JPH0526811B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a colored copolyester polyester having a high elastic modulus 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, tracing, and other applications. It is used. 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 characteristics, 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 g/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 magnification, and the reality is that this requirement cannot be fully satisfied. Therefore, as a new material, polyethylene-1,
2-bis(phenoxy)ethane-4,4'-dicarboxylate, polyethylene-1,2-bis(2
-Chlorphenoxy)ethane-4,4'-dicarboxylate, polyethylene-2,6-naphthalate, polyethylene-4,4'-dicarboxylate/polyethylene terephthalate, etc. have been studied in the past, and these polyesters have been used in yarns, films, etc. It is known to have a higher elastic modulus than polyethylene terephthalate. <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, 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 effects for solving the problems> That is, the present invention provides the following structural units [] and []
A melt-moldable copolyester characterized by having structural units [] of 0.05 to 50 mol% of the total, structural units [] of 99.95 to 50 mol% of the total, and an intrinsic viscosity of 0.5 to 0.9. This is what we provide. [-OCRCO ₂ (CH ₂ ) ₂ O] - ... [] (However, R is

【formula】

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[Formula] represents one or more dicarboxylic acid residues selected from). The copolymerized polyester 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
Terephthalic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-, consisting of 99.95 to 45 mol%, preferably 99.9 to 50 mol%. 4,4'-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,
By polycondensing a dicarboxylic acid component consisting of one or more dicarboxylic acids selected from 4,4'-diphenyldicarboxylic acid or an ester thereof and a diol component mainly consisting of ethylene glycol by a direct polymerization method or a transesterification method. This is a copolymerized polyester obtained by Here, when 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 when it is more than 55 mol%, the 3,9-perylene dicarboxylic acid or its ester is Homogeneous copolymerization 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, antimony,
Polycondensation reactions occur at temperatures of 220-300°C under high vacuum in the presence of catalytic compounds such as lead, germanium, and titanium. 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 - Transesterification reaction of ester of 3,9-perylene dicarboxylic acid with other dicarboxylic acid esters and ethylene glycol at 130 to 260°C in the presence of catalyst compounds such as calcium, magnesium, zinc, manganese, cobalt, and lithium. After cooling, a polycondensation reaction is carried out at a temperature of 220-300°C under high vacuum in the presence of catalytic compounds such as antimony, lead, germanium, and titanium. Alternatively, dimethyl 3,9-perylene dicarboxylate and ethylene glycol are added to the transesterification product to cause transesterification, followed by polycondensation reaction as described above. Here, specific examples of the above catalyst compounds include tetrabutyl titanate, monobutyltin oxide,
Dibutyltin oxide, antimony trioxide, lead dioxide, germanium dioxide, calcium acetate, magnesium acetate, zinc acetate, manganese acetate, cobalt acetate, lithium acetate, etc. are used, and the amount of these catalysts used depends on the polymer in the case of polycondensation catalysts. In contrast, 0.01 to 1% by weight is suitable, and in the case of a transesterification reaction catalyst, 0.03 to 0.3% by weight is suitable. Additionally, in order to prevent undesirable coloration during this polycondensation reaction, phosphorus compounds such as phosphoric acid, phosphate esters (trimethyl phosphate, etc.), phosphorous acid, and phosphite esters (trimethyl phosphite, etc.) may be added. I can do it. 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 succinic acid, adipic acid, sebacic acid, isophthalic acid, hexahydroterephthalic acid, 1,2-bis(2 -Promphenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2,6-dichlorophenoxy)ethane-4,4'-dicarboxylic acid, 1-
Dicarboxylic acids such as (2-chlorophenoxy)-2(phenoxy)ethane-4,4'-dicarboxylic acid and/or their ester-forming derivatives and polyethylene glycol, polypropylene glycol, hexamethylene glycol, 1,4-cyclohexane-dicarboxylic acid, etc. Small proportions of glycols such as methanol, diethylene glycol, neopentyl glycol, bis(β-hydroxyethoxy)bisphenol A, oxycarboxylic acids such as P-(β-oxyethoxy)benzoic acid, and/or their ester-forming derivatives, etc. If necessary, further copolymerization can be carried out. By melt-molding the polyester obtained by the method of the present invention by melt-spinning, melt-casting, etc., molded products such as fibers and films with high elastic modulus and good flexural strength and impact strength 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 described in further detail with reference to Examples below. Examples 1 to 4, Comparative Example 1 2.91 Kg (15 moles) of dimethyl terephthalate and 1.86 Kg0 (30 moles) of ethylene glycol were combined with 2.18 g (0.075 wt% to dimethyl terephthalate) of calcium acetate and 0.87 g (0.03 wt%) of antimony oxide.
150-250 in the presence of dimethyl terephthalate)
The transesterification reaction was carried out under stirring for 4 hours at 1.21 °C.
After distilling off methanol (98% of the theoretical amount), 191 g of ethylene glycol was distilled off.
3.75Kg of transesterification product was obtained. As shown in Table 1, a predetermined amount of 3,9-perylene dicarboxylic acid, ethylene glycol (twice the mole of the added amount of 3,9-perylene dicarboxylic acid) and tetrabutyl titanate (3,9-perylene dicarboxylic acid) are added to a predetermined amount of this transesterification product as shown in Table 1.
0.05% by weight of 9-perylene dicarboxylic acid) was added.
After carrying out the esterification reaction at 250°C for 3 hours with stirring, these reactants were transferred to a polymerization tube and the temperature was raised from 250°C to 290°C in 1 hour, and at the same time the vacuum level was reduced to 1 mm in 1 hour.
A high vacuum of Hg or less was applied, and polycondensation was further carried out for 2 hours under this high vacuum. After that, the pressure was returned to normal with nitrogen, and the polymer was discharged into a water tank under pressure.
Cutting was done into chips. These copolyesters had a yellow to red color. The melting points (measured with a differential calorimeter (Perkin-Elmer type)) and intrinsic viscosities (measured in orthochlorophenol at 25° C.) are shown in Table 1.

[Table] These copolymerized polyesters were dissolved in a mixed solvent of orthochlorophenol/deuterated benzene (5/2) and analyzed by IH-NMR at 400MHz at 120°C.
It was found that the following peaks appeared at 4.6, 4.7, and 4.85 ppm as shown in Table 2, and it was found that the copolymer composition and sequence distribution could be determined from the area of these peaks. As a result, it was found that all of these polyesters were random copolymerized and the copolymerization compositions matched well with the charged compositions.

[Table] After thoroughly drying this copolyester,
It was fed into an extruder (30 mmφ) and melted and 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 end-stretched film with a thickness of about 60 μm. TMLong this end stretched film
At 95℃ using a film stretcher manufactured by
It was uniaxially stretched to 4.5 times. Table 3 shows the elastic modulus of this uniaxially stretched film. From Table 3, the copolymerized polyester of the present invention (experimental
It can be seen that Nos. 1 to 3) have higher elastic modulus than PET. In addition, from a polymer with a terephthalic acid/3,9-perylene dicarboxylic acid (molar ratio) of 40/60,
- It was impossible to obtain a uniform stretched film because the perylenedicarboxylic acid was not uniformly polymerized.

[Table] Examples 5 to 8, Comparative Examples 2 to 5 1,2-bis(phenoxy)ethane-4,4'-
Dimethyl dicarboxylate, dimethyl 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl 4,4'-diphenyldicarboxylate/
1.5 mol each of dimethyl dicarboxylate consisting of dimethyl terephthalate (molar ratio 50/50) and 186 g (3 mol) of ethylene glycol were mixed at 150 to 250°C in the presence of tetrabutyl titanate (0.02% by weight to dimethyl dicarboxylate). 120ml or more (more than 97% of the theoretical amount) for transesterification reaction under stirring for an hour
After distilling off methanol, 53.8 g (0.17 mol) of 3,9-perylene dicarboxylic acid, 21.1 g (0.34 mol) of ethylene glycol, and 0.01 g of tetrabutyl titanate were added, and an esterification reaction was carried out under stirring at 250°C for 3 hours. After cooling, each of these reactants was transferred to a polymerization tube. Then, the temperature was raised from 250° C. to 290° C. in 1 hour, and at the same time the temperature was raised to a high vacuum of 1 mmHg or less in 1 hour, and polycondensation was further carried out under this vacuum for 2 hours. After that, the pressure was returned to heavy 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 (3,9-perylene dicarboxylic acid component was 10 mol % of the total dicarboxylic acid component) were red in color. Melting point and intrinsic viscosity (25 in orthochlorophenol
℃) are shown in Table 4. On the other hand, the melting points and intrinsic viscosities of polyesters not copolymerized with 3,9-perylene dicarboxylic acid are also shown in Table 4 as Comparative Examples 2 to 5.

[Table] These copolymerized polyesters were melt-extruded and uniaxially stretched in the same manner as in Example 1. Table 5 shows the elastic modulus of the uniaxially stretched film. From Table 5, the copolymerized polyester of the present invention is 3,
It can be seen that the modulus of elasticity is improved in all cases by copolymerizing 9-perylene dicarboxylic acid.

[Table] <Effects of the Invention> 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 industrial materials fields (tire cords, conveyor belts, power transmission belts, etc.), magnetic tapes, etc. without going through a dyeing process using dyes or the like.

Claims (1)

[Scope of Claims] 1 Comprised of the following main structural units [] and [], with the structural unit [] accounting for 0.05 to 55 mol% of the total, and the structural unit [] accounting for 99.95 to 45 mol% of the total, and having an intrinsic viscosity of 0.5 to 0.9. A melt-formable copolyester characterized by [-OCRCO ₂ (CH ₂ ) ₂ O] - ... [] (However, R represents one or more dicarboxylic acid residues selected from [Formula] [Formula] [Formula] [Formula] [Formula]).