JPS6268815A - Production of thermoplastic polyester - Google Patents

Abstract

PURPOSE:To obtain the titled polyester, having a high polymerization degree and rigidity and improved heat resistance and suitable for fibers, etc., by adding a metal compound soluble in a glycol to a specific compound and glycol. CONSTITUTION:A polyester obtained by mixing (A) a compound expressed by formula I (R1 and R2 are 1-4C alkyl) as a main acid component with (B) a glycol, e.g. ethylene glycol, adding (C) a metal compound, e.g. zinc acetate, soluble in the component (B)thereto so as to satisfy formula II [M is the total number of mol of the component (C) based on 10<6>g polyester] and further adding (D) a phosphoric acid compound, e.g. phosphoric acid, in an amount within the range expressed by formula III (P is the number of mol of the phosphoric acid compound based on 10<6>g polyester) to the resultant mixture and polycondensing the resultant mixture.

Description

[Detailed description of the invention] 〔Technical field〕 The present invention has a high degree of polymerization with high rigidity and excellent heat resistance.

The present invention relates to a method for producing thermoplastic polyester.

[Prior art and its problems]

Polyethylene terephthalate has excellent mechanical properties, heat resistance, weather resistance, and electrical insulation resistance, so it is widely used as films, fibers, and other molded products. However, in recent years, in the film field, there has been a trend toward smaller and lighter equipment in applications such as magnetic tapes and magnetic disks, and this has led to a strong demand for films with even higher rigidity than polyethylene terephthalate. has been done. Furthermore, in the textile field, fibers with high elastic modulus are required for industrial material applications. In order to meet these demands, various attempts have been made to improve the modulus of elasticity by modifying polyethylene terephthalate, but no satisfactory results have been obtained.

On the other hand, polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,41-dicarboxylate has been proposed in Japanese Patent Publication No. 49-1795 as a polyester that relatively meets the above-mentioned required properties.

However, when polyester is produced by the method disclosed in the above-mentioned publication, coarse particles are formed in the polymer or the polymer has insufficient thermal properties.

For this reason, it has drawbacks such as a decrease in electromagnetic conversion characteristics and an inability to obtain sufficient insulation performance when used in a capacitor.

As a result of intensive studies on these drawbacks, the present inventors have found that the above drawbacks can be significantly improved by allowing a specific amount of a specific type of metal compound to be present together with a phosphorus compound in the manufacturing process of the polyester. Reached.

[Purpose of the invention]

The purpose of the present invention is to eliminate the presence of coarse particles by adding a specific amount of a specific type of metal compound together with a phosphorus compound in the manufacturing process of polyethylene-1,2-bis(chlorophenoxy)ethane-4, idicarboxylate. ,
It is an object of the present invention to provide a method for producing a high degree of polymerization polyester having good thermal stability, high rigidity, and excellent heat resistance with good productivity.

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 the polyester is used in a film.

At least one of glycol-soluble zinc, cobalt, and tin compounds is used as a transesterification reaction catalyst when producing polyester from glycol and a compound as a component.
Species metal compounds and phosphorus compounds are shown below [■] and (I
II) This can be achieved by a method for producing a thermoplastic polyester characterized by adding the amount within the range of the formula.

0.05≦M≦20 ・・・・・・・・・・・・・・・
・・・・・・ [■]0.2≦%≦10 ・・・・・・・・・
Although the position of chlorine in the above compound [I] is not specified, the ortho position with respect to the ether group is particularly preferable. In addition, the present invention has the following structural formula [■] [■] in the raw material compound Cl3.
] may contain a small proportion of a carboxylic acid component as an impurity.

Examples of the glycol used in the present invention include lower alkylene glycol, cyclohexane dimetatool, and xylylene glycol, among which ethylene glycol and butanediol are preferred.

Furthermore, in the present invention, in addition to the above-mentioned carboxylic acid, its alkyl ester, and the above-mentioned glycol, a small proportion of other compounds having ester-forming ability can also be copolymerized.

For example, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthal fil, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, hexahydroterephthalic acid, 1,2-bis(phenoxy)ethane-4 ,4'-dicarboxylic acid, 1,2-bis(,2,6-
Dicarboxylic acids such as dichlorophenoxy)ethane-4,4'-dicarboxylic acid%1-(chlorphenoquine)-2(phenoxy)ethane-4,4'-dicarboxylic acid and their ester-forming derivatives and Polyethylene glycol, polypropylene glycol, hexamethylene glycol, 1,4-cyclohexane-dimetatool, diethylene glycol, neopentyl glycol, bis(
Dioxy compounds such as β-hydroxyethoxy)bisphenol A, oxycarboxylic acids such as p-(β-oxyethoxy)benzoic acid, and their ester-forming derivatives are used, but particularly preferred are 11(chlorophenoxy)-2( phenoxy)ethane-4,4-dicarboxylic acid and its ester-forming derivatives.

The glycol-soluble zinc and cobalt I compounds used in the present invention include acetate, oxalate, halide,
Examples of the tin compound include hydroxides, aliphatic carboxylic acids, borates, carbonates, and alcolades, and examples of the tin compound include organic tin compounds.

More specifically, lead acetate, cobalt acetate, zinc oxalate, cobalt oxalate, zinc chloride, cobalt chloride, zinc bromide, zinc hydroxide, cobalt hydroxide, zinc oxalate, cobalt adipate, cobalt glycolate, Motuptiltin oxide, di-n-butyltin diacetate, tri-n+-butyltin chloride, dimethyltin malate,
Examples include dibutyltin oxide, and two or more of these may be used in combination, but zinc compounds are particularly preferred.

The amount of the glycol-soluble metal compound used in the present invention is 0.05≦M≦20, more preferably 0.07≦M
≦15, more preferably 0.1≦M≦10.

In the formula, M is a glycol-soluble metal compound polyester 1
It is the number of moles per 0g. M is 0. ．． If it is less than 0.05, the transesterification reaction time and the subsequent polycondensation reaction time will be delayed, resulting in a decrease in productivity.

However, if M exceeds 20, the obtained polymer may be colored, the viscosity may decrease during melt extrusion during spinning or film forming, and coarse particles may be formed in the polymer. Significantly lower product value.

Furthermore, regarding the timing of addition of the above-mentioned metal compound, the entire amount may be added before starting the transesterification reaction, or it may be added in portions, but when added in one portion, 1.2-bis (Chlorphenoxy)ethane-4,4'-dicarboxylate t It is preferable to add it by the early stage of polycondensation.

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 phosphate, methylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, methylphosphonic acid methyl ester,
Examples include phosphonic acid esters such as phenylphosphonic acid methyl ester, phenylphosphonic acid ethyl ester, and benzylphosphonic acid phenyl ester.

This is undesirable because it causes a decrease in the molar ratio between the metal compound and the phosphorus compound used, and furthermore, the polycondensation reaction time is delayed, resulting in a decrease in productivity.

The polymer may become colored, cause a decrease in viscosity during melt extrusion for spinning or film forming, or become colored, resulting in a polymer with poor thermal stability. Furthermore, it is undesirable because coarse particles are generated in the polymer. These phosphorus compounds may be added at the same time as the metal compound or either may be added first, and the polycondensation reaction can be carried out at 220 to 500° C. using a known polycondensation catalyst such as a germanium compound.

〔Effect of the invention〕

As mentioned above, in the production of polyethylene-1,2-bis(chlorophenoxy)ethane-4,4'-) carboxylate, the present invention was obtained by adding a specific amount of a KW specified metal compound to the polyester along with a phosphorus compound. The polyester of the invention has the following properties.

(1) A highly rigid polyester containing no coarse particles in the polymer and having good thermal stability can be obtained.

+21 Even if an alkyl ester of 1,2-bis(chlorophenoxy)ethane-4,4'-dicarboxylic acid having a low +1E is used, a high-quality polyester can be obtained without impairing productivity.

(3) Compared to ordinary polyethylene terephthalate films, the film made of the polyester of the present invention has high rigidity even in a thin film, and a film with good flatness can be obtained.

Such films are extremely effective in miniaturizing and improving the performance of equipment when used for magnetic tapes such as metal tapes and vapor-deposited tapes, pace films for magnetic disks, base films for capacitors, and the like.

(4) Furthermore, when the above-mentioned polyester is formed 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, parts in Examples are parts by weight, and the measurement method of each characteristic is as follows.

(1) Sandwich 10 mL of particles in a dispersed state between two cover glasses.
Prepared preparations were prepared by melt pressing at 90° C., and were observed under a microscope and evaluated based on the number of coarse particles present according to the following criteria.

In addition, here, coarse particles are 1μ or more. means the particles above. Also, A and B are considered passing ranks.

Rank Number of coarse particles present (pieces/mf) A
0~10B
11-30 C31 50 D '51^100 (2) Measured in chip form using a polymer tone continuous color difference meter (Suga Test Instruments Co., Ltd.), and expressed as t) value (Hunter value).

(3) Polymer viscosity 29 parts ℃ using a high-speed flow tester The melt viscosity was measured at a shear rate of 200 S-'.

(4) Softening point Measured with a venetrometer.

(5) Young's modulus measured at 25°C and 65°C using an Instron type tensile tester according to the method specified in ASTM-D-882.
Measured at 4RH.

(6) Breakdown voltage of capacitor A capacitor (capacitance 0.5 μF) was
A DC voltage was applied at a boost rate of 00 V-8-, +, and the voltage at which the capacitor broke down was defined as the breakdown voltage, which was expressed as the breakdown voltage value per 1 μm of the base film.

Example 1 0.2 parts of 1.2-bis(2-chlorophenoxy)ethane-4-carboxymethyl-4-carboxylic acid, i,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid Dimethyl 1,2-bis(2-chlorophenoxy)ethane-4,4I-dicarboxylate containing 0.05 parts 1
00 parts, 32 parts of ethylene glycol, and 0.0 parts of zinc acetate.
1 part was charged into a rectification column and a reactor equipped with a stirrer, and the temperature was gradually raised from 190°C to 250°C over 4 hours while stirring. d) Transesterification was carried out while distilled methanol was extracted from the system. The reaction was completed. The reaction rate was 99.6%.

Subsequently, 0.003 parts of phosphoric acid and 0.00 parts of antimony trioxide were added.
After adding 01 parts, the mixture was transferred to a polycondensation reactor, and the polycondensation reaction was carried out under reduced pressure for 3 hours. The final temperature was 295°C and the degree of vacuum was 0.5 mHg.

The viscosity of this polymer was 2500 voids, the b value was 3o1, and the softening point was 277.5°C.

Examples 2 to 5, Comparative Examples 1 to 6 Types and amounts of metal compounds and phosphorus compounds used,
The same method as in Example 1 was followed except that the carboxylic acid content in the raw materials was changed. The results are shown in Table 1.2. When a metal compound other than zinc, cobalt, and tin was used as in Comparative Example 1.2, the reaction system became cloudy, productivity decreased, and the particles in the polymer became large.

In some cases, it was not possible to obtain a polymer with sufficient viscosity, the color tone deteriorated, the particles in the polymer became coarse, and the softening point of the polymer was low.

Example 6, Comparative Example 7 The polymer obtained in Example 2 was melt extruded and an unstretched film was obtained by casting drama.

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 750:9/-, indicating a high elastic modulus. After this film was deposited with aluminum, a capacitor element was made, and a capacitor with a capacitance of 0.5 μF was made by a conventional method. The breakdown voltage of this capacitor was 530 V/μ, and the capacitor had good insulation properties.

On the other hand, when a capacitor was obtained using the polymer obtained in Comparative Example 3 in the same manner as I, the Young's modulus in the longitudinal direction was 72.
Although the elastic modulus was high at 0 kg/mrIP, the breakdown voltage was 420 V/μ, which was an insufficient result as a capacitor.

Claims (1)

[Claims] When producing polyester from a compound having the following structural formula [I] as a main component and glycol, glycol-soluble zinc, cobalt,
A method for producing a thermoplastic polyester, which comprises adding at least one metal compound among tin compounds and a phosphorus compound within the range of formulas [II] and [III] below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼……[I] 0.05≦M≦20……………………[II] 0.2≦M/P≦10…………………………[ III] [However, in the formula, R_1 and R_2 represent an alkyl group having 1 to 4 carbon atoms, M is a polyester of zinc, cobalt, and tin compounds, the total number of moles per 10^6 g, and P is a polyester of a phosphorus compound. ^Represents the total number of moles per 6g. ]