JPH03126718A - Aromatic polyester - Google Patents

Abstract

PURPOSE:To obtain the title polyester useful as an engineering plastic, having excellent mechanical properties, heat resistance and improved fluidity, comprising a specific structural unit which satisfy a specific condition. CONSTITUTION:The objective polyester having a structural unit shown by formula I to formula IV (R is group shown by formula V to formula VII; X is H or Cl), comprising 40-95mol% formula l based on formulas (I+II+III), molar ratio of the formula II/formula III of (95/5)-(5/95) and formula IV substantially equimolar to formulas (II+III) and having 0.5-20.0dl/g logarithmic viscosity at 0.1g/dl concentration dissolved in pentafluorophenol at 60 deg.C.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention can obtain a polymer with a high degree of polymerization only by melt polymerization, can use a normal melt molding process, and has excellent mechanical properties,
The present invention relates to an aromatic polyester having heat resistance and improved molding fluidity.

<Conventional technology> In recent years, the demand for higher performance plastics has increased, and many polymers with various new performances have been developed and put on the market. Optically anisotropic liquid crystal polymers have attracted attention because of their excellent mechanical properties.

Fully aromatic polyesters are widely known as liquid crystal polymers, such as homopolymers of p-hydroxybenzoic acid and copolymers of 4,4-dihydroxybiphenyl and terephthalic acid.

However, the P-hydroxybenzoic acid homopolymers and copolymers often have too high a melting point and have insufficient melt flowability. For this reason, methods of copolymerizing p-hydroxybenzoic acid with various components to lower its melting point have been investigated.
A method of copolymerizing 6-naphthalene dicarboxylic acid (Publication Patent Publication No. 55-500215), a method of copolymerizing p-hydroxybenzoic acid with 2,6-hydroxynaphthalene and terephthalic acid (Japanese Unexamined Patent Publication No. 51-50594) and a method of copolymerizing p-hydroxybenzoic acid with 2,6-hydroxyanthraquinone and terephthalic acid (US Pat. No. 4,
224,433), 4.4- to p-hydroxybenzoic acid
A method for copolymerizing monodihydroxybiphenyl, terephthalic acid, and isophthalic acid (Japanese Patent Publication No. 57-24407,
Japanese Patent Publication No. 6025046 1 and a method of copolymerizing p-hydroxybenzoic acid with phenylhydroquinone and terephthalic acid (US Pat. No. 4,242.496) have been proposed.

Furthermore, a method has been proposed in which p-hydroxybenzoic acid is copolymerized with 4,4-dihydroxybiphenyl and/or hydroquinone, t-butylhydroquinone, and terephthalic acid (Japanese Unexamined Patent Publication No. 132920/1982), but the heat resistance Moreover, it had a low intrinsic viscosity and a small molecular weight, so it could not withstand actual use.

On the other hand, a method has been proposed in which p-hydroxybenzoic acid is copolymerized with 4,4-dihydroxybiphenyl, t-butylhydroquinone, and terephthalic acid to obtain a polymer with a high intrinsic viscosity and a sufficiently increased molecular weight (JP-A-Sho 62-1647
Publication No. 19).

However, although many of the aromatic polyesters obtained by these methods have relatively low melting points of 400'C or less, they also have insufficient fluidity or heat resistance, making it difficult to obtain even better results. It was found that fluidization and high heat resistance were necessary.

<Problems to be Solved by the Invention> The present invention solves the above-mentioned problems and provides an aromatic polymer having optical anisotropy with an excellent balance between heat resistance and fluidity without impairing the excellent mechanical properties of the liquid crystal polymer. The challenge is to obtain polyester.

Means for Solving the Problems> Therefore, as a result of intensive studies to achieve the above object, the present inventors found that p-hydroxybenzoic acid, 4,4-dihydroxybiphenyl, hydroquinone and 4,4-diphenyl ether dicarbonate Acid, 2,6-naphthalene dicarboxylic acid, ■, 2-bis(phenoxy)ethane-4,4”-
An aromatic polyester consisting of at least one aromatic dicarboxylic acid selected from dicarboxylic acid and 1,2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid preferably meets the above objectives. This discovery led to the present invention.

That is, the present invention is composed of the following structural units (I) to (IV), where the structural unit (■) is 40 to 90 mol% of [■+010], and the molar ratio of the structural unit @10 is 9515 to 5/95. , the structural unit ■ is substantially equimolar to the structural unit [@+([1)], and 0 in pentafluorophenol at 60°C.
．． Logarithmic viscosity when dissolved at a concentration of 1z/a is 05~
The present invention provides an aromatic polyester characterized in that it has a molecular weight of 20.0 a/g.

+OC R, -CO-)- (IV) Indicates one or more groups selected from the following. Note that X represents a hydrogen atom or a chlorine atom. ) In the aromatic polyester of the present invention, the mechanical structural unit (2) is a structural unit of the polyester produced from P-hydroxybenzoic acid.

In addition, the above structural unit 0 is a structural unit generated from 4,4-dihydroxybiphenyl, the structural unit is a structural unit generated from hydroquinone, and the structural unit ■ is a structural unit generated from 4,4--
Diphenyl ether dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1゜2-bis(phenoxy)ethane-4
, 4-dicarboxylic acid, and 1,2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid.

The above-mentioned structural unit (2) accounts for 40 to 90 mol%, preferably 60 to 90 mol% of [110].

Further, the above structural unit ['@+(E)] is 60 to 10 mol% of [■+01], preferably 40 to 10 mol%. If the structural unit (■) or [■+@+ (ID) exceeds 90 mol% or is less than 40 mol%, the fluidity will be insufficient, and both cases are unfavorable.

Moreover, the molar ratio of the structural unit o10 is 9515 to 5/95, preferably 90/10 to 10/90. If the molar ratio of 0/■ is outside of 9515 to 5/95, the fluidity will be poor and an aromatic polyester that meets the purpose of the present invention cannot be obtained.6 The aromatic polyester of the present invention is produced by polycondensation of conventional polyesters. According to the method 'M! There are no particular restrictions on the manufacturing method, and typical manufacturing methods include the following methods (1) to (4).

(1) Acylated products of hydroxycarboxylic acids such as P-acetoxybenzoic acid, acylated products of aromatic hydroxy compounds such as 4,4-monodiacetoxybiphenyl, and 4,4'
- A method for producing from an aromatic dicarboxylic acid such as diphenyl ether dicarboxylic acid by deacetic acid polycondensation reaction.

(2) Aromatic dihydroxy compounds such as p-hydroxybenzoic acid, 4.4-dihydroxybiphenyl and 4.4
A method for producing by deacetic acid polycondensation reaction from an aromatic dicarboxylic acid such as '-diphenyl ether dicarboxylic acid and acetic anhydride.

(3) Manufactured by dephenol polycondensation from aromatic dihydroxy compounds such as p-hydroxybenzoic acid phenyl ester and 4,4-dihydroxybiphenyl and diphenyl ester of aromatic dicarboxylic acid such as 4,4'-diphenyl ether dicarboxylic acid. how to.

(4) Aromatic dicarboxylic acids such as p-hydroxybenzoic acid and 4,4′-diphenyl ether dicarboxylic acid are reacted with a desired amount of diphenyl carbonate to form diphenyl esters, and then aromatic dicarboxylic acids such as 4,4′-dihydroxybiphenyl are prepared. A method of manufacturing by adding a group dihydroxy compound and performing a phenol-free polycondensation reaction.

Typical catalysts used in polycondensation reactions include metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, antimony dioxide, magnesium, and sodium acetate, which are particularly effective in dephenol polycondensation. .

Further, the melt viscosity of the aromatic polyester of the present invention is 50 to
15. OOO boys are preferred, especially 100 to 10.
000 voids is more preferred.

The melt viscosity is a value measured using a Koka type flow tester at a liquid crystal start temperature +40° C. and a slip rate of 1.000 (1/sec).

The logarithmic viscosity of these aromatic polyesters is 0.5 to 20°0d1/g when dissolved in pentafluorophenol at a concentration of 0.1g/a at 60°C.
．． 8~1! 5. Oa/g is preferable, especially 6:1.0
~10. Oa/g is preferred.

In addition, when polycondensing the aromatic polyester of the present invention, in addition to the components constituting the above (I) to (IV), terephthalic acid, isophthalic acid, 4.4-1 diphenyl dicarboxylic acid, 3.3 -monodiphenyldicarboxylic acid, 3
．． Aromatic dicarboxylic acids such as 4-1 diphenyldicarboxylic acid and 2゜2-diphenyldicarboxylic acid, alicyclic dicarboxylic acids such as hexahydrophthalic acid, and fatty acids such as adipic acid, acelaic acid, sebacic acid, and dodecanedioic acid. Group dicarboxylic acids, methylhydroquinone, chlorohydroquinone, t-butylhydroquinone, phenylhydroquinone, 4.4”-dihydroxydiphenyl sulfide, 4,4-dihydroxybenzophenone, 2.2-
Bis(4-hydroxyphenyl)propane, bis(4-
Aromatic dihydroxy compounds such as hydroxyphenyl) sulfone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, diethylene glycol, polyethylene glycol,
Aliphatic, cycloaliphatic diols such as 1,4-cyclohexane dimetatool, aromatic hydroxycarboxylic acids such as m-hyroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and p-aminobenzoic acid, p- Aminophenol and the like may be further copolymerized within a small proportion that does not impair the purpose of the present invention.

The aromatic polyester of the present invention thus formed has a melting point of 40
The temperature is below 0℃, and it can be used for normal melt molding such as extrusion molding, injection molding, compression molding, and blow bottom molding, and can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc. be.

In addition, during molding, for the aromatic polyester of the present invention,
Reinforcing agents such as glass fiber, carbon fiber, asbestos, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants,
Additives such as mold release agents and flame retardants, and other thermoplastic resins can be added to impart desired properties to the molded article.

Moreover, the molded article obtained from the aromatic polyester of the present invention is not limited in its use. In addition to general electronic components and structural materials, it can also be preferably used for C sealants, speaker diaphragms, and magnetic materials.

Note that the strength of the thus obtained molded article can be increased by heat treatment, and the elastic modulus can also be increased in many cases.

This heat treatment can be carried out by heat treating the molded article in an inert atmosphere (for example nitrogen, argon helium or water vapor) or in an oxygen-containing atmosphere (for example air) or under reduced pressure 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 several tens of minutes to several days.

The molded article obtained from the aromatic polyester of the present invention has good optical anisotropy and heat resistance due to its parallel molecular arrangement, and has extremely excellent mechanical properties and fluidity.

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

Example 1 3- p-hydroxybenzoic #884+r<6.4 mol>, 4
．． 4-dihydroxybiphenyl 198 g (1,06 mol), hydroquinone 59 g (0,54 mol), acetic anhydride 1,078 + r<10,6 mol) and 4,4-diphenyl ether dicarboxylic acid 413 g (1,6 mol)
was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and acetic acid depolymerization was carried out under the following conditions.

First, under a nitrogen gas atmosphere at 100 to 250°C for 5 hours,
After reacting at 50-340℃ for 2 hours, 340'C1
The pressure was reduced to 1 +++ nH () for 1.5 hours, and the reaction was allowed to proceed for an additional hour to complete polycondensation, whereupon an almost theoretical amount of acetic acid was distilled out, and a resin having the following theoretical structural formula was obtained.

k/j! /m/n=80/13.3/6.7/20 Also, as a result of placing this polyester on four polarizing microscope samples and increasing the temperature to confirm the optical anisotropy, 3
02°C, showing good optical anisotropy. The logarithmic viscosity of this polyester (measured at 60 °C in pentafluorophenol at a concentration of 0.1 g/d) is 2.1.0 a
/g, and it had excellent melt fluidity and was extremely tough.

Example 2 829 g (6.0 mol) of p-hydroxybenzoic acid, 4.
249 g (134 moles) of 4”-dihydroxybiphenyl
, 72.7 g (0°66 mol) of hydroquinone, 1.123 g (11.0 mol) of acetic anhydride, and 432 g (2.0 mol) of 2,6-naphthalene dicarboxylic acid were placed in a reaction vessel equipped with a stirring blade and a distillation tube. As a result of carrying out acetic acid depolymerization under the same conditions as in Example 1, a resin having the following theoretical structural formula Wj was obtained.

k/evening, /m/n=75/ 16.7/8.3/25 In addition, this polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy. C, and showed good optical anisotropy. The logarithmic viscosity of this polyester (measured at 60 °C in pentafluorophenol at a concentration of 0.1 g/d) is 5.30 a/z;
It was found to have good liquidity.

This polymer was also extremely strong.

Example 3 829 g (6.0 mol) of p-hydroxybenzoic acid, 4.
249 g (1,34 mol) of 4-monodihydroxybiphenyl, 72.7 g (066 mol) of hydroquinone, 1.123 g (11,0 mol) of acetic anhydride and 604 f of 1,2-bis(phenoxy)ethane-4,4-dicarboxylic acid.
(2.0 mol) was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and deacidification polymerization was performed under the same conditions as in Example 1. As a result, a resin having the following theoretical structural formula was obtained.

6 ni/j! /m/n, =75/ 16.7/8.3/
25 In addition, we placed this polyester on the sample stage of a polarizing microscope and confirmed the optical anisotropy by raising the temperature.
It showed good optical anisotropy. The logarithmic viscosity of this polyester (measured at 60°C in pentafluorophenol at a concentration of 0.1 g/d) is 3. L 6 a/g
It was found that the liquidity was good.

This polymer was also extremely strong.

Comparative Example 1 884 g (6.4 mol) of p-hydroxybenzoic a, 4.
298 g (1.6 mol) of 4-dihydroxybiphenyl
, 1,082 g (10,6 mol) of acetic anhydride, 4.4--
413 g (1.6 mol) of diphenyl ether dicarboxylic acid was charged into the same container as in the example, and the final polymerization temperature was set to 360 ml.
As a result of carrying out acetic acid depolymerization under substantially the same conditions as in Example 1 except that the temperature was changed to .degree. C., a resin having the following theoretical structural formula was obtained, but foaming occurred during the vacuum polymerization and fluidity was extremely poor.

k/j! /m=80/20/20 This polymer was placed on the sample stage of a polarizing microscope, and the temperature was raised to confirm the optical anisotropy. As a result, the temperature was 325°C, and it was found to be significantly more fluid than the polymer with the structure of the example. The quality was poor.

Comparative Example 2 p-hydroxybenzoic acid 884g <6.4 mol), hydroquinone 176g (1.6 mol>, anhydrous vinegar al, 08
The procedure was almost the same as in Example 1, except that 2 g (10.6 mol) and 413 g (1.6 mol) of 4,4-diphenyl ether dicarbonate vi were charged into the same reaction vessel as in Example, and the final polymerization temperature was 360°C. Under similar conditions, a polymer having the following theoretical structural formula was subjected to deacetic acid polymerization.

k/j! /m=80/20/20 As a result, the polymer was fixed during vacuum polymerization, and a polymer with melt fluidity could not be obtained.

<Effects of the Invention> According to the present invention, an aromatic polyester having excellent mechanical properties and IF thermal properties as well as improved fluidity can be provided, and can be used for various purposes such as engineering plastics.

Claims (1)

[Claims] The structural unit (I) to (IV) is composed of the following structural units (I) to (IV).
I) is 40 to 95 mol% of [(I) + (II) + (III)], and the molar ratio of structural units (II)/(III) is 95/5 to
5/95, the structural unit (IV) is substantially the structural unit [(II)
+(III)] and has a logarithmic viscosity of 0.5 to 20.0 dl/g when dissolved in pentafluorophenol at 60°C at a concentration of 0.1 g/dl. aromatic polyester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) ■OC-R-CO■・・・・・・(IV) (However, R in the formula ▲ has a numerical formula, chemical formula, table, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ Indicates one or more groups selected from. Note that X represents a hydrogen atom or a chlorine atom. )