy-2-
naphthoic acid, (b) 15.4 g (0.06 mol) of 4-acetoxy-4'-
Carboxybiphenyl, and (c) 10.8 g (0.06 mole) of 4-acetoxybenzoic acid were added to the flask. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. Polymerization was carried out at 250-340°C for 3 hours. At this point, the yield of acetic acid was 16.0 ml. Finally, while stirring the contents of the flask in the molten state, 0.4 mmHg
and heated to 340° C. for 30 minutes. The resulting polymer is yellow-brown and opaque, presents an anisotropic melt phase, has an internal viscosity of approximately 6.4 measured in a 0.1% strength by weight solution of pentafluorophenol at 60°C, and a melting endotherm at 286°C. showed that. The produced polymer was 0.14g/at 285°C.
It was melt spun at a pass speed of 1 minute and wound at a speed of 213 m/minute. The as-spun fiber fragments produced were 4.3 denier and had the following monofilament properties: Tensile strength 9.26 g/d Tensile modulus 573 g/d Elongation 2.6% Example 7 The method described in Example 3 was substantially repeated. However, different molar concentrations of reactants were used. More specifically: (a) 17.3 g (0.075 mol) of 6-acetoxy-2
-naphthoic acid, (b) 38.4 g (0.150 mol) of 4-acetoxy-4'-
Carboxybiphenyl, and (c) 13.5 g (0.075 moles) of 4-acetoxybenzoic acid were added to the flask. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. Polymerization was carried out at 250°C to 340°C for 3 hours. lastly,
While stirring the contents of the flask in a molten state,
It was evacuated to 0.2 mmHg and heated at 340°C for 30 minutes. The resulting polymer was melt spun by passing it through a spinneret having a diameter of 0.007 inches at a rate of 0.14 g/min at 286°C, and
It was wound up at a speed of 114 m/min. The as-spun fiber fragments produced were 12.7 denier and had the following monofilament properties: Tensile strength 5.2 g/d Tensile modulus 502 g/d Elongation 1.4% Example 8 The method of Example 3 was substantially repeated. However, different molar concentrations of reactants were used. More specifically: (a) 15.33 g (0.066 mol) of 6-acetoxy-2
-naphthoic acid, (b) 51.2 g (0.200 mol) of 4-acetoxy-4'-
The following reactants and catalyst were added to the flask: carboxybiphenyl, (c) 12.00 g (0.066 moles) of 4-acetoxybenzoic acid, and (d) 0.01 of sodium acetate catalyst. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. Polymerization was carried out at 270°C to 360°C for 3 hours. lastly,
While stirring the contents of the flask in a molten state,
Evacuated to 0.5 mmHg and heated at 360°C for 20 minutes. The resulting polymer is pale cream colored and opaque, exhibits an anisotropic melt phase, is virtually insoluble in pentafluorophenol at 60°C, and
It exhibited a melting endotherm at 320°C. The produced polymer was 0.42g/at 330°C.
It was melt spun at a pass speed of 1137 m/min and wound at a speed of 1137 m/min. The as-spun fiber produced was 2.50 denier and had the following monofilament properties: Tensile strength 8.6 g/d Tensile modulus 592 g/d Elongation 1.8% Example 9 The method of Example 3 was substantially repeated. However, different molar concentrations of reactants were used. More specifically: (a) 24.15 g (0.105 mol) of 6-acetoxy-2
-naphthoic acid, (b) 38.4 g (0.150 mol) of 4-acetoxy-4'-
The following reactants and catalyst were added to the flask: carboxybiphenyl, (c) 8.10 g (0.045 mole) of 4-acetoxybenzoic acid, and (d) 0.07 g of potassium acetate catalyst. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. Polymerization was carried out at 250°C to 340°C for 3 hours. Finally, the contents of the flask were evacuated to 0.5 mm Hg and heated to 340° C. for 30 minutes while stirring in the molten state. The resulting polymer was pearlescent and opaque, provided an anisotropic melt phase, was virtually insoluble in pentafluorophenol at 60°C, and exhibited a melting endotherm at 303°C. Example 10 The method of Example 3 was substantially repeated. However, the optional component () is omitted, and the optional component () and ()
brought into existence. More specifically: (a) 34.5 g (0.150 mol) of 6-acetoxy-2
-naphthoic acid, (b) 38.4 g (0.150 mol) of 4-acetoxy-4'-
The following reactants and catalyst were placed in a flask: carboxybiphenyl, (c) 20.00 g (0.103 mole) hydroquinone diacetate, (d) 16.6 g (0.100 mole) terephthalic acid, and (e) 0.020 g potassium acetate catalyst. added to. After purging and evacuating with dry argon, the flask was heated on an oil bath with a slow stream of argon. Polymerization was carried out at 250-340°C for 3 hours. 27.0 ml of acetic acid was collected during this time. Finally, the flask contents were evacuated to 0.13 mmHg and heated to 340 °C.
and heated for 25 minutes. The resulting polymer is pale cream-colored and opaque when measured in a 0.1% concentration by weight pentafluorophenol solution at 60°C, presenting an anisotropic melt phase and removing low-molecular impurities by extraction with acetone. It had an internal viscosity of about 7.8 and exhibited a melting endotherm at 256°C. The polymer was passed through the polymer at a rate of 0.14 g/min at 285°C.
It was melt spun through a spinneret having a diameter of 0.007 inches and wound at a speed of 50 m/min. The as-spun fiber produced was 10.7 denier and had the following monofilament properties: Strength: 9.5 g/d Tensile modulus: 614 g/d Elongation: 1.9% Example 11 A 300 ml three-necked round-bottomed flask equipped with a closed paddle stirrer, a gas suction tube, and a distillation device connected to a condenser. (a) 2.88 g (0.012 mol) of 6-acetoxy-2
-naphthoic acid, (b) 30.40 g (0.12 mol) of 4-acetoxy-4'-
carboxybiphenyl, and (c) 21.38 g (0.12 moles) of 4-acetoxybenzoic acid were added. No catalyst was added at this stage. After purging and evacuation with dry argon,
While slowly flowing argon (0.15/min),
The flask was heated on an oil bath. While continuing to stir, heat the contents of the flask to 260°C.
and observed that the initial rate of acetic acid distillation was very low. After heating at 260℃ for 10 minutes,
Raise the temperature of the bath to 290 °C and hold at 290 °C for 40 minutes,
Raised to 310°C and held at 310°C for 1 hour. At this point in the polymerization reaction, 7 ml of acetic acid was collected and 0.01 g of potassium acetate catalyst and 0.5 ml of acetic acid were added to the flask. After heating at 310°C for an additional 30 minutes, the bath temperature was increased to 330°C and held at 330°C for several minutes. A tendency for the molten polymer in the flask to solidify was then observed, and the flask was then heated to 360°C. The flask was evacuated to 0.7 mm Hg and the melt rapidly became viscous after heating at 360° C. for 11 minutes. Finally, the temperature of the bath was increased to 370°C and a pale blue opaque melt began to solidify. After heating for a total of 36 minutes under 0.7 mm pressure, the flask was filled to normal pressure with argon and allowed to cool. The total yield of acetic acid was 8 ml. 31.3 g of produced polymer was removed by breaking the flask. The product was milled in a Wiley mill and was found to be pentafluorophenol insoluble even at 90°C. Therefore, it was not possible to measure the internal viscosity of this product. The polymer was measured using a differential scanning calorimeter (heating rate 20
℃/min), it showed a melting endotherm at 327℃. The polymer melt was optically anisotropic. While melting the polymer at 361℃, 0.42g/
It was extruded through a 0.007 inch diameter single hole spinneret at a pass rate of 1 minute. The as-spun filament was exposed to ambient air (i.e., 72°C, 65% relative humidity).
The material was rapidly cooled inside and then wound up at a speed of 1,786 m/min. The as-spun polyester fiber produced is
It was 2.34 denier and had the following monofilament properties. Strength: 7.6 g/d Tensile modulus: 540 g/d Elongation: 1.52% After heat treatment in a relaxed state at 300° C. for 16 hours in a stream of dry nitrogen, the properties of the single filament were as follows. Strength: 10.1 g/d Tensile modulus: 761 g/d Elongation: 1.4% Although preferred embodiments of this invention have been described above, many other variations can be used within the scope of this invention.

Claims (1)

[Claims] First-order components (), () and (): [In the formula, the bond is in the meta configuration and/or para configuration] A wholly aromatic polyester consisting of When present, the substituent is selected from alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, halogen atoms, phenyl groups, and mixtures thereof, where the wholly aromatic Component () is present in the polyester at a concentration of about 20-60 mol%, component () is present at a concentration of about 20-60 mol% and component () is present at a concentration of about 10-40 mol%. , However, the total molar concentration of component () and component () is approximately 50 ~
It is 90 mol%. A melt-processable wholly aromatic polyester capable of forming an anisotropic melt phase at temperatures below 325°C. 2 An anisotropic melt phase can be formed at temperatures below 300°C. A melt-processable wholly aromatic polyester according to claim 1. 3. The melt processable wholly aromatic polyester of claim 1 capable of exhibiting a differential scanning calorimeter melting temperature at temperatures of about 250<0>C to 325<0>C. 4. The melt-processable wholly aromatic polyester according to claim 1, which does not have the ring substituent. 5 said component () is present in a concentration of about 20-60 mol%, said component () is present in a concentration of about 20-60 mol%, and said component () is present in a concentration of about 15-40 mol%.
The melt processable wholly aromatic polyester of claim 1, wherein the total molar concentration of component () and component () is about 50 to 85 mole percent.