JPS5978232A - Anisotropically melting fully aromatic polyester - Google Patents

Abstract

PURPOSE:The titled polyester capable of forming moldings showing high retentivity of mechanical properties at high temperatures, comprising specified proportions of units derived from an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and a p-orienting aromatic dicarboxylic acid. CONSTITUTION:A polyester which either comprises a unit (a) derived from an aromatic dicarboxylic acid component containing at least about 90mol% p-orienting aromatic dicaroboxylic acids and a unit (b) derived from an aromatic dihydroxy compound component containing at least about 90mol% monosubstituted hydroquinone (MQ) substituted with a 7-10C alkyl group on its nucleus or containing at least about 90mol% total of said MQ and substituted hydroquinones other than MH, said MQ being present in an amount of at least 80mol%, or comprises said units (a) and (b) and a unit (c) derived from a p-orienting aromatic hydroxycarboxylic component containing at least about 70mol% p- hydroxybenzoic acid and/or a monosubstituted p-hydroxybenzoic acid, wherein each of the unit derived from the p-orienting dicarboxylic acids and the unit derived from MH occupies at least about 9mol% of the total structural units.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a melt anisotropic wholly aromatic polyester. More specifically, the present invention relates to melt anisotropic wholly aromatic polyesters containing units derived from monosubstituted hydroquinones which are nuclearly substituted with specific substituents. Although the novel melt anisotropic wholly aromatic polyester exhibits melt anisotropy, it can be easily melt-molded from its optically anisotropic melt, producing molded products with excellent mechanical properties, such as fibers. Or give a film.

[Prior art]

Polyethylene terephthalate has traditionally been used as fibers and films due to its excellent mechanical strength, heat resistance, and chemical resistance.

Widely used as a material for plastics, etc. However, it is difficult to say that polyethylene terephthalate fibers, for example, are still sufficient for industrial applications (such as tire cords) that require high strength and high Young's modulus.

On the other hand, aromatic polyamides such as poly p-phenylene terephthalamide and poly p-benzamide are known as fiber materials that provide extremely high Young's modulus 2 strength and the like. However, while polyethylene terephthalate can be easily made into fibers by melt spinning, these aromatic polyamides are difficult to melt spin, and in fact, they have no choice but to be made into fibers by solution spinning (dry or wet spinning). Therefore, in addition to the necessity of recovering the solvent, the shape of the obtained product is also limited by the molding method, and is limited to, for example, fibers, and still has many disadvantages from an industrial perspective.

In order to improve these drawbacks, fully aromatic copolyesters made of aromatic oxycarboxylic acids, aromatic dihydroxy compounds, and aromatic dicarboxylic acid components such as terephthalic acid and isophthalic acid and fibers thereof have been proposed (!
Samurai Kai No. 50-43223). However, even in this case, a wholly aromatic polyester using, for example, p-oriented terephthalic acid as the dicarboxylic acid component has an extremely high melting point. Therefore, even if it were possible to produce a polymer with a high degree of polymerization, it would be difficult to mold it by melt molding, such as melt spinning. Moreover, it is difficult to manufacture efficiently.

On the other hand, fully aromatic polyesters that use p-orientation, such as isophthalic acid, as the dicarboxylic acid component have significantly lower melt viscosity than the above-mentioned fully aromatic polyesters that use terephthalic acid. Although it has the advantage of being moldable, it does not have melt anisotropy, so it has the disadvantage that molded products with excellent mechanical properties such as Young's modulus, such as fibers and films, cannot be manufactured by melt molding alone. There is.

Although butylhydroquinone is disclosed as an aromatic dihydroxy compound in the above specification, there is no description or suggestion of a wholly aromatic polyester using butylhydroquinone or a method for producing the same.

In addition, terephthalic acid or 2,6
- Optically anisotropic wholly aromatic polyesters using naphthalene dicarboxylic acid and unsubstituted phenylhydroquinone or substituted phenylhydroquinone as an aromatic dihydroxy compound are known (see US Pat. Nos. 4,159,365 and 4,153,779). Fibers made from fully aromatic polyester obtained using unsubstituted phenylhydroquinone have high strength retention at high temperatures! This feature is disclosed in US Pat. No. 4,159,365.

Further, JP-A-56-84718 discloses a wholly aromatic polyester using hydroquinone together with unsubstituted phenylhydroquinone as the main aromatic dihydroxy compound. These wholly aromatic polyesters contain hydroquinone at a ratio of 50 to 3 to the total hydroxyl component.
It is characteristic in that it has a relatively high melting point even though it is used in a relatively large amount of 0 mol. It also has the property of being soluble in organic solvents.

[Purpose of the invention]

An object of the present invention is to provide a wholly aromatic polyester exhibiting novel melt anisotropy.

Another object of the present invention is to develop a novel melt anisotropic total melt material which has a relatively low melting point and flow initiation temperature despite exhibiting melt anisotropy, and which can be easily melt-molded from an optically anisotropic melt. Our objective is to provide aromatic polyester.

Still another object of the present invention is to provide a wholly aromatic polyester that exhibits excellent solubility in organic solvents that can be melt-molded as well as sludge-molded. The object of the present invention is to provide a wholly aromatic polyester having excellent moldability and capable of carrying out the following steps.

Yet another object of the present invention is to provide a wholly aromatic polyester that is easy to melt mold and exhibits excellent solvent resistance to organic or inorganic solvents.

Still another object of the present invention is to provide a novel wholly aromatic polyester that can be melt-molded to give molded articles exhibiting excellent mechanical properties, such as strength and Young's modulus.

Still another object of the present invention is to provide a wholly aromatic polyester with excellent thermal stability that provides molded articles with high retention of mechanical properties at high temperatures.

Still another object of the present invention is that the melting point and flow start temperature are relatively low, so the melt forming temperature can be made relatively low, and thermal deterioration or oxidative deterioration due to heating during molding can be suppressed as much as possible. The purpose of the present invention is to provide a wholly aromatic polyester that provides molded products with excellent performance.

Still another object of the present invention is that the melting point and flow initiation temperature are relatively low, so that the polymerization temperature during the production of the polymer can be relatively low, and the thermal deterioration or oxidative deterioration during the production of the polymer can be reduced. The object of the present invention is to provide a fully aromatic polyester with a high polymer content as suppressed as possible.

Further objects of the invention will become apparent from the description below.

[Construction and effect of the invention]

Such objects and advantages of the present invention are that according to the present invention p
-Unit (a) in which the oriented aromatic dicarboxylic acid is derived from an aromatic dicarboxylic acid having about 90 mol or more of aromatic dicarboxylic acid and -OH 几-
Mono-substituted nuclear substituted with an aralkyl group having 7 to 10 carbon atoms represented by Ar (where R is hydrogen or an alkyl group having 1 to 3 carbon atoms, and Ar is an aromatic group having 6 to 8 carbon atoms) An aromatic compound having about 90 moles or more of hydroquinone, or about 9 moles or more of the monosubstituted hydroquinone and a substituted hydroquinone other than the monosubstituted hydroquinone, and about 80 moles or more of the monosubstituted hydroquinone. Units derived from dihydroxy compounds (
1)) or consists essentially of the above units (,),
(1)) and l) -hydroxybenzoic acid and/
or the monosubstituted p-hydroxybenzoic acid is substantially composed of units (C) derived from a p-oriented aromatic oxycarboxylic acid having a molar ratio of about 70 or more, and is derived from a p-oriented aromatic dicarboxylic acid. unit and -OH几-Ar (where,
(2) is hydrogen or an alkyl group having 1 to 3 carbon atoms, Ar1j is an aromatic group having 6 to 8 carbon atoms, and has 7 to 1 carbon atoms.
At least about 9 of the total units are derived from monosubstituted hydroquinone substituted with 0 aralkyl groups.
This is achieved by means of a fiber- or film-forming melt anisotropic wholly aromatic polyester that is molten.

As mentioned above, the melt anisotropic wholly aromatic polyester of the present invention consists essentially of units (-) derived from an aromatic dicarboxylic acid and units (t) derived from an aromatic dihydroxy compound, or (I) ]).

)) and units (c) derived from a p-oriented aromatic oxycarboxylic acid. The latter wholly aromatic polyester differs from the former wholly aromatic polyester in that it contains p-oriented aromatic oxycarboxylic acid as a main component, but both wholly aromatic polyesters have the above (, )and(
The unit of 1)) is particularly one of the features of the present invention - CIg -Ar (where ■ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and Ar is an aromatic group having 6 to 8 carbon atoms) ) are common in that they contain a unit derived from a monosubstituted hydroquinone whose nucleus is substituted with an aralgyl group having 7 to 10 carbon atoms, and all fully aromatic polynisdels have excellent linearity in their molecular chains. They also have in common that they provide optically anisotropic melts.

The units (3) derived from the aromatic dicarboxylic acid forming the wholly aromatic polynisder of the present invention have about 90 or more molar proportions occupied by units derived from the p-oriented aromatic dicarboxylic acid. Here, the p-oriented aromatic dicarboxylic acid means that the two carboxyl groups bonded to the aromatic nucleus are 1,4-phenylene, 1,4-naphthylene, 4.4
'-biphenylene, coaxially arranged in opposite positions on the aromatic nucleus, or 1,5-naphthylene, 2゜6-
A plurality of benzene rings are directly condensed or bonded, such as naphthalene, 3.3'-(or 3.5') biphenylene, on an aromatic nucleus consisting of a plurality of benzene rings in opposite or symmetrical positions along parallel axes. refers to an aromatic dicarboxylic acid arranged in

Examples of p-oriented aromatic dicarboxylic acids include terephthalic acid, chlorterephthalic acid, and bromoterephthalic acid.
．． 5-Dibromoterephthalic acid.

Terephthalic acids such as methyl terephthalic acid; Naphthalenedicarboxylic acids such as 1.4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2.6-naphthalenedicarboxylic acid: 4,4'-diphenyldicarboxylic acid; 4,4'-diphenyldicarboxylic acid;
l s 3,3'-diphenyldicarboxylic acid, 3,3'
-dibromo-4,4'-diphenyldicarboxylic acid and the like. These may be used alone or in combination. Among these, terephthalic acids, particularly terephthalic acid, are preferred.

The unit (a) derived from an aromatic dicarboxylic acid preferably consists essentially of units derived from a p-oriented aromatic dicarboxylic acid as described above. However, units derived from aromatic dicarboxylic acids with m-orientation other than p-orientation, or units derived from aromatic dicarboxylic acids bonded via multiple benzene rings, heteroatoms, etc. may contain up to about 10 molar.

m-oriented aromatic dicarboxylic acid means that the two carboxyl groups bonded to the aromatic nucleus are 1,3-phenylene or 1
．． 3-, 1.6-, 1.7- or 2,7-naphthylene or 3,4'-biphenylene, which are not adjacent on the aromatic nucleus, and are coaxial with the aromatic nucleus. Refers to an aromatic dicarboxylic acid in which VC is not arranged in opposite positions on the parallel axis.

Such m-oriented aromatic dicarboxylic acids include, for example, isophthalic acid, 1,3-naphthalene dicarboxylic acid, 1
, 6-naphthalene dicarboxylic acid.

1.7-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 314'-diphenyldicarboxylic acid, 4
-Methylisophthalic acid, 5-methylinphthalic acid, 5
- tert-butyl isophthalic acid.

Examples include 5-methoxyisophthalic acid and naphthalene-2,7-dichloro-1,6-dicarboxylic acid.

In addition, aromatic dicarboxylic acids that are bonded via multiple benzene rings or heteroatoms include fl, l t r
X diphenyl ether-4,4'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid.

Examples include diphenoxyethane-4,4'-dicarboxylic acid, diphenoxyethane-3,4'-dimerboxylic acid, and diphenyl ether-4,47-dichloro-3,3'-dicarboxylic acid. Among the above, isophthalic acid,
Diphenyl ether-4,4'-dicarboxylic acid is preferably diphenoxyethane-4,4'-dicarboxylic acid.

The unit (b) derived from the aromatic dihydroxy compound forming the wholly aromatic polyester of the present invention is -OH-Ar
(Here, 几 is hydrogen or an alkyl group having 1 to 3 carbon atoms,
(Ar is an aromatic group having 6 to 8 carbon atoms) Mono-substituted with an aralkyl group having 7 to 10 carbon atoms
It contains about 90 moles or more of stone units formed from hydroquinone, or about 80 moles or more of units derived from such monosubstituted hydroquinones, and about 10 moles or more of substituted hydroquinones other than such monosubstituted hydroquinones.

Examples of the alkyl group having 1 to 3 carbon atoms for R include methyl, ethyl, propyl, etc.
Examples of aromatic groups include phenyl, m-chlorophenyl, p-chlorophenyl 0-7+F
− So = Quantity Specialist Miko Daigo Chio + rr+ −Mata B p
y fluorophenyl, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, 3°4-dimethylphenyl and the like.

Examples of the above-mentioned monosubstituted hydroquinone include etc. can be mentioned.

Such monosubstituted hydroquinone can be obtained by subjecting hydroquinone to a corresponding alcohol or an unsaturated compound having a vinylic double bond to a heating reaction in an aromatic hydrocarbon such as benzene in the presence of an acidic catalyst such as phosphoric acid or sulfuric acid.
It can be produced by methods known per se.

Unit (I]) derived from the above aromatic dihydroxy compound
may contain about 10 mol or more of substituted hydroquinone other than units derived from the monosubstituted hydroquinone. Such other substituted hydroquinones are preferably alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, phthylapentyl, hexyl, heftyl, octyl, nonyl, decyl, etc., or 9 to 1 carbon atoms.
0 tertiary aralkyl groups, e.g. 2-phenyl glob-
2-yl, 2-(p,m-1i0-chlorophenyl)prog-2-1l.

2-(p-, m- or 0-fluorophenyl)prog-2-yl, 2-(p-bromophenyl)prop-
2-'l+2-(p~iodophenyl)prop-2-
yl, etc., or an aralkyl group having 11 or more carbon atoms, such as 2-(su7t-1- or -2-yl)prop-2-yl, 2-(4-).

3- or 2-(2-0, alkyl-prog-2-yl)phenyl]-furof-2-4, etc., is a hydroquinone substituted by a halogen atom, such as chloro or bromo.

Examples of such substituted hydroquinone include methylhydroquinone and ethylhydroquinone.

t-butylhydroquinone, croconohydroquinone,
Bromohydroquinone, 2-1-amylhydroquinone, 2-t-hequinulnohydroquinone, 2-1-hebutylhydroquinone, 2-1-octylhydroquinone,
2-nonylhydroquinone, 2-1-decylnohydroquinone, 2-(2,5,5-)dimethylhexyl-2-yl)hydroquinone, 2-(2,6
, 6-trimethylhebutyl-2-yl)/\hydroquinone, 2sec-amylhydroquinone, ' 2-5e
e-hexylhydroquinone, 2-sec-heptylneutroquinone, 2-sec-octylhydroquinone.

2-(e,6-dimethylhepto-2-yl)-hydroquinone; 2-(2-phenylglogu-2-yl)hydroquinone, 2-C2-(4-methylphenyl)flobu-2-ylcono-itoquinone, (diphenylmethyl )
No Idroquinone.

(Phenyl 4-tolylmethyl)-hydroquinone.

(Phenyl 2-butylphenylmethyl)nohydroquinone, (1-naphthylmethyl)nohydroquinone, (2-
nano-hydroquinone.

(triphenylmethyl)-hydroquinone, (α.

α-diphenylethyl) no\troquinone, (α.

α-diphenyl-n-furovir) nohydroquinone,
(α-1-naphthylethyl)-hydroquinone, (α-
2-Naphthylethyl)-hydroquinone, cyclopentyl-hydroquinone, (1-ethylcyclopentyl)-hydroquinone, cyclohexylhydroquinone, (1-ethylcyclopentyl)-hydroquinone, (1-ethylcyclopentyl)-hydroquinone,
-methylcyclohexyl)hydroquinone, (1-butylcyclohexyl)hydroquinone, (4-butylcyclohexyl)hydroquinone, and the like.

More preferably, the substituted hydroquinone has a substituted alkyl group or an aralkyl group bonded to the hydroquinone skeleton via a tertiary carbon atom.

The wholly aromatic polyester of the present invention has units derived from monosubstituted hydroquinone with such substituents, which are bonded to the hydroquinone skeleton by a tertiary carbon atom,
Excellent oxidation stability and solvent resistance at high temperatures.

At the J'fJ position in (I) above, as mentioned above, units derived from mono-substituted hydroquinone account for about 90 or more moles, or mono-substituted hydroquinone and substituted hydroquinone other than mono-substituted hydroquinone It is necessary that the total amount of derived units account for about 90 moles or more. Up to about 10 molar units of the above (b) coronation can therefore be occupied by units derived from other aromatic dihydroquine compounds.

Examples of such other aromatic dihydroxy compounds include resolcif, 2,2-bis(4-hydroxyphenyl)furobukun, bis(4-hydroxyphenyl)sulfone, and 1,1-bis(4-hydroxyphenyl)cyclohexane. .

Examples include 4.4'-dihydroxydiphenyl, 4.4'-dihydroxydiphenyl ether, and 4-j-butylresorcinol.

- Unit (b) derived from an aromatic dihydroxy compound
According to the present invention, "2" consists essentially of units derived from the mono-substituted hydroquinone, or consists of units derived from the mono-substituted hydroquinone and substituted units other than the mono-substituted hydroquinone. The unit derived from hydroquinone and the unit (C) derived substantially from the radioactive aromatic oxycarboxylic acid contain approximately 70 moles of units derived from p-hydroxybenzoic acid and/or monosubstituted p-hydroxybenzoic acid. Contains at least 100%.

As substituted p-hydroxybenzoic acid, for example, carbon number 1
~4 alkyl groups, such as methyl.

Preferably used is p-hydroxybenzoic acid substituted with ethyl, propyl, butyl or halogen atoms, such as chloro, bromo, etc. For example, 3-chloro-
4-Hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid.

3.5-dichloro-4-hydroxybenzoin, 3-
Methyl-4-hydroxybenzoic f11. ．． a-I-butyl-4-hydroxybenzoic acid and the like can be mentioned.

As the units contained in an amount of 70 mol% or more, units derived from p-hydroxybenzoic acid are more desirable.

p-hydroxybenzoic acid and/' or monosubstituted p-
Units derived from hydroxybenzoic acid preferably account for about 80 moles or more of units (c), more preferably about 90 moles or more.

It is also particularly preferred that the unit (c) consists essentially of coronations derived from p-hydroxybenzoic acid and/or monosubstituted ρ-hydroxybenzoic acid.

The above unit (c) is derived from p-hydroxybenzoic acid and/or mono-substituted p-hydroxybenzoic acid with approximately 30 molar units. unit.

Here, p-oriented aromatic oxycarboxylic acid means that the relationship between the hydroxyl group bonded to the aromatic nucleus or the group derived from the hydroxyl group and the carboxyl group is such that the p-oriented aromatic dicarboxylic acid Refers to the same relationship between two carboxyl groups as described for acids. Examples of other p-oriented aromatic oxycarboxylic acids include p-(β-hydroxyethoxy)benzoic acid, p-(4-
Hydroxyphenoxy)benzoic acid, 4-hydroxy-1
-naphthoic acid, 6-hydroxy-2-naphthoic acid, p-
(4-hydroxyphenyl)benzoic acid and the like can be mentioned.

The melt anisotropic wholly aromatic polyester of the present invention has the above (a
) and (+)), or consists essentially of units (a), (b) and (c) above.

The latter wholly aromatic polyester containing the unit (c) is represented by the unit derived from the above p-oriented aromatic dicarboxylic acid and 10HR-Ar (where R and Ar are the same as defined above). Each contains at least about 9 moles, preferably about 20 moles, and more preferably about 30 moles of units derived from a monosubstituted hydroquinone substituted with an aralkyl group having 7 to 10 carbon atoms.

As is well known in the art, the fully aromatic polyester of the present invention is one in which equal amounts of hydroxyl groups and carboxyl groups react to form an ester bond forming the main chain. Generally, the above (a) unit and the above (b) unit are contained in equal equivalent amounts.

Therefore, a wholly aromatic polyester containing the above (C) units formed, for example, from 10 moles of terephthalic acid, IQ moles of 2-α-phenethylhydroquinone and 90 moles of p-oxybenzoic acid, has units derived from terephthalic acid ( a
) and the unit (b) derived from 2-α-quenethylhydroquinone are both contained in an amount of about 9 mol based on the total structural units (110 mol).

The wholly aromatic polyester of the present invention has excellent linearity in its molecular chain, and its melt has optical anisotropy, as can be understood from the constituent components listed in section 2. The wholly aromatic polyesters of the present invention nevertheless have relatively low melting points and flow onset temperatures as defined below, e.g., from about 250 to about 360°C, and therefore have excellent melt formability and melt formability. It is greatly protected from deterioration due to oxidative decomposition and thermal decomposition, and can provide a variety of excellent molded products.

In particular, the fully aromatic polyester of the present invention can be used in organic solvents such as chlorophenol, a mixture of phenol and tetrachloroethane, a mixture of p-fucrophenol and tetrachloroethane, a mixture of trifluoroacetic acid and chloroform, and a mixture of trifluoroacetic acid and tetrachloroethane. Shows solubility in mixed liquids, etc. In addition, such wholly aromatic polyesters exhibit solubility in organic solvents and, for example, exhibit affinity for various vinyl compounds, and therefore, their molded articles cannot be treated with vinyl compounds. A vinyl compound can be introduced into a molded article by this method. This means that various desired properties such as dimensional stability, oxidation resistance, chemical resistance, etc. can be further imparted to the wholly aromatic polyester of the present invention by post-processing.

The solid viscosity measured as a solution of tan in a mixed solvent is preferably 0.8 or more, more preferably 2.0 or more, and particularly preferably 3.0 or more.

In the present invention, "melt anisotropy" means that the polymer exhibits optical anisotropy even in a molten state. For example, JP-A-53-109598 describes in detail the characteristics of wholly aromatic polyesters exhibiting melt anisotropy.

The melt anisotropic wholly aromatic polyester of the present invention can actually be produced by various methods. For example, a method of heating and polycondensing a predetermined component in the presence of an aryl carbonate, using at least one of an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and a p-oriented aromatic oxycarboxylic acid as an ester; Examples include a method of heating and polycondensing components.

Preferred embodiments encompassed by these methods are described below, for convenience of explanation, for the production of fully aromatic polyesters of the present invention consisting of units derived from terephthalic acid, cosatylhydroquinone, and p-oxybenzoic acid. Explain.

1) Add aryl carbonate such as diphenyl carbonate to terephthalic acid and p-oxybenzoic acid and heat 1
．． After carrying out the esterification reaction, 2-α-phenegluhydroquinone is added and heat polycondensation is carried out (hereinafter referred to as the first method) 2) phenyl ρ-oxybenzoate, terephthal fl
Schiff: A method of subjecting a mixture of c-nyl and 2-α-7 enethylhydroquinone to single polycondensation by heating (hereinafter referred to as the second method) The first method will first be explained.

Examples of the aryl carbonate include diphenyl carbonate and ditolyl carbonate.

Mention may be made of polycarbonates such as di-chlorophenyl carbonate, phenyltolyl carbonate and poly-2-α-phenethylphenylene carbonate. Among these, diphenyl carbonate has stable quality and purity.

It is preferably used from the viewpoint of reactivity, etc. The amount of aryl carbonate to be used is 0.9 to 1.1 times the amount of free carboxyl group of terephthalic acid and p-oxybenzoic acid in terms of force-bonate bond, especially #1 is 1 times equivalent. It is preferable that

The reaction is usually carried out at 200-300°C, preferably at 200-28°C.
The reaction is carried out at a temperature of 0° C. until the generation of carbon dioxide gas produced by the reaction substantially stops. This reaction is suitable for 1 to 6 hours and is preferably carried out in the presence of a catalyst. Examples of the catalyst include titanium compounds such as gu-tantetrabutoxide, titanyl oxalate, titanium acetate, etc.; tin compounds such as stannous acetate; others such as zinc carbonate, lead oxide, antimony dioxide, andimony pentoxide, bismuth trioxide,
Lead, antimony, bismuth, cerium, lanthanum, lithium, sodium, potassium, zinc, such as cerium acetate, lanthanum oxide, lithium oxide, potassium benzoate, calcium acetate, magnesium oxide, magnesium acetate, etc.
Examples include compounds containing gold such as magnesium and calcium. Among these, compounds containing titane, tin, and antimony are preferred because they can be used in common with the following polycondensation reaction. The amount of the catalyst to be used is from 0.00 to 0.5 mole, and more preferably from 0.00 to 0.5 mole based on terephthalic acid.
It is preferable that the amount is 0.01 to 0.1 mol.

When the reaction between terephthalic acid and aryl carbonate is completed in this way, the temperature in the reaction system is reduced to 200 to 280°C.
1.0 to 1.0% per mole of terephthalic acid component while maintaining
3 moles, more preferably 1.01 to 1.2 moles of 2-α
- Add phenethylhydroginone and carry out the next polycondensation reaction.

Although the polycondensation reaction proceeds substantially without a catalyst, it is preferably carried out using a conventionally known transesterification catalyst. Among these transesterification catalysts, calcium and magnesium are preferred.

Strontium, barium, cerium, manganese, cobalt, am, germanium.

Examples include compounds containing metals such as tin, lead, antimony, and bismuth, and specific examples include magnesium acetate, calcium benzoate, strontium acetate, barium propionate, lanthanum carbonate, cerium oxide, manganese acetate, cobalt acetate, and zinc acetate. , germanium oxide, stannous acetate, lead oxide, antimony trioxide, bismuth dioxide, and the like.

It is also preferred to use stabilizers with these transesterification (polycondensation) catalysts. Examples of preferred stabilizers are conventionally known trivalent or pentavalent phosphorus compounds or esters thereof, such as tinous acid, phosphoric acid, phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, etc. Phosphonic acid, benzylphosphonic acid, trimethyl phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphite.

Triphenylphonufate, diethylphenylphosphonate, dimethyl-(butyl)phosphonate, dimethyl-
(ethyl)phosphonate, dimethyl(benzyl)phosphonate, and the like. Such stabilizers improve the melt stability of the polymer by one shade, but depending on the type of catalyst they deactivate the polycondensation catalyst. When the catalyst is to be inactivated, it is preferable to add the stabilizer after the polycondensation reaction is completed. Since polycondensation catalysts containing antimony or germanium are not inactivated by stabilizers,
#When a catalyst is used, 77 IJ of the stabilizer can be added from the beginning of the polycondensation reaction.

The amount of these transesterification (polycondensation) catalysts used is 0.005 of the total number of moles of terephthalic acid and p-oxybenzoic acid.
It is preferably 0.5 to 0.5 molar, more preferably 0.01 to 0.1 molar. The amount (p) of the stabilizer used is preferably o,s<P/N<1.5 (where P: mole of stabilizer) relative to the amount (N moles) of the polycondensation catalyst used.

Such amounts of catalyst, optionally stabilizer and 2-α-7
After adding ethylhydroquinone to the reaction system, the reaction system is heated to, for example, 250 to 300°C, and the reaction is carried out under normal pressure, and the resulting monohydroxy aromatic compound, such as phenol, is leached out of the system to advance polycondensation. The polycondensation reaction is carried out initially under normal pressure and then under reduced pressure while allowing the monohydroxy aromatic compound to be produced to be leached out of the system.

The reaction under normal pressure is preferably carried out by successively increasing the reaction temperature. Such reaction under normal pressure is preferably carried out at as low a reaction temperature as possible, as long as the aromatic monohydroxy compound can be leached out. For example, 250°C
The polycondensation reaction proceeds slowly even at temperatures below, but at such temperatures, almost no aromatic monohydroxy compound produced remains outside the reaction system, so the polycondensation reaction soon reaches equilibrium.

Therefore, in practice, the polycondensation reaction is started at a reaction temperature of about 260°C, and the temperature is gradually raised, and when it reaches about 35 to 60% of the theoretical distillation amount of the aromatic monohydroxy compound, the temperature reaches 290°C.
Preferably, the reaction temperature is approximately .degree. If the reaction temperature is set at a high temperature of 290°C or higher from the beginning and the reaction is allowed to proceed, gelation etc. may occur! ! It may cause undesirable side reactions. After the aromatic monohydroxy compound of the gauze has wetted out of the system, the pressure of the reaction system is then reduced, and while the aromatic monohydroxy compound produced is further wetted out of the system, the degree of vacuum and reaction temperature are gradually increased to reach the final stage. 320~3 under pressure of about 1 inch or less
7 is preferred if the reaction is carried out at a reaction temperature of 70°C to produce a polymer with a predetermined degree of polymerization.

Next, the second method will be explained.

Phenyl p-oxybenzoate and diphenyl terephthalate can be prepared, for example, by reacting p-oxybenzoic acid or terephthalic acid with diphenyl carbonate or phenol according to methods known per se.

A process line for heating and polycondensing a mixture of p-oxybenzoate phenyl, diphenyl terephthalate, and 2-α-7 enethylhydroquinone, conditions that are exactly the same as the polycondensation reaction conditions described in the first method above. It can be carried out below.

According to this second method, p-oxybenzoic acid phenyl and terephthalic acid diphenyl are purified in a highly pure state.
Since it can be reacted with -7 enethylhydroquinone, the quality of the obtained wholly aromatic polyester jJq is further improved.

In this sense, the second method is more preferable than the first method.

As mentioned above, the wholly aromatic polyester of the present invention thus obtained has a relatively low melting point and flow initiation temperature, although it exhibits @melting anisotropy, and therefore can be easily converted from an optically anisotropic melt. It has the characteristic of being melt moldable.

Therefore, according to the invention, the melt-anisotropic wholly aromatic polyester of the invention is thermally melted to form an optically anisotropic melt, and the melt is formed into a film or fiber according to melt-forming methods known per se. There is also provided a method for producing a film or fiber of a melt anisotropic wholly aromatic polyester, characterized in that:

Conventionally known melting anisotropic wholly aromatic polyesters generally have a relatively high melting point and flow initiation temperature, and therefore the temperature range in which a stable melt can be formed avoiding the thermal decomposition temperature of the polyester is very narrow and relatively low. Due to the fact that melts exhibit high melt viscosities, it has been difficult or impossible to obtain molded articles exhibiting good mechanical properties according to melt molding methods.

According to the method of the invention, a wholly aromatic polyester is heated to a temperature between its melting point and its decomposition temperature to form an optically anisotropic melt. Generally, it is preferred that the Calothermal temperature be between the onset of flow temperature of the fully aromatic polyester and a temperature about 50° C. above the melting point.

Since the fully aromatic polyesters of the present invention preferably have flow onset temperatures between about 250 and about 360<0>C, for example, such fully aromatic polyesters can be run at temperatures below about 400<0>C. Generally about 250 to about 400℃
A temperature of is preferably employed.

According to the method of the present invention, molded articles of various shapes can be manufactured from the wholly aromatic polyester of the present invention. More specifically, for example, fibers are produced by melting wholly aromatic polyester at, for example, 300 to 400°C and extruding it from a spinneret at a draft rate of 5 to 5,000 m and a winding speed of 10 to 500 m.
/xtfn. The obtained polyester fiber does not necessarily need to be subjected to stretching or heat treatment. Just by melt spinning and winding, for example, strength 5
It is possible to produce 49 fibers with high strength and high Young's modulus, f/de or more and Young's modulus of 2500 KF/- or more. If this fiber is heat treated at, for example, 200 to 300° C. for about 10 hours while maintaining its fiber form, its strength can be further increased several times. This fiber can be advantageously used for tire cords, rubber reinforcing materials, fillers, and other heat-resistant industrial materials.

Further, the film can be obtained by melt extruding from a gouey at 300 to 400° C. and winding it around a drum. A conventionally known device can be used as the film forming machine. Draft during extrusion is 1-5Q, preferably 1-5Q
It is 10. The film extruded onto the drum may be left to cool at room temperature, or may be rapidly cooled in water.

The polyester film thus obtained can then be biaxially stretched, if necessary. Biaxial stretching can be carried out using methods and equipment known per se. Usually, biaxial stretching can be carried out by stretching about 1.1 to about 5 times in both the machine axis direction and the direction perpendicular thereto. Stretching can be carried out at a temperature of about 150 to about 250°C.

The films obtained by the method of the invention, even as unstretched films, have a strength of, for example, about 30 K9/, 4 or more, about 70
It shows a Young's modulus of 0 Kr/- or more.

Such a film of the present invention exhibiting high strength and Young's modulus is
Utilizing their excellent mechanical properties, they can be used, for example, as films for magnetic tapes, films for metal deposition, films for flexible printed wiring, films for electrical insulation, and the like.

The wholly aromatic polyester of the present invention, in particular, the wholly aromatic polyester containing units derived from monosubstituted hydroquinone having a substituent bonded to the hydroquinone skeleton through a primary or secondary carbon atom, Since it is soluble in organic solvents, it is also possible to prepare a dope in an organic solvent and convert it into a film according to methods known per se, for example casting methods.

The film produced in this manner also has high strength and Young's modulus, similar to the film obtained by the melt-forming method described above.

〔Example〕

The present invention will be explained below with reference to Examples. In addition, example 1
All parts are 1 part by weight. In addition, the intrinsic viscosity in the present invention is 10 cm for fully aromatic polyester.
- dissolved in a mixed solvent (p-chromitzenol/tetrachloroethane-1/1 vot/vol mixture), 5
The relative viscosity (η'') at 0°C was determined by the Ostwald viscosity set and determined by the following formula.

Intrinsic viscosity -1n 77+20.1 In addition, the flow start temperature is 0.5 in diameter for fully aromatic polyester.
The polyester is placed in a tester equipped with a nozzle having a length of m and a length of 4u, and the temperature is raised at a rate of 2°C per minute under a pressure of 60 Kp/- to the temperature at which the polyester starts to flow out from the nozzle. I asked for it as.

Furthermore, the specific gravity was determined by heat-treating the polymer at 200° C. for 3 hours to crystallize it, and using a mixed solvent of carbon tetrachloride and 〇-hexane to measure the specific gravity using a pycnometer.

Furthermore, water decomposition resistance of polymer 1.02 at 240℃
After crystallization by heat treatment for 15 hours at a temperature of 10-
of distilled water, and then heated at 120℃ for 48℃.
The intrinsic viscosity before the heat treatment (ηinh
) and the intrinsic viscosity after treatment (ηinh) were determined using the following formula.

Example 1 Diphenyl terephthalate aXS part Monomethylbenzylhydroquinone 225 parts Antimony trioxide 0.1 part was heated under normal pressure at 260°C for 30 minutes and at 270°C for 30 minutes for an additional 2
The reaction was carried out at 90°C for 30 minutes while distilling off the phenol.

Then, while gradually raising the temperature and increasing the degree of vacuum by 100 degrees per 20 minutes, phenol was distilled off to carry out the polycondensation reaction, and finally the temperature reached about 16 degrees. 20 at 360℃ under high vacuum of Iν
Partial polycondensation was carried out.

The resulting polyester had a flow initiation temperature of 345° C. and an intrinsic viscosity of 3.55.

This polyester was melted at 380° C., extruded using a spinning machine with a spindle having a diameter of 0.3%, and wound up at a draft of 20 at a speed of 50 m/min. The resulting fiber had a fineness of 40 denier, a strength of 6.2 f/de, and a Young's modulus of 5000 Ky/de.
ym, and elongation was 2.4%. Further, the specific gravity of the polyester was 1.200, and the #I hydrolysis property was 95%.

In addition, the heat distortion temperature of the molded product obtained by melt-molding this polyester at 370°C (the heat distortion temperature was measured using A8TM NOD
-648) has an extremely high heat distortion temperature of 300°C or higher.

Examples 2 to 4 Polyesters were produced in the same manner as in Example 1 using raw materials having the compositions shown in Table 281, and were further melt-spun and molded.

Table 1 Heat distortion temperature of the obtained polyester molded product.

The viscosity and thread physical properties were as shown in Table 2.

@2 Table Examples 5 to 7 Polyester was produced in the same manner as in Example 1 using the raw materials having the compositions shown in Table 3.

Table 3 The viscosity of the polyester obtained, the heat distortion temperature of the molded article, and the physical properties of the thread were as shown in Table 4.

Table 4 Examples 8 to 10 About 1 Question The same procedure as in Example 1 was carried out except that the temperature of "j' under high vacuum was set at 330 DEG C., to obtain the napolyesters shown in Table 5.

Table 5 (■) Note) The polyesters of Examples in the table each contain equimolar amounts of each structural unit listed in the table.

Example Day The polyester having an intrinsic viscosity of 1.9 obtained in Example 9 was ground into about 10 to 16 meshes, and the temperature was gradually raised from 200°C to 290°C over 5 hours, and the mixture was heated at 290°C for 5 hours. Heated for a period of time to polymerize in the same phase in a nitrogen stream, and the intrinsic viscosity was 6.4.
of polymer was obtained.

This polymer was mixed with p-chlorophenol at 1.1°2.2
- Tetrachloroethane was dissolved in a mixed solvent of 6:4 (weight ratio) at 140°C to prepare a triple dope of the polymer.

The dope was poured onto a glass plate and immersed in a large amount of acetone to remove most of the solvent and form a self-supporting film. Next, this product was fixed with a metal frame, dried and heat treated under vacuum at 60°C for 5 hours, at 100°C for 5 hours, and further at 150°C for 5 hours to obtain a film with a thickness of about 30μ.

Table 6 shows the physical properties of the obtained polyester film.

Table 6 Example 12 Diphenyl terephthalate axg part Benzylhydroquinone 220 parts Antimony trioxide 0.1 part was added under normal pressure at 260°C for 30 minutes, at 270°C for 30 minutes, and then at 290°C for 30 minutes while distilling off the phenol. Made me react. Then, while gradually increasing the temperature, the temperature was increased to 100℃ for 20 minutes.
While increasing the degree of vacuum in mHl increments, phenol was distilled off and the polycondensation reaction was carried out.
Polycondensation was carried out at ℃ for 20 minutes.

The obtained polyester was pulverized into approximately 10 to 16 meshes, gradually heated from 200°C to 290°C over 5 hours, and then heated at 290°C for 5 hours to undergo in-phase polymerization in a nitrogen stream. A polymer with a viscosity of 7.1 was obtained.

A dope was prepared in the same manner as in Example 11 using a polymer of 100% polyester, and a film was further obtained.

Table 7 shows the physical properties of the obtained polyester film.

Table 7 Also “l,”+”

Claims (1)

[Scope of Claims] i, a unit (a) in which the p-oriented aromatic dicarboxylic acid is derived from an aromatic dicarboxylic acid having about 90 moles or more, and -〇H㇠-Ar (where R is hydrogen or the number of carbon atoms 1 to 3 alkyl group, Ar is an aromatic group having 6 to 8 carbon atoms) The monosubstituted hydroquinone which is nuclear-substituted with an aralkyl group having 7 to 10 carbon atoms is about 90 molti or more, or the above-mentioned Substantially consists of degree (b) derived from an aromatic dihydroxy compound in which the monosubstituted hydroquinone and the substituted hydroquinone other than the monosubstituted hydroquinone have a molecular weight of about 90 molar or more, and the monosubstituted hydroquinone has a molecular weight of about 8θ molar or higher. or the above unit (3), (
b) and p-hydroxybenzoic acid and/or monosubstituted p-hydroxybenzoic acid containing about 70 molar or more p-
consisting essentially of units (c) derived from an oriented aromatic oxycarboxylic acid, and consisting essentially of units derived from a p-oriented aromatic dicarboxylic acid and -OHR-Ar (where R and Ar
is the same as defined above), in which at least about 9 mol of the total structural units are derived from mono-substituted hydroquinone which is nuclear-substituted with an aralkyl group having 7 to 10 carbon atoms. Melting anisotropic wholly aromatic polyester. Z p-oriented aromatic dicarboxylic acid is terephthalic acid,
4,4'-diphenyl dicarbon It, 2゜6-
The wholly aromatic polyester according to claim 1, which is naphthalene dicarboxylic acid or 1,5-naphthalene dicarboxylic acid or a nuclear substituted derivative of these acids. 1 The monosubstituted p-hydroxybenzoic acid has 1 to 1 carbon atoms.
The wholly aromatic polyester according to claim 1, which is mono-substituted with an alkyl group or a halogen atom of 4% FF. 4 Units derived from the above aromatic dihydroxy compound (b
) consists essentially of units derived from the monosubstituted hydroquinone, or consists essentially of units derived from the monosubstituted hydroquinone and units derived from a substituted hydroquinone other than the monosubstituted hydroquinone The wholly aromatic polyester of item 1. & The unit (,) derived from the above aromatic dicarboxylic acid is
The wholly aromatic polyester of claim 1, which consists essentially of units derived from a p-oriented aromatic dicarboxylic acid. 6. Claim No. 6, wherein the unit (c) derived from the p-oriented aromatic oxycarboxylic acid consists essentially of units derived from p-hydroxybenzoic acid and/or monosubstituted p-hydroxybenzoic acid. 1. Fully aromatic polyester. 7. The wholly aromatic polyester according to any one of claims 1 to 7, wherein the wholly aromatic polyester has an intrinsic viscosity of 0.8 or more. a The flow start temperature of fully aromatic polyester is about 250~
A wholly aromatic polyester according to any one of claims 1 to 7, having a temperature of between about 360°C.