JPS6195021A - Copolymerized polyester - Google Patents

Abstract

PURPOSE:To prepare a colored polyester copolymer moldable in molten state, having high elastic modulus and excellent flexural strength and impact strength and suitable for tire cord, belt, magnetic tape, etc., by copolymerizing a dicarboxylic acid component having a specific structure. CONSTITUTION:The objective copolymer can be produced by the polycondensa tion of (A) an acid component composed of (i) 0.05-55mol% 3,9- perylenedicarboxylic acid (ester) of formula I and (ii) 99.95-45mol% dicarboxylic acid (ester) of formula II (R is dicarboxylic acid residue selected from the groups of formula III, formula IV, etc.) and (B) a diol component (e.g. ethylene glycol) e.g. by direct polymerization process, ester exchange process, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a colored copolyester polyester having a high modulus of elasticity and good flexural strength and impact strength.

<Conventional technology> Polyethylene terephthalate is widely used as a fiber in industrial materials such as tire cords, conveyor belts, and power transmission belts, and as a film for magnetic tape, photography, printing, and tracing materials. has been done.

In these industrial materials fields, there are strong demands for higher speeds and higher loads, and in the film field, there are stronger demands for smaller sizes and lighter weights, and in order to satisfy these required properties, higher elastic modulus is required. desired. However, in polyethylene terephthalate, even if the fibers are stretched and oriented at a high magnification, the Young's modulus is at most about 120 y/d, and the reality is that this requirement cannot be fully satisfied. On the other hand, in the film field, it is difficult to stretch polyethylene terephthalate to a high stretching ratio, and the reality is that this requirement cannot be fully satisfied.

Therefore, we developed new materials such as polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate. , polyethylene-2,6-naphthalate, polyethylene-4,4'-
Dicarboxylate/polyethylene terephthalate and the like have been studied in the past, and it is known that these polyesters have a higher modulus of elasticity than polyethylene terephthalate in yarns, films, and the like.

<Problems to be Solved by the Invention> However, in recent years, there has been a strong demand for further miniaturization and weight reduction in the field of these industrial materials, and along with this, there has been a strong demand for higher elastic modulus. It has become clear that these materials alone cannot fully satisfy these requirements.

Therefore, the present inventors conducted intensive studies with the aim of obtaining a high elastic modulus polyester by introducing a small amount of copolymerization component into these polyesters, and found that the purpose of the present invention could be achieved by copolymerizing a dicarboxylic acid component with a specific structure. The present inventors have discovered that it is possible to achieve this goal, and that it is also possible to obtain a colored polyester.

Means and operation for solving the above problems> That is, the present invention consists of the following structural units CI) and (1).
II] is 0.05 to 50 mol% of the total, the structural unit [II
] is comprised of 99.95 to 50 mol% of the total, and provides a melt-moldable copolyester.

(OCRCoz (CH2)20) ・・・
...(1) (However, R is (Yl(koto0(Cf(2)20
4) represents one or more dicarboxylic acid residues selected from the following.

The copolyester in the present invention is 0.05 to 55
mol %, preferably 0.1 to 50 mol % of 3.9-perylene dicarboxylic acid or its ester and 99.95 to 4
5 mol%, preferably 99.9 to 50 mol% of terephthalic acid, 1,2-bis(phenoxy)ethane-4,
One or more types selected from 4'-dicarboxylic acid, l,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-diphenyldicarboxylic acid It is a copolymerized polyester obtained by polycondensing a dicarboxylic acid component consisting of a dicarboxylic acid or its ester and a diol component mainly consisting of ethylene glycol by a direct polymerization method or a transesterification method.

Here, if 3,9-perylene dicarboxylic acid or its ester is less than 0.05 mol%, the effect of improving the elastic modulus of the obtained molded product is small, and if it is more than 55 mol%, 3,9-perylene dicarboxylic acid or its ester Homogeneous copolymerization with ester becomes difficult, making it impossible to achieve the object of the present invention.

The specific conditions for the above direct polymerization method or transesterification method are as follows.

Direct polymerization method - After esterifying 3,9-perylene dicarboxylic acid with other dicarboxylic acids and ethylene glycol, it is heated at 220 to 300°C under high vacuum in the presence of catalytic compounds such as antimony, lead, germanium, and titanium. Polycondensation reaction occurs at high temperatures. Alternatively, 3,9-perylene dicarboxylic acid and ethylene glycol are added to the transesterification product or the esterification product to cause an esterification reaction, followed by a polycondensation reaction as described above.

Transesterification method - Esters of 3,9-perylene dicarboxylic acid and other dicarboxylic acid esters
After transesterification at 130-260°C in the presence of catalytic compounds such as magnesium, zinc, manganese, cobalt, and lithium, transesterification was carried out under high vacuum at 220-300°C in the presence of catalytic compounds such as antimony, lead, germanium, and titanium. Polycondensation reaction occurs at a temperature of ℃. Alternatively, 3,9-berylene dicarbo/dimethyl acid and ethylene glycol are added to the transesterification product to cause transesterification, followed by polycondensation reaction as described above.

Specific examples of the above-mentioned catalyst compounds include tetrabutyl titanate, motuputyltin oxide, dibutyltin oxide, antimony dioxide, lead dioxide, germanium dioxide, calcium acetate, magnesium acetate, zinc acetate,
Examples include manganese acetate, cobalt acetate, lithium acetate, etc. The amount of these catalysts used is 0.01-1% by weight based on the polymer in the case of a polycondensation catalyst, and 0.01% by weight in the case of a transesterification catalyst. 0.03 to 0.3% by weight is preferred. In addition, to prevent undesirable coloring during this polycondensation reaction, phosphorus compounds such as phosphoric acid, phosphoric acid esters (trimethyl phosphate, etc.), phosphorous acid, and phosphite esters (trimethyl phosphite, etc.) may be added. can.

In addition, when producing the polyester of the present invention, dicarboxylic acid components other than the above-mentioned dicarboxylic acids and ethylene glycol and glycol components such as cono-phosphoric acid, adipic acid, sebacic acid, isophthalic acid, hexahydroterephthalic acid, 1,2-bis (2-Bromphenoxy)ethane-
4,4'-dicarboxylic acid, 1,2-bis(2゜6-dichlorophenoxy)ethane-4,4'-di''
1 carboxylic acid, L-(2-chlorophenoxy)-2(
Dicarboxylic acids such as phenoxy)ethane-4,4'-dicarboxylic acid and/or their ester-forming derivatives and polyethylene glycol, polypropylene glycol, hexamethylene glycol, l,4-cyclohexane-dimetatool, diethylene glycol, neopentyl glycol, bis (β-hydroxyethoxy)bisphenol A and other hydroxycarboxylic acids such as p-(β-oxyethoxy)benzoic acid and/or
Alternatively, an ester-forming derivative thereof can be further copolymerized if the proportion thereof is small.

By melt-forming the polyester obtained by the method of the present invention by melt-spinning, melt-casting, etc., fibers with high elastic modulus and good bending strength and impact strength can be obtained.
Molded products such as films can be obtained. Furthermore, it has been found that the polyester of the present invention is colored yellow to red, and has the advantage that a dyeing process using a dye or the like is not required in industrial applications.

<Example> The present invention will be explained in further detail by giving examples below.

Examples 1 to 4, Comparative Example 1 Dimethyl terephthalate 2.91# (15 mol), ethylene glycol L86# (30 mol), calcium triacetate 2.18F (0,075% by weight to dimethyl terephthalate), antimony oxide 0. 150-250°C in the presence of 87y (0,03% by weight to dimethyl terephthalate)
A transesterification reaction was carried out under stirring for 4 hours, methanol of L21J was distilled off (98% of the theoretical amount), and ethylene glycol 191 F was distilled off to obtain 3.75 kq of transesterification product. As shown in Table 1, a predetermined amount of 3,9-perylene dicarboxylic acid, ethylene glycol (twice the mole of the amount of 3,9-perylene dicarboxylic acid added) and tetrabutyl titanate (3,9-perylene dicarboxylic acid) were added to a predetermined amount of this transesterification product as shown in Table 1. 0.05 weight of 9-perylene dicarboxylic acid9
After adding 6) and causing an esterification reaction under stirring at 250°C for 3 hours, these reactants were transferred to a polymerization tube and heated at 250°C to 29°C.
Raise the temperature to 0℃ in 1 hour and at the same time raise the vacuum level to 1 in 1 hour.
A high vacuum of less than mHp was applied, and polycondensation was further carried out for 2 hours under this high vacuum. Thereafter, the pressure was returned to normal with nitrogen, and then a polymer gut shape was discharged into a water tank under pressure, and the material was cut into chips. These copolyesters had a yellow to red color. The melting point (measured with a differential calorimeter (Perki/Elmer type)) and the intrinsic viscosity (measured in orthochlorophenol at 25° C.) are shown in Table 1.

In addition, these copolymerized polyesters were dissolved in a mixed solvent of orthochlorophenol/deuterated benzene (5/2) and measured by IH-NMR at 400 M)h at 120°C, and the results were 4.6.4 as shown in Table 2. , 7, and 4.85 F, and found that the copolymer composition and sequence distribution can be determined from the area of this peak.

As a result, it was found that all of these polyesters were random copolymers, and the copolymer compositions matched well with the charged compositions.

Table 2 After thoroughly drying this copolymerized polyester, use an extruder (
30° C.) and melt-extruded at 20 to 40° C. higher than the melting point, wound around a drum with a surface temperature of 60° C., and cooled and solidified to produce an unstretched film with a thickness of about 60 μm. This unstretched film was uniaxially stretched 45 times at 95° C. using a film stretcher manufactured by T, M, Long. Table 3 shows the elastic modulus of this -axially stretched film.

From Table 3, the copolymerized polyester of the present invention (Experiments 21 to 3)
) has a higher elastic modulus than PET.

In addition, terephthalic acid/3,9-perylene dicarboxylic acid (
Since 3,9-perylene dicarboxylic acid was not uniformly polymerized from the polymer having a molar ratio of 40/60, it was impossible to obtain a uniform stretched film.

Table 3 Examples 5 to 8, Comparative Examples 2 to 5 Dimethyl 1.2-bis(phenoxy)ethane-4,4'-dicarboxylate, 1.2-bis(2-chlorophenoxy)ethane-4,4 '-Dimethyl dicarboxylate, 2,6-
Dimethyl naphthalene dicarboxylate, 1 dimethyl dicarboxylate consisting of dimethyl 4,4'-diphenyl dicarboxylate/dimethyl terephthalate (molar ratio 50150)
Transesterification reaction was carried out in the presence of 5 mol of ethylene glycol 186F (3 mol) (0.02% by weight to dimethyl dicarboxylate) at 150 to 250°C for 4 hours under continuous stirring. After distilling methanol or more (more than 97% of the theoretical amount), 3,9-
Perylene dicarboxylic acid 53.8F (0.17 mol), ethylene glycol 2Llf (0.34 mol) and tetrabutyl titanate 0.01F were added and an esterification reaction was carried out under stirring at 250°C for 3 hours. were each transferred to a polymerization tube. Then, the temperature is raised from 250℃ to 290℃ in 1 hour, and at the same time, the degree of vacuum is 1 txHy in 1 hour.
Polycondensation was further carried out under the following high vacuum for 2 hours.

Thereafter, the pressure was returned to normal with nitrogen, and then the polymer was discharged into a water tank under pressure in a gut shape and cut into chips.

These copolymerized polyesters (the 3,9-perylene dicarboxylic acid component was 10 mol % of the total dicarboxylic acid components) had a red color. The melting points and intrinsic viscosities (measured in chlorophenol at 25° C.) are shown in Table 4.

Table 4 These copolymerized polyesters were melt-extruded and then axially stretched in the same manner as in Example 1.

- The elastic modulus of the axially stretched film is shown in Table 5.

It can be seen from Table 5 that the modulus of elasticity of the copolymerized polyesters of the present invention is improved by copolymerizing 3,9-perylene dicarboxylic acid.

Effects of the present invention shown in Table 5> The copolymerized polyester of the present invention has a high elastic modulus and is colored from yellow to red. Therefore, it can be widely used in various industries (tire cords, conveyor belts, power transmission belts, etc.), magnetic tapes, etc. without going through a dyeing process using dyes or the like.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Scope of Claims] Consisting of the following main structural units [I] and [II], the structural unit [I] is 0.05 to 55 mol% of the total, and the structural unit [
II] is comprised of 99.95 to 45 mol% of the total melt-moldable copolymer polyester ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... [I] - [OCRCO_2 (CH_2) ＿２O〕－・・・・・・
[II] (However, R has ▲ 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,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ indicates one or more dicarboxylic acid residues selected from).