JPH04136028A - Aromatic polyester carbonate - Google Patents

Abstract

PURPOSE:To prepare a liq. crystalline arom. polyester carbonate having a wide processing range in melt molding and giving a molded article usable in areas where a high strength and a high elastic modulus are required by selecting a polyester carbonate comprising specific structural units in specified molar ratios. CONSTITUTION:An arom. polyester carbonate which comprises structural units (A) derived from p-hydroxybenzoic acid or a substd. p-hydroxybenzoic acid, units (B) derived from 2,6-dihydroxynaphthalene, units (C) derived from a dihydroxy compd. other than 2,6-dihydroxynaphthalene, units (D) derived from carbonic acid, and, if required, units (E) derived from an arom. dicarboxylic acid in such molar ratios that B+C=D+E, B/(B+C)>0.5, D/(D+E)=0.2-1.0, and A=0.1-0.9 provided that A+B+C=1, is insol. in p-chlorophenol or has, if soluble in p-chlorophenol, an inherent viscosity of 0.1g/dl soln. in p- chlorophenol at 30 deg.C of 0.5dl/g or higher, and has liq. crystalline properties is selected.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a novel aromatic polyester carbonate, and more specifically, to a novel aromatic polyester carbonate, and more specifically, to easily produce molded products having good melt moldability and excellent physical properties. The present invention relates to an aromatic polyester carbonate which can provide liquid crystallinity and has liquid crystallinity.

[Conventional technology]

In recent years, with the advancement of technology in various industrial fields and the trend toward energy conservation due to concerns about the supply of energy resources, organic polymer materials are also required to have higher performance and lighter weight. There is also a need for high performance materials that can be used as metal substitutes.

In response to the demand for higher performance in these plastics, optically anisotropic liquid crystal polymers, which are characterized by parallel alignment of molecular chains, are attracting attention as polymers with excellent mechanical properties. be.

A representative example of this liquid crystalline polymer is wholly aromatic polyester. For example, p-hydroxybenzoic acid homopolymers and copolymers have been provided for some time and are commercially available. However, this wholly aromatic polyester is often difficult to mold because it exhibits a very high transition temperature to a liquid crystal phase or has a decomposition temperature below the liquid crystal phase transition temperature. For this reason, with such materials, although molding methods such as compression molding can be applied, molding methods such as injection molding and melt spinning cannot be applied, or even if they can be applied, there is a problem in that they are accompanied by great difficulty.

On the other hand, in addition to wholly aromatic polyesters, polyester carbonates having various liquid crystal properties are known. For example, Japanese Patent Publication No. 59-30.727 and Japanese Patent Publication No. 59-30.
30.728, aromatic dihydroxy compounds based on p-hydroxybenzoic acid, hydroquinone or 4,4'-dihydroxydiphenyl, aromatic polyester carbonates based on carbonic acid and optionally aromatic carbonic acid. or known. However, because
Most of the molding temperatures for polyester carbonate disclosed in these published patent publications are 330 to 350.
It requires a high temperature of 26°C, and the injection temperature is 26°C.
Polymers at 0°C also have a problem of high melt viscosity and poor moldability.

Moreover, JP-A-1-153.720 discloses an aromatic polyester carbonate based on aromatic hydroxycarboxylic acid, 4,4-dihydroxydiphenyl, and carbonic acid. The polymer described in the examples of this patent publication has a melting point of 205 to 294°C and good moldability, but has low mechanical properties and is suitable for fields where high elastic modulus and high strength are required. There is a problem that it cannot be used as a molding material.

On the other hand, JP-A No. 2-29.424 discloses p-hydroxybenzoic acid, 4,4°-dihydroxydiphenyl, 2
Aromatic polyester carbonates based on dihydroxynaphthalene and carbonic acid are disclosed.

The polymers described in the examples of this patent publication also have good moldability, and since the use of 2,7-dihydroxynaphthalene greatly disturbs the linearity of the liquid crystalline polymer, However, we have not been able to obtain anything that is fully satisfactory in terms of physical properties.

[Problem to be solved by the invention]

The purpose of the present invention is to solve the problems of the prior art described above,
In addition to easily providing molded products that can be used in fields where melt molding processing range is wide and high strength and high modulus of elasticity are required,
An object of the present invention is to provide an aromatic polyester carbonate having liquid crystallinity.

[Means to solve the problem]

That is, the present invention provides (all)-hydroxybenzoic acid or nuclear substituted p-hydroxybenzoic acid, (b) 2,6-dihydroxynaphthalene, (c12,6
- a dihydroxy compound other than dihydroxynaphthalene, fd) carbonic acid, and optionally fe) aromatic sicarphonic acid, consisting of structural units based on (a), (b), (c
), (d) and fe) are respectively expressed as aXb, c, d and e, and a+b+c-1
When, b + c = d + e b/ (b + c) > 0.5 d / (d + e) - o, 2 ~ 1.0 a = 0.1 ~ 0.9 and satisfies the relationship, and parachlorophenol is used as a solvent. 0.1g/d! It is an aromatic polyester carbonate which has an inherent viscosity (H') at 300C of a solution with a concentration of 0.5 dl/g or more, or is insoluble in the above solvent and has liquid crystallinity.

The present invention will be explained in detail below.

The unit (a) constituting the wholly aromatic polyester carbonate obtained by the present invention is a substituted p-hydroxybenzoic acid composed of p-hydroxybenzoic acid, a nuclear-substituted p-hydroxybenzoic acid, or a derivative such as an ester thereof. The acids include C1-C4 alkyl, C1-C, alkoxy, C6-CIO aryl, C6-C1゜aralkyl (e.g. phenyl, tolyl or naphthyl) or halokene (preferably chlorine or bromine) with one or more aromatic rings. Nucleically substituted p-hydroxybenzoic acids which are further substituted, such as 4-hydroxy-2-methylbenzoic acid, 2-ethyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid, 2- or 3- Examples include chloro-4-hydroxybenzoic acid, 4-hydroxy-2-phenylbenzoic acid, and 4-hydroxy-3-phenylbenzoic acid. Preferably p-hydroxybenzoic acid or p-
-Hydroxybenzoic acid esters are used.

Further, the unit (b) constituting the wholly aromatic polyester carbonate of the present invention is derived from 2,6-dihydroxynaphthalene.

Furthermore, the unit (c) constituting the wholly aromatic polyester carbonate of the present invention is derived from dihydroxy compounds other than 2,6-dihydroxynaphthalene. Preferred dihydroxy compounds include hydroquinone,
Methylhydroquinone, ethylhydroquinone, propylhydroquinone, butylhydroquinone, chlorohydroquinone, bromohydroquinone, phenylhydroquinone, resorcinol, 1,4-dihydroxynaphthalene, 1,5-
Dihydroxynaphthalene, (1), 6-cyhydroxidinaphthalene, 2,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bis-(4-hydroxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)- Ethane, bisphenol-A, 1. l-bis-(4
-hydroxyphenyl)-cyclohexane, bis-(4
-hydroxyphenyl)-sulfone, 4,4°-dihydroxydiphenyl ether, 4,4°-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, and nuclear-substituted derivatives thereof. Note that one or two of other diols such as aliphatic diols such as ethylene glycol, neopentyl glycol, etc., and ring diols such as cyclohexane dimethylol, cyclohexane diol, etc., may be used within a range that does not impair liquid crystallinity.
You can also use substitutes of more than one species.

In the present invention, diaryl carbonates are used to introduce carbonate units (d). Preferred diaryl carbonates include cyphenyl carbonate, ditolyl carbonate, phenyl-tolyl carbonate, dinaphthyl carbonate, and the like.

In the present invention, the unit (e) consists of an aromatic dicarboxylic acid residue. The aromatic dicarboxylic acid residue is 8
~24 carbon atoms and may be substituted by up to 4 C1-C4 alkyl groups, C1-C4 alkoxy groups or halogen atoms per aromatic ring, e.g. naphthalene-1,5-dicarboxylic acid, diphenyl-
2,2'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, terephthal Acids such as isophthalic acid, naphthalene 2,6-dicarboxylic acid and their nuclear substituted derivatives are included. Further, a part of the unit (e) may be replaced with a residue of an aliphatic dicarboxylic acid such as succinic acid, adipic acid, etc., a ring dicarboxylic acid such as cyclohexanedicarboxylic acid, etc., within a range that does not impair liquid crystallinity.

The molar ratio of the respective components of the aromatic polyester carbonate consisting of the units (a), (b), (c1, (dl, and (el) according to the present invention is, when a+b+c=1, b+c=d+6 b/ (b+c)>0.5 d/(dle)~0.2-1.0 a=0.1-0.9, more preferably b/(b+c
)>0.6 d/(d+e) ~0.3-1.0 a=0.1-0.8. Within this range, it exhibits liquid crystallinity and has excellent moldability and mechanical properties. In particular, to improve the elastic modulus and strength, (b
The content of 2,6-dihydroxynaphthalene, which is a unit of An aromatic polyester carbonate is obtained.

O6Lg/d of the aromatic polyester carbonate obtained by the present invention using p-chlorophenol as a solvent! The inherent viscosity (IV) of a concentrated solution at 50°C is not particularly limited as long as it exhibits liquid crystallinity, but those with a low IV value may detach or elute from the surface of the molded product. It may cause mold stains during molding,
Since there is a risk of contamination with food and drink, this IV value should be set at 0.
It is necessary that it is 1 dl/g or more, preferably 0.5 dl/g or more. If the aromatic polyester carbonate according to the invention is partially soluble or insoluble in p-chlorophenol, it may also be considered to have the aforementioned minimum viscosity.

In addition, the aromatic polyester carbonate of the present invention may have a significantly large inherent viscosity or become insoluble in the solvent after being subjected to in-phase polymerization by so-called heat treatment. It is included in the range of aromatic polyester carbonates.

The aromatic polyester carbonates according to the invention may contain as terminal groups -H1-OH, -0CsHs or groups resulting from terminal cappers.

The aromatic polyester carbonate according to the present invention may contain the units (a) to (e) above in a random distribution or in blocks.

The aromatic polyester carbonate resin of the present invention can be produced according to a conventional polyester polycondensation method, and there are no particular restrictions on the production method, but a preferred production method will be described below.

That is, under reduced pressure below atmospheric pressure, at 160°C.
Temperature above 260°C, preferably above 180°C 26
After reacting at a temperature of less than 0°C, it is necessary to further react at a temperature of 260°C or more and 400°C or less, preferably 260°C or more and 360°C or less, under a pressure of lommHg or less.

The reason for this is that first of all, under reduced pressure below atmospheric pressure,
It is not preferable to carry out the reaction at a temperature of 60° C. or higher and lower than 260° C., since if the reaction is carried out under high temperature and high vacuum conditions from the beginning, the monomer will be distilled out of the reaction system, resulting in a decrease in yield.

In addition, the polymerization reaction was carried out under the pressure of 110 mm1 (26 mm
Completing the polymerization at a temperature of 0°C or higher and 400°C or lower is as follows:
This is to efficiently distill reaction by-products out of the system and obtain high molecular weight polyester carbonate. That is, 10m
Completing the polymerization at a pressure exceeding mHg or at a temperature below 260°C is undesirable, since a high molecular weight polymer cannot be obtained, and at a temperature exceeding 400°C, deterioration of the polymer occurs, which is undesirable.

Typical embodiments include, for example, the following two methods.

(2) A method for producing by dephenol polycondensation from p-hydroxybenzoic acid ester, aromatic dicarboxylic acid diester, diaryl carbonate, and a dihydroxy compound that provides the units (b) and (c).

(2) A method for producing by dephenol polycondensation from p-hydroxybenzoic acid, aromatic dicarboxylic acid, diaryl carbonate, and a dihydroxy compound that provides the units (b) and (c).

The reaction is preferably carried out in the presence of a catalyst. Suitable examples of such catalysts include magnesium acetate, manganese acetate, sodium acetate, potassium acetate, zinc acetate, titanium tetrabutylade, titanium tetraphenolate, sodium phenolate, zirconium butylade, titanium tetraphenolate, cobalt acetate, germanium dioxide,
Examples include antimony trioxide, dibutyltin diacetate, dibutyldimethoxytin, and n-butylstanoic acid. The amount of this catalyst used is preferably 0.000, based on the total weight of monomers used. 0001-1. 0 parts by weight,
More preferably, it is 0.001 to 0.2 parts by weight.

In addition, the obtained product is preferably heated under reduced pressure to
Further solid state polymerization can be carried out at a temperature of 300°C. 2
After ~48 hours, the molecular weight increases and the properties of the resulting aromatic polyester carbonate are further improved.

The polyester carbonate of the present invention exhibits a liquid crystal state when melted. The liquid crystal state referred to here can be observed using a polarizing microscope. That is, if in an optical system equipped with a pair of polarizers crossed at 90 degrees in a molten state, the polyester carbonate exhibits the property of allowing light to pass through the entire range or a portion thereof, then the polyester carbonate is classified as a thermotropic liquid crystal.

Further, the transition temperature from the crystal phase to the liquid crystal phase was measured by differential scanning calorimetry (DSC) at a temperature increase rate of 100 C/min.

The aromatic polyester carbonate of the present invention thus obtained has a transition temperature from a crystalline phase to a liquid crystalline phase of 4000°C.
It has low C or less, optical anisotropy, and particularly excellent mechanical properties in the uniaxial direction, and can be used for ordinary melt molding such as extrusion molding, injection molding, compression molding, and blow molding to form fibers, films, and LFF1 types. It can be processed into products, containers, hoses, etc.

In addition, for the aromatic polyester carbonate of the present invention, reinforcing agents such as glass fibers, carbon fibers, and asbestos, fillers, nucleating agents, flame retardants, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, etc. Additives such as or other thermoplastic resins can be added to impart desired properties to the molded product. These blends can be carried out at any stage from polymerization to compounding.

The aromatic polyester carbonate of the present invention has good melt moldability and extremely excellent mechanical properties due to the parallel molecular alignment resulting from its liquid crystallinity.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 124.3 parts by weight of p-hydroxybenzoic acid, 48.1 parts by weight of 2,6-dihydroxydinaphthalene, 308.5 parts by weight of diphenyl carbonate, and 0.04 parts by weight of loubyl orthotitanate as a catalyst. The mixture was charged into a polymerization reactor equipped with a stirrer and a vacuum distillation device, the pressure was set at 650 mmHg, and the mixture was heated to 200° C. under a nitrogen stream. The reaction temperature was gradually raised to 300° C. over 2 hours and 30 minutes, and phenol was further distilled off. Then, gradually increase the pressure to 0.5 mmH.
The reaction was carried out for 30 minutes.

After the reaction was completed, a light brown polyester carbonate was obtained. The yield was 162.8 parts by weight, which was 99%. The inherent viscosity was 1°91. Also,
As measured by DSC, the transition temperature from the crystal phase to the liquid crystal phase was 264°C.

Then, an optically anisotropic phase was observed at 265°C or higher using a polarizing microscope.

The obtained polyester carbonate was dried under reduced pressure at 120'C for 8 hours, and then spun at a spinning temperature of 280C using a melt spinning device equipped with a spinning hole of 1.0M in diameter.

The obtained polyester carbonate fiber has a tensile strength of 5
8, 1 kg/mm2, tensile modulus 5940 kg
/ mm” and elongation of 2.3%, which showed extremely high strength and high elastic modulus.

Practical Example 2 96.7 parts by weight of p-hydroxybenzoic acid, 48.1 parts by weight of 2,6-dihydroxynaphthalene, 24 parts by weight of terephthalic acid
．． A reaction was carried out in the same manner as in Example 1 using 9 parts by weight, 334.2 parts by weight of diphenyl carbonate, and 0.04 parts by weight of n-butyl orthotitanate as a catalyst.

After the reaction was completed, a light brown polyester carbonate was obtained. The yield was 149.3 parts by weight, or 96%. The inherent viscosity was 2.91°. Further, as measured by DSC, the transition temperature from the crystal phase to the liquid crystal phase was 238°C.

The optically anisotropic phase was observed using a polarizing microscope at temperatures above 240°C.

The obtained polyester carbonate was dried under reduced pressure at 120'C for 8 hours, and then spun at a spinning temperature of 2900C using a melt spinning device equipped with a spinning hole having a diameter of 1.0+r++++. The obtained polyester carbonate fiber had a tensile strength of 50.3 kg/mm''1, a tensile modulus of 5460 kg/mn+2, and an elongation of 2.1%, which was extremely high strength and high modulus.

Example 3 138.1 parts by weight of p-hydroxybenzoic acid, 34.3 parts by weight of 2,6 dihydroxynaphthalene, 3 parts by weight of diphenyl carbonate
A reaction was carried out in the same manner as in Example 1 using 12.5 parts by weight and 0.05 parts by weight of butyl orthotitanate as a catalyst.

After the reaction was completed, a dark brown polyester carbonate was obtained. The yield was 155.9 parts by weight, or 97%. The polymer was insoluble in p-chlorophenol and the inherent viscosity could not be measured. Furthermore, as measured by DSC, the transition temperature from crystal phase to liquid crystal phase is 30
The temperature was 4°C. Then, with a polarizing microscope, the optically anisotropic phase was determined.
Observed at temperatures above 0°C.

The resulting polyester carbonate was heated at 120'C for 8
After drying under reduced pressure for an hour, spinning was performed at a spinning temperature of 3200 C using a melt spinning device equipped with a spinning hole having a diameter of 1.0 mm. The resulting polyester carbonate fiber had a tensile strength of 42. l kg/mm2, tensile modulus 4850
kg/mm', elongation 1. It had an extremely high strength and high modulus of elasticity of 9%.

Example 4 96.7 parts by weight of p-hydroxybenzoic acid, 56.1 parts by weight of 2,6-dihydroxynaphthalene, 2 parts by weight of diphenyl carbonate
69.9 parts by weight, and as a catalyst, orthotitanic acid n-
0.04 parts by weight of butyl was reacted in the same manner as in Example 1.

After the reaction was completed, a dark brown polyester carbonate was obtained. The yield was 146.6 parts by weight, which was 98%. The polymer was insoluble in p-chlorophenol and the inherent viscosity could not be measured. Also, according to measurement by DSC, the transition temperature from crystal phase to liquid crystal phase is 33
It was 5°C. Then, with a polarizing microscope, the optically anisotropic phase was determined to be 3.
Observed at temperatures above 45°C.

After drying the obtained polyester carbonate under reduced pressure at 120°C for 8 hours, a spinning hole with a diameter of 1.0+nm was provided. Spinning was carried out at a spinning temperature of 350° C. using a spinning device. The obtained polyester carbonate fiber has a tensile strength of 39.3 kg/mm2 and a tensile modulus of 3670.
kg/mm2 and elongation of 2.0%, which showed extremely high strength and high modulus.

Example 5 165.7 parts by weight of p-hydroxybenzoic acid, 51.7 parts by weight of 2,6 dihydroxynaphthalene, 3 parts by weight of diphenyl carbonate
91.5 parts by weight, and as a catalyst, orthotitanic acid n-
0.06 parts by weight of butyl was reacted in the same manner as in Example 1.

After the reaction was completed, a dark brown polyester carbonate was obtained. The yield was 199.5 parts by weight, which was 98%. The polymer was insoluble in p-chlorophenol and the inherent viscosity could not be measured. Furthermore, as measured by DSC, the transition temperature from crystal phase to liquid crystal phase is 28
The temperature was 7°C. Then, with a polarizing microscope, the optically anisotropic phase was determined.
Observed at temperatures above 0°C.

The obtained polyester carbonate was dried under reduced pressure at 120'C for 8 hours, and then spun at a spinning temperature of 320C using a melt spinning device equipped with a 11.0 mm diameter spinning hole. The obtained polyester carbonate fiber has a tensile strength of 45, 2 kg/mm2, and a tensile modulus of 5350.
kg/mm' and elongation of 2.2%, which showed extremely high strength and high modulus.

〔Effect of the invention〕

The aromatic polyester carbonate of the present invention has a low transition temperature from a crystal phase to a liquid crystal phase of 400° C. or less, and has excellent moldability. Furthermore, due to the parallel molecular alignment resulting from its liquid crystallinity, it has excellent mechanical properties such as high strength and high elastic modulus.

Therefore, the aromatic polyester carbonate of the present invention is
By conventional melt molding such as extrusion molding, injection molding, blow molding, etc., useful molded bodies such as fibers, films, molded articles, containers, and hoses having excellent performance can be obtained.

Claims (1)

[Scope of Claims] (a) p-hydroxybenzoic acid or nuclear-substituted p-hydroxybenzoic acid, (b) 2,6-dihydroxynaphthalene, (c) dihydroxy compounds other than 2,6-dihydroxynaphthalene, (d) carbonic acid, and optionally (e) an aromatic dicarboxylic acid, consisting of a structural unit based on (a), (b), (c
), (d) and (e), the existence molar ratios of the structural units are a, b, c, d and e, respectively, and a+b+c=1
When, b+c=d+e b/(b+c)>0.5 d/(d+e)=0.2~1.0 a=0.1~0.9 and satisfies the following relationships and uses parachlorophenol as a solvent. An aromatic polyester carbonate characterized by having an inherent viscosity (IV) at 30° C. of a solution with a concentration of 0.1 g/dl of 0.5 dl/g or more, or being insoluble in the above-mentioned solvent and having liquid crystallinity.