JPS6248722A - Optically anisotropic polyester - Google Patents

Abstract

PURPOSE:To provide the titled novel polyester composed of plurality of specific structural units, moldable by melt molding and giving a molded article having excellent mechanical properties and optical anisotropy. CONSTITUTION:The objective polyester having a melting point of <=400 deg.C and melt viscosity of 10-15,000 poise is produced by the polycondensation of (A) p-hydroxybenzoic acid to give the structural unit of formula I, (B) hydroquinone to give the structural unit of formula II, (C) an aromatic dihydroxy compound to give the structural unit of formula III (X is phenyl, etc., substituted with Cl), (D) an aromatic dicarboxylic acid to give the structural unit of formula IV (e.g. 4,4'-diphenyldicarboxylic acid) and (E) an aromatic dicarboxylic acid to give the structural unit of formula V (Y is phenyl, etc.). The amount of the component A is 0-90mol% of the whole composition, that of B+C+D+E is 100-10mol% of the whole composition, that of B+C is equimolar to D+E, the ratio of B/(B+C) is 100-20mol% and the ratio of D/(D+E) is 100-50mol%.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel optically anisotropic polyester that can be melt-molded at temperatures below 450°C and can provide molded products having excellent mechanical properties and optical anisotropy. It is something.

(Conventional technology) In recent years, there has been an increasing demand for higher performance glass materials, and many polymers with new performance properties have been developed and offered on the market. The optically anisotropic liquid crystal polymer is attracting attention because of its excellent mechanical properties.

Fully aromatic polyesters are widely known as such liquid crystal polymers, and for example, p-hydroxybenzoic homopolymers and copolymers are commercially available under the trademark "EKONOL." However, p-hydroxybenzoic homopolymers have a low melting point. Since the temperature is too high and it is possible to melt and mold it, methods of lowering the melting point by adding various components to p-hydroxybenzoic acid have been studied.
A method of co-combining phenylhydroquinone, terephthal wt and/or 2,6-natsuta Vundicarbo/d (Publication Patent Publication No. 55-500)
A method of copolymerizing 215 (ri, p-hydroxybenzoic acid) with 2,6-dihydroxy767talene and terephthalic acid (Japanese Unexamined Patent Publication No. 54-50594) has been proposed.

<Problems to be solved by the invention> However, although the optically anisotropic polyester obtained by these methods has a relatively low melting point of 450°C or more, the elastic modulus of the spun yarn is still insufficient, and Even higher modulus of elasticity is desired.

Therefore, the present inventors conducted intensive studies with the aim of obtaining an optically anisotropic polyester that is melt moldable and has excellent balance between mechanical properties represented by superelastic modulus and optical anisotropy.
- and dorokiku benzoic end and hydroino 7.4.4'-Diphenyldicarboxylic acid and terephthalic acid polyester (JP-A-58-91721 II) and 7-enylhydroquinone and 4.4'-yyenyl Polyester consisting of nocarboxylic acid (JP-A-59-41329
They discovered that a polyester consisting of p-hydroxybenzoic acid and 7 ether hytroΦ knots 4,4'-diphenyldicarboxylic acid (Japanese Unexamined Patent Publication No. 11859-41328) could give a molded article with a high elastic modulus and filed an application. However, it was discovered that a polyester consisting of three structures (F) has an even higher modulus of elasticity, and the present invention was completed.

Means for Solving the Problems> That is, the present invention consists of the following structural units (I) to V)] constitutes 100 to 10 mol% of the total, and the units [(I) 10(2)] and [■ + (V)] constitute substantially equal molar proportions (Jl) / ((I) 10 ■
] is 100 to 20 mol% and q0/[(to)
+(V)] is 100 to 50 mol%.

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However, in the optically anisotropic polyester of the present invention, the structural unit (I) is composed of units (I8 (I), 0W, (V)), and the structural unit (I) is p-hydroxy7benzoic acid. (Indicates 4 units.

In addition, the structural unit (I) 1@ is -11 such as hydroquinone
1f88 is a structural unit obtained by removing the 7 hydrogen atoms in human cI of a dihydroxy compound, and ■ is a structural unit obtained by removing the hydrotinle group of an aromatic dicarboxylic acid such as 4,4'-diphenyldicarboxylic acid. The structural units of the aromatic dihydroxy compound and the aromatic radical 17 are shown when the aromatic dihydroxy compound and the aromatic radical are mixed together in a substantially equimolar ratio.

The optically anisotropic polyester of the present invention has a melting point j! 45
The temperature is 0°C or lower, and it is possible to easily mold pongees, films, various molded products, etc. with excellent mechanical properties by ordinary melt molding. Here, for example,
The polyester consisting of P-hydrobycinbenzoin, hydroquinone, 4,4'-diphenyldicarboxylic acid, and terephthalic acid described in Publication No. 8-91721 has a relatively low melting point of 450°C or less and an elastic modulus of 66 GPa. However, the optically anisotropic polyester of the present invention has the advantages of better melt fluidity and significantly higher elastic modulus than the polyester described in the above-mentioned publication.

In the optically anisotropic polyester of the present invention, the content of the structural unit (I) is preferably 0 to 90 mol%, particularly preferably 15 to 80 mol%. This is undesirable because the physical properties deteriorate. The ratio of (I)/((I) + ([)) is 100 to 20 mol%, preferably 100 to 30 mol%.

On the other hand, the -T=le ratio of (V')/((n+(V)) is 10
It is 0 to 50 mol%, preferably 100 to 56 mol%.

The aromatic dihydroxy component forming the structural unit I in the optically anisotropic polyester of the present invention is chlorohydroquinone, methylhydroquinone, phenylhydroquinone, tert-butylhydroquinone7.4.4
'-Dihydroxybi-7-Dyl, 216':'Human a
It is a component selected from 4-sinaphthalene, 2,7-dihydroxynaphthalene.

In addition, the dicarboxylic acid component forming the above structural unit (■) is
Terephthalic acid, 2,6-naphthalenedicarbone fi,l
, 2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chloro/l/phenoxy)ethane-4,4'-dicarboxylic acid and 4,4'-dicarboxydiphenyl ether One or more selected dicarboxylic acid components.

Among these, the aromatic dihydroxy component forming the surface is phenylhydroquinone or tert-methylhydroquinone.

The optically anisotropic polyester of the present invention can be purified according to the conventional SRA method for polyester, and there are no particular restrictions on the manufacturing method, but typical manufacturing methods include the following (I) ~
(3) One example is the law.

(I) P-a seven to? 7 Benzoic acid and diesters of aromatic dihydroquine compounds such as hydroginone diacetate and hydroquinone dipropionate and 4.4'
- A method for producing aromatic dicarboxylic acids, mainly diphenyldicarboxylic acid, by demonocarboxylation/acid condensation.

(2) Aromatic didrochic compounds such as the phenyl ester of P-ogi7 benzoin moth, Oyohihite I2, and 4,
A method for producing 4'-diphenyldicarboxylic acid from cylphenyl ester by dephenolization condensation.

(3) After reacting aromatic dicarboxylic acids mainly consisting of P-ochynebenzoic acid and 4,4'-diphenyldicarboxylic acid with a desired amount of diphenyl carbonate to form diphenyl esters, aromatic dicarboxylic acids such as hydroquinone etc. A method of manufacturing by adding a dihydroxy compound and performing a phenol-free polycondensation reaction.

Typical examples of the fleet used in the polycondensation reaction are metal compounds such as stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate and potassium acetate, and anti-7-dioxide, which are particularly effective in dephenolization condensation. It is.

Some of the optically anisotropic polyesters of the present invention can be measured for their intrinsic viscosity in pentanfluorophenol, at a concentration of 0.1 (weight/volume 1)96
The value measured at °C is preferably 0.35 or more, particularly 0.4
~15.0 is preferred.

Further, the elution viscosity of the optically anisotropic polyester of the present invention is l
0 to 15,000 voids is preferred, particularly 50 to 10,
000 voids is more preferred.

In addition, this melt viscosity is (liquid crystal starting temperature + 40 to 100℃
) at a sliding speed of 2,000 to 4,000 (I/sec) using a Koka type flow tester.

In addition, when condensing the optically anisotropic polyester of the present invention, in addition to the components constituting the above structural units (I) to (V)), 1 m of isophthal d and 3.3'-diphenyl dicarbonate are added.
, 3.4'-diphenyl dihydropyIJ! , 2.2'-
Aromatic dicarboxylic acid 7a1 such as diphenyldicarboxylic acid
Cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid,
and other aromatic acid dicarboxylic acids such as n-oquineic acid, monofluoroic acid, and 2,6-oquine-7toic acid, etc., in a small proportion that does not impair the purpose of the present invention. You can force it.

The optically anisotropic polyester of the present invention thus obtained has a low melting point of 400°C or less, and can be used for extrusion molding, injection molding, compression molding,
Can be subjected to normal melt molding such as blow molding,
It can be processed into la fibers, films, three-dimensional molded products, weights, hoses, etc.

In addition, during molding, reinforcing agents such as glass a fiber, carbon fiber, asbestos, etc. are added to the optically anisotropic polyester of the present invention.
Fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers,
Additives such as lubricants, mold release agents, and flame retardants, as well as other thermoplastic resins, can be added to impart desired properties to the molded article.

The molded article obtained from the novel optically anisotropic polynisdel of the present invention has good optical anisotropy due to its parallel molecular arrangement, and has extremely excellent four-dimensional properties.

In addition, the molding obtained in this way, ~7. can be made stronger by heat treatment, and the elastic modulus can also be increased in many cases.

This heat treatment can be carried out in an inert atmosphere (e.g. nitrogen, argon, helium or water vapor) or in an oxygen-containing fJ
This can be done by heat treatment in B gas (eg air) at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension and can be carried out for a period of several minutes to several days.

<Example> The present invention will be briefly explained below with reference to Examples.

Example 1 P-acetoquine benzoic acid 6.48F (6 x 10 mol) and hydroquino/diacetate lsp in a polymerization test tube
(I2x 10 mol), tert-butyA/ /Itidrothinone diacet3. Op (L2x 10' mol) and 4,4'-2 phenyldicarboxylic acid 5.81
1 (Z4
Acetic acid depolymerization was carried out.

First, the reaction was carried out at 250 to 350°C for 3.0 hours in a nitrogen gas atmosphere, then the pressure was reduced to 0.5f (g) at 350°C, and the reaction was further carried out for 10 hours to complete the polycondensation.
A stoichiometric amount of acetic acid was extracted and a brown polymer was obtained.

The theoretical structural formula of this polymer is as follows, and the elemental analysis results of the polyester showed good agreement with the theoretical values as shown in Table 1. Further, the thermal properties of this polymer were measured with a differential scanning M) 1 meter (PerkinElmer type 1), and the melting point was 265°C.

m/2 n = 6/4 (molar ratio) Table 1 (with the exception of oxygen) was calculated from (I00%-C%-H%).

In addition, this polyester was placed on a sample stage of a polarized light microscope (g: Ia), the temperature was raised, and air was applied to confirm the optical anisotropy.As a result, the liquid crystal initiation temperature was 260°C, indicating good optical anisotropy. showed that.

This polyester was subjected to a flow tester at a spinning temperature of 34
Spinning was carried out at 0°C with a spinneret hole diameter of 0.3mmφ and 0.08ff.
A spun yarn of - was obtained. Note that the core viscosity is at a shear rate of 2,500
(I/sec) was 1,800 voices.

The elastic modulus of this spun yarn was measured using a Rheopyglon DDV-1-EA manufactured by Toyo Bold Kui Co., Ltd. at a frequency of 110 degrees, a temperature increase rate of 2°C/min, and a distance between chucks of 4ow, it was 108 GPa at 30°C. The elastic modulus was extremely high.

Example 2 P-acetoquinobenzoic acid 5.4f (3X1
0'mol), hydroquinone diacetate 5.82F
(3X10 moles), 4.4'-dibutenyl dicarboxylic acid 3.631 (L5X1O" moles), 2.6-naphthalene dicarboxylic acid 3.241 (I5X1O" moles)
A Jt condensation reaction was carried out under the same conditions as in Example 1.

The theoretical structural formula of this polyester is as follows, and the elemental analysis results of this polyester were in good agreement with theory 1 as shown in Table 2. In addition, the heat retention of this polymer was measured using differential scanning and a tokimeter (Perkin Elma 15).
The point was 279°C.

l /+n/n = 5/2.5/ 2.5 (molar ratio) Table 2 However, oxygen content ik (%) is (I00%-C%-H%)
Calculated from.

Further, this polyester was placed on a sample stand of a polarizing microscope and the temperature was raised to check the optical anisotropy. As a result, the liquid crystal initiation temperature was 256° C., indicating good optical anisotropy.

This polyester was subjected to a 70-tester and the spinning temperature was 34
Spinning was carried out at 0°C with a spinneret hole diameter of 0.3Wφ and 0.07Wφ.
A spun yarn was obtained. The melt viscosity is the sliding speed of 2,800
(I/l) 1,500, j? It was Is. This spun yarn is used as Toyo Boldfin (I) 1% Leo Bif a y
DDV-1-EA ヲItem frequency allOA, rising speed 2℃/min, chuck 1 distance! P-acetoquinobenzoic acid 10.08 => (5
, 6
+ 7 tannic carboxylic acid 2.27 t (L05
x 10 mol), isophtha k ea 0.581
(0.35X 10 -v=L) was charged and 11 condensations were carried out at a reaction temperature of 330°C according to the conditions of Example 1 to obtain an optically anisotropic polyester having a melting point of 281°C.

Using this polyester, spinning was carried out at a spinning temperature of 340°C (t) to obtain a spun yarn with a diameter of 06" and the elastic modulus was measured. The elastic modulus was 56 GPa at 30°C, which was lower than the polyester of the present invention.

Examples 3 to 13, Comparative Examples 2 to 4 P-1 setoxybenzoic acid (I) - idroginone diacetate (I), chlorno-1 hydroquino/dir-acetate ■, and methyl-hydroquinone diacetate in a Chiaikawa test tube. Acetate GL phenyl/S hydroquinone diacetate (7)
, tert-butylno-hydroquinone noacetate (V
T), 4,4'-dihydroxy/biphenyl G1.2.6
-dihydrocoxyf7 sauce; 101), 1217-dihydrokoxy7naphthavy CX) diacetate component consisting of 4.4'-diphenyldicarbonoic acid <X>, 2.6
-nanotaledicarbonoic acid (XI), 1,2-bis(2
-10rufenoquine) ethano-4,4'-cicarbo/acid (4), 1,2-bis(phenoxy7)ethane-4,4'
- deer kg: / acid (XI), te v p #
Combine the dicarboxy and Iti components consisting of Ia (Iff) as shown in Table 3, and add the acetate component and dicarboxylic acid component to a single test tube in the same manner as in Example 1. A polycondensation reaction was carried out. When the optical anisotropy of the obtained polymer was confirmed, Example 2~
Sample 4) had a high melting point and high melt viscosity, resulting in poor fluidity.

<Effects of the Invention> Since the aromatic polyester of the present invention can be melt-molded and molded products with high elastic modulus can be obtained, it can be used in various applications such as nearing glass as a metal substitute glass. I can do it.

Claims (1)

[Claims] Consisting of the following structural units (I) to (V), the unit (I) is 0 to 90 mol% of the total, and the unit [(II) + (III) + (IV)
+(V)] consists of 100 to 10 mol% of the total, the units [(II) + (III)] and [(IV) + (V)] consist of substantially equimolar proportions, and (II) / [(II) + (III)]
The molar ratio of (IV)/[(IV)
+(V)] is 100 to 50 mol%. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) −(O−X−O)−・・・・・・(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V) (However, X in the formula is ▲Mathematical formula, chemical formula There are tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, Y indicates a group selected from ▼ There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and Y indicates ▲ There are mathematical formulas, chemical formulas, tables, etc.
Indicates one or more groups selected from ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. . However, combinations where Y consists of units (I), (II), (IV), and (V) and where Y consists of X is ▲
There are mathematical formulas, chemical formulas, tables, etc. (excluding combinations consisting of ▼).