KR930003712B1 - Aromatic polyester polymer and produce for preparation of the aromatic polyester polymer - Google Patents

Abstract

The wholly aromatic polyester crystal polymer comprises: (A) the units of the oxybenzoil component of formulas (I) and (II); (B) the units of the dioxy component of formulas (III) and (IV); and (C) the units of the dicarboxy component of formulas (V) and (VI). The said polymer contains 10-70 No % of the unit of (A) component; 15-45 No % of the unit of (B) component; and the same No of the unit of (C) with (A) w.r.t. total number of all units in the polymer. Pref. the polymer is prepd. by polymerization of hydroxy benzoic acid, metahydroxy benzoic acid, bi-phenol, bis-(4-hydroxy phenyl) sulfon, terephthalic acid, isophthalic acid or derivs, thereof.

Description

Wholly aromatic polyester liquid crystal polymer and preparation method thereof

FIELD OF THE INVENTION The present invention relates to Wholly aromatic polyester liquid crystal polymers, more particularly parahydroxybenzoic acid, metahydroxybenzoic acid, biphenol, bis- (4-hydroxyphenyl) sulfone, terephthalic acid, isophthalic acid or The present invention relates to a wholly aromatic polyester liquid crystal polymer having excellent physico-mechanical properties including heat stability prepared by copolymerizing derivatives of these compounds as starting materials and being easy to be molded and processed.

Generally, the aromatic aromatic polyester has a high thermal stability, heat resistance, physical and mechanical properties, chemical resistance, oil resistance, radiation resistance, and morphological stability due to the thermodynamic stability of the aromatic ring and the rigid structural properties of the molecular chain. very good. For this reason, the wholly aromatic liquid-crystalline polymer is widely used in various fields such as mechanical, electrical, electronic parts, automobile parts, etc., and much attention and expectation are attracted to its potential applicability.

However, such an wholly aromatic polyester has a very high melting point, which is a significant difficulty in forming, and since the loss of properties due to decomposition during processing is severe, studies have been continuously conducted since the development of the wholly aromatic polyester.

Therefore, the present invention is to solve the problem of moldability and loss of properties of the wholly aromatic polyester polymer, which has been conventionally problem as described above, a wholly aromatic polyester liquid crystal polymer of a novel structure composed of a new component and composition and a manufacturing method thereof The purpose is to provide.

Hereinafter, the present invention will be described in detail.

The present invention, in the wholly aromatic polyester polymer, the repeating unit represented by the following structural formula (I), the repeating unit of the oxybenzoyl component which is a repeating unit represented by the following structural formula (II), and the repeating represented by the following structural formula (III) Unit and a repeating unit of the dioxy component which is a repeating unit represented by the following structural formula (IV), and a repeating unit represented by the following structural formula (V) and a repeating unit of the dicarboxy component which is a repeating unit represented by the structural formula (VI). It is characterized by the wholly aromatic polyester liquid crystal polymer.

Hereinafter, the present invention will be described in more detail.

The present invention basically consists of the repeating units of the oxybenzoyl component, the dioxy component and the dicarboxy component, and the repeating units of the structural formulas (I) and (II) are composed of the repeating units of the oxybenzoyl component. It is preferable that their total composition ratio is 10 to 70%, preferably 20 to 50% with respect to the number of repeating units of the whole component.

In addition, the repeating units of the deoxy component are composed of the repeating units of the structural formulas (III) and (IV), and their total composition ratio is preferably 45 to 15%, preferably 40 to 25%.

The repeating units of the dicarboxy component include a repeating unit of the structural formula (V) and a repeating unit of the structural formula (VI), and their total composition ratio is determined by the total constituent ratio of the repeating unit of the deoxy component. It is configured in the same way.

At this time, according to the present invention, the repeating unit of the structural formula (II) is composed of 10 to 70%, preferably 20 to 50% of the total number of repeating units of the oxybenzoyl component, and the repeating unit of the structural formula (III) Is composed of 30 to 80%, preferably 40 to 70% of the total number of repeating units of the deoxy component, and the repeating unit of the formula (VI) is 5 to 70% of the repeating units of the total dicarboxy component, Preferably it consists of 20-50%.

On the other hand, looking at the process for producing a wholly aromatic polyester liquid crystal polymer as described above according to the present invention, it is prepared by melt polymerization, the structural formula (3) in the three-necked glass flask equipped with agitator, nitrogen inlet, condenser and temperature indicator ( A compound capable of inducing repeating units of I) to (VI), namely parahydroxybenzoic acid inducing repeating unit of formula (I), metahydroxybenzoic acid inducing repeating unit of formula (II), structural formula [III ] 4,4'-biphenol which induces repeating units of bis, bis- (4-hydroxyphenyl) sulfone inducing repeating units of formula (IV), terephthalic acid inducing repeating units of formula (V), and structural formula Using isophthalic acid, which derives the repeating units of (VI), as a starting material, each is added in the same number of mole% ratios corresponding to the number of repeating units described above.

More specifically, 10 to 70 mol% of the total content of oxybenzoyl component of parahydroxybenzoic acid and metahydroxybenzoic acid, and the total content of dioxy component of 4,4'-biphenol and bis- (4-hydroxyphenyl) sulfone 45-15 mol% and 45-15 mol% of terephthalic acid and the total content of the dicarboxy components of isophthalic acid are added, At this time, the dioxy component and the dicarboxy component are added in equimolar amount.

After adding the reactant and copolymerizing acetic anhydride before copolymerization, the reaction flask is appropriately immersed in a stainless salt bath heated by an electric heater, and preferably at 140 ° C to 180 ° C, preferably The copolymerization reaction is carried out at reflux of acetic anhydride for 2 to 10 hours at 145 ° C to 160 ° C.

In the present invention, just before the reaction, the air in the flask is completely replaced with high-purity nitrogen containing no moisture, and nitrogen is supplied through the nitrogen inlet to keep the nitrogen atmosphere until the pressure is reduced. After sufficient reflux at this temperature, the temperature is raised to about 320 ° C. over 1 to 3 hours, in which excess excess acetic anhydride flows out. After that, when the temperature reaches 240 ℃ ~ 270 ℃, the reactants in the reactor form an anisotropic melt phase, and after polymerization for about 1 hour in the vicinity of 320 ℃, if it has some viscosity, it is gradually reduced to 20 ~ 90 More minutes are polymerized and the resulting polymer is obtained.

According to the present invention, a catalyst may be used to increase the efficiency of the synthesis of the polymer. Preferred catalysts include salts of alkali metals or alkaline earth metals, organic vanadium compounds such as methyl stenophosphoric acid, methoxy or butoxy, germanium oxides, and the like. Mixtures thereof and the like can be used.

The wholly aromatic liquid crystal polyester prepared through the reaction composition and the reaction process as described above significantly reduces the fibrillation phenomenon, and is a high viscosity polymer having good moldability and high strength, which is a general characteristic of the wholly aromatic liquid crystal polyester. It has high modulus, thermal stability and heat resistance.

In addition, the intrinsic viscosity of the synthesized polymer was 1.0 to 1.4 g / dl in a parachlorophenol solution having a measurement temperature of 45 ° C. solute concentration of 0.5 g / dl, and the polymer was spun at a temperature range of 300 ° C. to 350 ° C. to give a strength of 3.8 to 5.4. g / d, elongation 1.7-2.5%, elastic modulus 460-510g / d can be obtained. When the spun fiber is heat-treated stepwise at 180 ° C. to 250 ° C. over 10 hours under nitrogen gas flow or reduced pressure (≦ 2 mmHg), strength and elongation are 12 to 16.5 g / d, 1.9 to 2.8%, and elasticity, respectively. Modulus increased from 892 to 1004 g / d.

Hereinafter, the present invention will be described in more detail with reference to Examples.

In this embodiment, the intrinsic viscosity ηinh of the aromatic polyester was calculated from the following equation.

Where rel is the relative viscosity, ln is the commercial log and C is the concentration of the solution (0.5 g / dl).

Example 1

165.7 g (12 mol) of parahydroxybenzoic acid, 41.4 g (0.3 mol) of metahydroxybenzoic acid, and 167.59 g of 4,4'-biphenol in a 1 L three-necked reaction flask equipped with a stirrer, a nitrogen inlet tube and a condenser 0.9 mole), bis- (4-hydroxyphenyl) sulfone 150.17 g (0.5 mole), terephthalic acid 166.13 g (1.0 mole), isophthalic acid 83.07 (0.5 mole), acetic anhydride 551.29 g (5.4 mole) Replace the part with nitrogen. The temperature is raised to 150 ° C while maintaining the nitrogen atmosphere through continuous nitrogen inflow. When the temperature reaches 150 ° C., the reaction is refluxed for 3 hours 30 minutes, and the temperature is raised to 320 ° C. at a temperature rising rate of 15 ° C. per 10 minutes.

At the beginning of the temperature increase process, excess acetic anhydride and acetic acid, which is a effluent of the acetylation reaction, come out vigorously, and when it reaches 250 ° C. to 260 ° C., a cloudy and opaque anisotropic liquid phase is formed. When the temperature reaches 320 ° C., the reaction is further carried out at this temperature for 1 hour to raise the molecular weight to some extent, and then the pressure is gradually reduced to 100 mmHg and the product polymer is collected after 1 hour.

The resulting product polymer is viscous and melts with a filament forming property, which has a dark brown color with slightly red color. The polymer had an intrinsic viscosity of 1.4 dl / g, a softening point of 198 ° C, and a flow temperature of 310 ° C. After spinning at 320 ° C, the physical properties of the polymer were 4.5g / d, 1.8% elongation and 490g / d elastic modulus. Got it.

At this time, the fiber was heat-treated under reduced pressure (≤2mmHg) while gradually increasing the temperature from 180 ° C to 250 ° C to obtain a fiber having an intensity of 15.8g / d, an elongation of 2.7%, and an elastic modulus of 920g / d. The obtained fiber was injection molded at 320 ° C. to obtain a molded product having a tensile strength of 997 kg / cm ² .

Example 2

138.12 g (1.0 mol) of parahydroxybenzoic acid, 69.06 g (0.5 mol) of metahydroxybenzoic acid, 167.59 g (0.9 mol) of 4,4'-biphenol, and bis- (4-hydride) in the same reactor as in Example 1 Roxyphenyl) sulfone 150.17 g (0.6 mole), terephthalic acid 166.13 g (1.0 mole), isophthalic acid 83.07 g (0.5 mole), acetic anhydride 551.29 g (5.4 mole) was added and the polymer was prepared in the same manner as in Example 1. Synthesize

The obtained polymer had an inherent viscosity of 1.25 dl / g, a softening point of 189 ° C, and a flow temperature of 298 ° C. The fiber was spun at 310 ° C to obtain a fiber having a strength of 4.2 g / d, a signal of 2.1%, and an elastic modulus of 473 g / d. When the fiber was heat-treated under the same conditions as in Example 1, the strength was increased to 14.7 g / d, the elongation was increased to 2.1%, and the elastic modulus was 892 g / d.

The obtained fiber was molded at 310 ° C. to obtain a molded product having a tensile strength of 945 kg / cm ² .

Example 3

165.7 g (1.2 mole) parahydroxybenzoic acid, 41.4 g (0.3 mole) metahydroxybenzoic acid, 167.59 g (0.9 mole) 4,4'-biphenol, 150.17 g bis- (4-hydroxyphenyl) sulfone Mole), 124.6 g (0.75 mole) of terephthalic acid, 124.6 g (0.75 mole) of isophthalic acid, and 551.29 g (5.4 mole) of acetic anhydride were added to the same reactor as in Example 1, and prepared in the same manner. The obtained polymer had an inherent viscosity of 1.32 dl / g, a softening point of 191 ° C., and a flow temperature of 295 ° C., and was spun at 310 ° C. to obtain fibers having a strength of 4.0 g / d, elongation of 2.0% and elastic modulus of 465 g / d.

Heat treatment was performed in the same manner as in Example 1 to obtain a fiber having a strength of 13.2 g / d, elongation of 2.5% and an elastic modulus of 902 g / d, and a molded product having a tensile strength of 932 kg / cm ² was formed at 330 ° C.

Claims (5)

In the wholly aromatic polyester polymer, the repeating unit represented by the following structural formula (I), the repeating unit represented by the oxybenzoyl component which is the repeating unit represented by the following structural formula (II), the repeating unit represented by the following structural formula (III), and the following Consisting of a repeating unit of the dioxy component, the repeating unit represented by the structural formula (IV), and a repeating unit of the dicarboxy component, the repeating unit represented by the following structural formula (VI) A wholly aromatic polyester liquid crystal polymer, characterized in that.

According to claim 1, wherein the repeating unit of the oxybenzoyl component consists of 10 to 70% of the constituent ratio based on the number of repeating units contained in the entire polymer, the repeating unit of the deoxy component is the whole polymer Based on the number of repeating units contained in the composition ratio of 15 to 45%, the repeating unit of the dicarboxy component is characterized in that the same number as the repeating unit of the deoxy component Aromatic Polyester Liquid Crystal Polymer. The repeating unit of the structural formula (II) is contained in 10 to 70% of the repeating unit of the total oxybenzoyl component, and the repeating unit of the structural formula (III) It is contained in 30 to 80%, the repeating unit of the formula (VI) is a wholly aromatic polyester liquid crystal polymer, characterized in that contained in 5 to 70% relative to the repeating unit of the total dicarboxy component. In preparing the wholly aromatic polyester polymer, a total amount of 10 to 70 mol% of the total oxybenzoyl component of parahydroxybenzoic acid and metahydroxybenzoic acid as a starting material, 4,4'-biphenol and bis- (4-hydroxy 45-15 mol% of total dioxy components of phenyl) sulfone and 45-15 mol% of total dicarboxy components of terephthalic acid and isophthalic acid are used, and it is made by mixing and reacting acetic anhydride here. Method for producing aromatic polyester liquid crystal polymer. The method for producing an wholly aromatic polyester liquid crystal polymer according to claim 4, wherein the dicarboxy component is added and used in an equimolar amount with the dioxy component.