JPS6181432A - Production of thermoplastic polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester free from coarse particles and having excellent thermal stability, etc., by preparing polyethylene 1,2-bis(2-chlorophenoxy) ethane-4,4'-dicarboxylate in the presence of a metallic compound and a phosphorus compound. CONSTITUTION:In the production of a polyester from an alkyl ester of 1,2-bis(2- chlorophenoxy)ehtane-4,4'-dicarboxylic acid and a glycol, the polycondensation reaction is carried out in the presence of one or more glycol-soluble compounds of Mg, Mn, Li, Na or K and a phosphorus compound in an amount to satisfy the formulas; 0.5<=M<=50 and 0.3<=M/P<=10 (M is total molar number of Mg, Mn, Li, Na and K compounds per 10<6> g of the polyester; p is total molar number of the phosphorus compound per 10<6> g of the polyester).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing a highly polymerized thermoplastic polyester having high rigidity and excellent heat resistance.

<Prior art and its problems> Polyethylene terephthalate has excellent mechanical properties, heat resistance, weather resistance, and electrical insulation resistance, and is therefore widely used as films, fibers, and other molded products.

However, in recent years, in the field of film, magnetic recording media such as magnetic tape and magnetic disk, which are typical applications,
There is a trend toward smaller and lighter devices for applications such as capacitors, and as a result, there is an increasing need for films with high rigidity. Furthermore, in the textile field, fibers with high elastic modulus are required for industrial material applications.

In order to satisfy these required properties, various attempts have been made to improve the elastic modulus of polyethylene terephthalate by modifying it, but these required properties have not yet been fully satisfied.

On the other hand, polyethylene-α,β-bis(2-chlorophenoxy)ethane-4,4′-ih lupoquinlate has been proposed in Japanese Patent Publication No. 1795-1987 as a polyester that relatively meets the above-mentioned required properties.

However, when polyester is manufactured by the method disclosed in the above publication and used for magnetic tape, the electromagnetic conversion characteristics deteriorate due to the influence of coarse particles present in the polyester, and when a capacitor is used, The disadvantage is that it does not provide adequate insulation performance.

Furthermore, since the polyester has insufficient thermal stability, it has the disadvantage of causing a decrease in viscosity and a change in color tone during the molding process.

As a result of intensive study on these drawbacks, the inventors discovered that the above-mentioned drawbacks could be greatly improved by adding a specific amount of a metal compound or phosphorus compound to the polymer, and thus arrived at the present invention. .

<Object of the Invention> The object of the present invention is to produce 8 tons of polyethylene 7-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate using a specified amount of metal compounds and phosphorus compounds. By adding , there are no coarse particles,
It is an object of the present invention to provide a method for producing a polyester having good thermal stability, high rigidity, and excellent heat resistance.

Another object of the present invention is to provide a method for producing a polyester having improved electromagnetic characteristics and insulation performance, high rigidity, and excellent heat resistance when a film is used.

<Structure of the Invention> The object of the present invention described above is to produce a polyester from an alkyl ester of 1,2-bis I (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and a glycol using the following general formula t. This can be achieved by a method for producing a thermoplastic polyester, which is characterized by polycondensation in the presence of a phosphorus compound and at least one glycol-soluble metal compound of magnesium, manganese, lithium, sodium, and potassium.

0.5≦M≦50・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
CD0.3≦T;≦10・・・−・−・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
... [■] [In the formula, M is polyester 106 of magnesium, manganese, lithium, sodium, and potassium compounds.
Total number of moles per g, P is phosphorus compound polyester 10
6) Represents the total number of moles per unit. ] The glycol used in the present invention includes lower alkylene glycol, chlorhexanemethanediol, quinrylene glycol, etc. Among them, ethylene glycol and butanediol are preferred.

Furthermore, in the present invention, a small proportion of other compounds having ester-forming ability can be copolymerized with the above-mentioned dicarboxylic acid ester and the above-mentioned ethylene glycol compound. For example, succinic acid, ampic acid, sepanonic acid, terephthalic acid.

inophthalic acid, 2,6-naphthalene dicarboxylic acid.

4.4'-diphenyldicarboxylic acid, hexahydroterephthalic acid, 1.2-bis(phenoxy)ethane-4,4
'-Dicarboxylic acid, 1,2-bis(2,6-dichlorophenoxy)ethane-4,4'-dicarboxylic acid, 1(chlorophenoxy)-2(phenoxy)ethane-4,4'-
Dicarboxylic acids and/or their ester-forming derivatives such as dicarboxylic acids and polyethylene glycol, polypropylene glycol, hexamethine/glycol, 1,4-cyclohexane-dimetatool, diethylene glycol, neopentyl glycol.

Dioxy compounds such as bis(β-hydroxyethoxy)bisphenol A, oxycarboxylic acids such as p-(β-oxyethoxy)benzoic acid and/or ester-forming derivatives thereof, etc. are used, but 1 is particularly preferred.
-(2-chlorophenoxy)-2(phenoxy)ethane-4,4'-dicarboxylic acid and/or its ester-forming derivative.

Examples of the glycol-soluble metal compounds of magnesium, manganese, lithium, sodium, and potassium used in the present invention include acetates, phosphates, halides, hydroxides, aliphatic carboxylic acids, and alcoholades. are magnesium acetate, manganese acetate, and lithium acetate.

Potassium acetate, sodium acetate, magnesium oxalate, manganese oxalate, lithium oxalate, potassium oxalate, sodium oxalate.

Magnesium chloride, manganese chloride, lithium chloride, potassium chloride, sodium bromide, magnesium hydroxide, manganese hydroxide, lithium hydroxide.

Examples include potassium hydroxide, sodium hydroxide, lithium propionate, sodium ethylate, potassium glycolate, and two or more of these may be used in combination.

The amount of the glycol-soluble metal compound used in the present invention is 0.5≦M≦50. More preferably 1.0≦
M≦4.0. If M is less than 0.5, the transesterification reaction time and the subsequent polycondensation reaction time will be delayed, resulting in a decrease in productivity.

On the other hand, if M exceeds 50, the obtained polymer will be colored, the viscosity will decrease during melt extrusion during spinning and film forming, and coarse particles will be generated in the polymer, which will greatly reduce the commercial value. to lower the width. In addition, the above metal compound may be added in its entirety before the start of the transesterification reaction, or it may be added in parts, but if it is added in parts, the polyester oligomer is polycondensed. It is preferable to add it by the early stage of the process.

Further, as the phosphorus compound used in the present invention, one or more types selected from phosphoric acid, phosphorous acid, phosphonic acid, and lower alkyl esters and phenyl esters thereof can be used. Specifically, phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, acidic phosphoric acid, phosphoric acid esters such as methyl ester, phosphorous acid,
Phosphite esters such as trimethyl phosphite and triethyl phosphite, and methylphosphonic acid.

Phosphonic acid esters such as phenylphosphonic acid, benzylphosphonic acid, methylphosphonic acid ester, phenylphosphonic acid methyl ester, phenylphosphonic acid ethyl ester, and benylphosphonic acid phenyl ester can be mentioned.

The phosphorus compound used is indicated by the metal compound added.

This is undesirable because it causes a decrease in the conversion point and further delays the polycondensation reaction time, resulting in a decrease in productivity.

The polymer may become colored, cause a decrease in viscosity during melt extrusion for spinning yarn or film production, or become colored, resulting in a polymer with poor thermal stability. In addition, it is not preferable to do so because it causes the formation of coarse particles in the polymer.

These phosphorus compounds may be added at the same time as the metal compound or may be added first.

The reaction product thus obtained is a conventional polycondensation reaction catalyst,
For example, using a known polycondensation catalyst such as an antimony compound, a titanium compound, or a germanium compound,
The polycondensation reaction can be carried out at ℃.

<Effects of the Invention> As mentioned above, the alkyl ester of 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid is added to the polyester for producing glycol or polyester. The polyester of the present invention obtained by adding a specific amount of a specific metal compound or phosphorus compound exhibits the following effects.

(1) Highly rigid polyester containing no coarse particles and having good thermal stability can be obtained.

(21 The film made of polyester of the present invention has high rigidity even in a thin film compared to ordinary polyethylene terephthalate film, etc., and a film with good flatness can be obtained. Such a film can be used with metal tape, vapor-deposited tape, etc. When used in magnetic tapes, magnetic disks, etc., magnetic tapes, magnetic disks, capacitor base films, etc., it is extremely effective for downsizing and improving the performance of equipment.

(31 Furthermore, when the above polyester is molded into fibers, fibers with high strength and high modulus of elasticity can be obtained, and can be effectively used for various purposes including industrial materials.

The present invention will be explained in detail below using Examples. In addition, the part in an Example is a heavy melon part. The measurement method for each characteristic is as follows.

Polymer color tone> Measured in chip form using a direct reading color difference meter (Suga Test Instruments Co., Ltd.) and expressed as bIvL()・inter value].

Softening point Measured with a petrometer.

Particle dispersion state> Sandwich 10 m7 of chips between two cover glasses,
Preparations were made by melt pressing at 0°C, observed under a dark field polarizing microscope and evaluated according to the following criteria.

Rank Average particle diameter (μ) Class A: 1.0 or less Class B: 1.0 to 2.0 Class 0: 2.0 to 5.0 Polymer viscosity> Using a high-speed flow tester, 290°C, sliding speed 200
Melt viscosity at 7 seconds was measured.

Thermal stability of polymer> 30g of polyester was dissolved in air at 300℃,
The melt viscosity after minutes was measured and expressed in Δpoise.

Δvoise = viscosity before heat treatment - viscosity after heat treatment Young's modulus> According to the method specified in A S TM-D-882,
25℃ using an Instron type tensile tester.
Measured at 65% RH.

Breakdown voltage of capacitor> A capacitor (capacity 0.5 μF) is
A DC voltage is applied at a boost rate of 00 V/sec, the voltage at which the capacitor breaks down is taken as the breakdown voltage, and the base film 1
It is expressed as the breakdown voltage value per μ.

Example 1 1.2-bis(2-chlorophenoxy)ethane t a/
- 100 parts of methyl dicarboxylate, 31 parts of ethylene glycol, and 0.1 part of magnesium acetate were charged into a reactor equipped with a rectification column and a stirring device, and the temperature was gradually raised from 190°C to 240°C over 4 hours while stirring. It was warm. The transesterification reaction was completed while distilled methanol was extracted from the system. The reaction rate was 99.8%.

Subsequently, 0.02 part of trimethyl phosphate and 0.04 part of antimony dioxide were added and then transferred to a polycondensation reactor, and the polycondensation reaction was completed under reduced pressure. The final temperature was 295℃,
The degree of vacuum was 0.5 Hfi.

He was a child.

Examples 2 to 4, Comparative Examples 1 to 5 Polymers were obtained in the same manner as in Example 1, except that the types and additions of the metal compounds and phosphorus compounds used were changed.

The results are shown in Table 1. In the polymer obtained by the method of the comparative example, the particles in the polymer became coarse and the thermal stability was unsatisfactory.

However, it was not possible to obtain a polymer with sufficient viscosity and the softening point was low.

Example 5. Comparative Example 6 The polymer obtained in Example 2 was melt extruded and an unstretched film was formed using a casting drum. I Ta.

Next, the film was biaxially stretched by 3.5 times in both the longitudinal and width directions, and then immediately heat treated to obtain a 5 μm film. The Young's modulus of this film in the longitudinal direction was 720 kg/-, indicating a high elastic modulus.

After aluminum was deposited on this film, a capacitor element was made, and a capacitor with a capacitance of 0.5 IJF was made by a conventional method.The breakdown voltage of this capacitor was 540
v/μ, and the capacitor had good insulation properties.

On the other hand, a capacitor was obtained in the same manner using the polymer obtained in Comparative Example 1 all around.

Although the Young's modulus in the longitudinal direction was 700 kg/7, which was a high elastic modulus, the breakdown voltage was 430 V/μ, which was insufficient as a capacitor.

Procedural amendment 1. Indication of fact 1981 Special d1 Application No. 201810 2, Name of the invention Method for manufacturing thermoplastic polyester 5, Relationship with the supplementary iE person + 11 cases Patent application Person's home 5, Amendment (increasing number of inventions) Number 1)
On page 7, line 18 of the specification, "10≦M≦4.0" is corrected to "1.0≦M≦40."

(2) On page 10, line 10 of the specification, ``in the course of manufacturing'' is amended to ``in the entire manufacturing process.''

(3) Page 14, line 15 of the specification - Amend "Immediately after heat treatment," to "Immediately after heat treatment."

that's all

Claims (1)

[Claims] 1,2-bis(2-chlorophenoxy)ethane-4,4
When producing polyester from alkyl ester of dicarboxylic acid and glycol, in the presence of at least one glycol-soluble metal compound of magnesium, manganese, lithium, sodium, and potassium and a phosphorus compound that satisfies the following general formula. A method for producing thermoplastic polyester, which comprises polycondensation. 0.5≦M≦50……………………………………〔I〕
0.3≦M/P≦10……………………………………[I
I] [In the formula, M represents the total number of moles of magnesium, manganese, lithium, sodium, and potassium compounds per 10^6 g of polyester, and P represents the total number of moles of phosphorus compounds per 10^6 g of polyester. ]