KR100841175B1 - Atmospheric cationic dye dyeable copolyester polymer, manufacturing method thereof, and atmospheric cationic dye dyeable copolyester fiber using the same - Google Patents

Abstract

A room temperature cationic dye dyeable copolyester polymer, a method for preparing the polymer, and a room temperature cationic dye dyeable copolyester fiber prepared by using the polymer are provided to improve dyeing property of a cationic dye at a low temperature of 100 deg.C or less and to lower the manufacturing cost of a copolyester fiber. A room temperature cationic dye dyeable copolyester polymer comprises 1-20 mol% of an aliphatic dibasic acid component; and 1.0-2.0 mol% of a bishydroxyethyl isophthalate containing a metal sulfonate represented by the formula 1 based on the total dibasic acid component, wherein M is an alkali metal. Preferably the polymer contains 1.5-3.5 wt% of diethylene glycol, 20 ppm or less of the unreacted terephthalic acid and 30-50 eq/ton of a carboxyl terminal group.

Description

Atmospheric cationic dye dyeable copolyester polymer, manufacturing method etc, and atmospheric cationic dye dyeable copolyester fiber using the same}

1 is a process diagram of a three-tube TPA polymerization reactor used to prepare a polymer of the present invention.

* Description of the symbols for the main parts of the drawings *

1 Preparation 2 Slurry Storage Tank

3: DE-1 4: feed line filter

5: DE-2 6: Feed Line Filter

7: polycondensation reactor 8: pelletizer

  The present invention relates to an atmospheric pressure cationic dye chlorinated copolyester polymer, a method for producing the same, and an atmospheric pressure cationic dye salted copolyester fiber using the same, which is inexpensive to manufacture, using terephthalic acid (hereinafter abbreviated as TPA) as a raw material. By using the polymerization method, to provide a copolyester polymer and the fiber excellent in the dyeability to the cationic dye at a normal pressure of 100 ℃ or less with uniform quality and low production cost.

Regarding atmospheric pressure cationic dye saltable copolyester polymers and fibers thereof which can be dyed with cationic dyes at atmospheric pressure of 100 ° C. or lower, the following is disclosed. Japanese Patent Application Laid-Open No. 2002-284863 discloses a method for continuously preparing an atmospheric pressure cationic dye saltable polyester polymer, specifically, the polyester has a metal sulfonate salt of 2.0 to 3.0 mol% of an acid component. , Polyalkylene glycol having a molecular weight of 400 to 1000 is included in the polymer as 4.0 to 6.0% by weight, the content of diethylene glycol in the polymer is 4.5 to 6.0 mol%, 20 to 30 carboxyl end groups Equivalent / tonne, and has a small physical variation with extreme viscosity.

However, the atmospheric pressure cationic dye chlorinated polyester fibers produced by the present invention have a high content of metal sulfonate salts, so that the weight loss rate is too fast during weight loss processing, making it difficult to maintain the shape as a fiber and diethylene glycol as a by-product of the reaction. Too high a content of the polymer and a problem that makes the heat resistance of the fiber to be made weak.

Japanese Patent Laid-Open No. 2001-55626 discloses that a metal sulfonate salt is copolymerized at 0.1 to 10 mol% and HO (CH ₂ CH ₂ O) _l (RO) _m (CH ₂ CH ₂ O) _n to improve heat resistance. 0.1 to a substance represented by H (wherein R is an aliphatic hydrocarbon group having 3 to 25 carbon atoms, l and n are the same or different integers, 1 ≦ l + n ≦ 40, and m is an integer of 2 to 50). Disclosed is a polyester fiber containing 10% by weight. However, according to the present invention, in order to prepare an atmospheric pressure cationic salt type polyester fiber, HO (CH ₂ CH ₂ O) _l (RO) _m (CH ₂ CH ₂ O) _n (wherein R is an aliphatic hydrocarbon group of 3 to 25 carbon atoms, l, n is the same or different integer, 1≤l + n≤40, m is an integer of 2-50) Although it should be used, this material is not suitable because of the high cost of manufacturing, and the manufacturing cost is further increased when the dimethyl terephthalate manufacturing method disclosed in the embodiment of the present invention is prepared. In addition, the isophthalic acid derivatives among the copolymerized components having the cation salted seat disclosed in the present invention are difficult to use because of their high price. it's difficult.

 Japanese Patent Application Laid-Open No. 5-331719 proposes to produce atmospheric pressure chlorinated fiber by copolymerizing sulfonic acid phosphonium base and polyoxyalkylene glycol, but the price of sulfonic acid phosphonium base is too high. Therefore, it is difficult to apply industrially.

Japanese Patent Application Laid-Open No. 2006-63215 discloses 0.5 to 8.0 mol% of metal sulfonate salt, copolymerizes aliphatic dibasic acid having 5 to 10 carbon atoms at 0.5 to 8.0 mol% relative to the total acid component, and magnesium as a copolymerization catalyst. Although a method of using a compound or an aluminum compound is disclosed, there is a disadvantage that the price of the compound used as a copolymerization catalyst is too expensive for industrial application.

Therefore, there has been a demand for research into a manufacturing method for providing a low pressure manufacturing cost and excellent atmospheric pressure cationic dye salt copolyester polymer and its fiber.

The technical problem to be achieved by the present invention is to use a TPA polymerization method that can lower the production cost of the polyester, the polymer for atmospheric pressure cationic dye saltable copolyester fibers that can be dyed by the cationic dye at a normal pressure of 100 ℃ or less and the preparation thereof To provide a way. .

The present invention, by using the above method, to provide a low-pressure cationic dye salt-coating copolyester fiber having a low glass transition temperature and excellent dyeability.

The technical problem of the present invention can be achieved by the present invention described below.

One aspect of the present invention is an atmospheric pressure cationic dye comprising 1 to 20 mol% of an aliphatic dibasic acid and 1.0 to 2.0 mol% of bishydroxy ethylisophthalate containing a metal sulfonate salt, based on the total dibasic acid component. The present invention relates to a polymer for caustic copolyester fibers.

Another aspect of the invention, (a) mixing the terephthalic acid and ethylene glycol to prepare a slurry, and adding a aliphatic dibasic acid to the slurry to prepare a slurry,
(b) adding the prepared slurry to a first reactor to perform an esterification reaction,
(c) transferring the product of step (b) to a second reactor and kneading by adding bishydroxy ethylisophthalate represented by Chemical Formula 1 of the present invention to a second reactor;
(d) polycondensing the flame retardant polyester by transferring the product of step (c) to a polycondensation reactor; and
(e) a method for preparing an atmospheric pressure cationic dye saltable copolyester polymer comprising the step of discharging the product of step (d) from a pelletizer to chip the polymer.
Another aspect of the present invention relates to a fiber using an atmospheric pressure cationic dye saltable copolyester polymer.

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

The present invention has been developed in a way to lower the glass transition temperature of the polymer in order to lower the dyeing temperature. Only when the glass transition temperature of the polymer is low, the molecular chain at low temperature is free, so that the dye molecules can easily penetrate into the fiber, and as a copolymerization monomer, aliphatic dibasic acid is more preferable than polyoxyalkylene glycol. Do. The polyoxyalkylene glycol is effective in lowering the glass transition temperature of the polymer, but is not suitable for improving the fluidity of the entire molecular chain. Therefore, the study was conducted mainly on aliphatic dibasic acids, and its content is suitably 1-20 mol% of the total dibasic acids. If the aliphatic dibasic acid component is less than 1 mol% of the total dibasic acid component, the effect of lowering the glass transition temperature is less. If the aliphatic dibasic acid component is more than 20 mol%, the crystallinity of the polymer is too low, and workability such as spinning is poor. In addition, the injection position of the aliphatic dibasic acid in the polymerization process was introduced during the production of slurry of TPA and EG (hereinafter, abbreviated as EG). Since aliphatic dibasic acid is dissolved in EG and its reactivity is higher than that of TPA, it is advantageous in terms of increasing the reaction rate.

Metal sulfonate salt-containing bishydroxy ethyl isophthalate (hereinafter abbreviated as DES) represented by the formula (1) was used as the metal sulfonate component to be added to exhibit the cationic dye saltability.

Wherein M is an alkali metal.
The alkali metal of Formula 1 may include, for example, Na, Li, K, but is not limited thereto.

 In addition to bishydroxy ethyl isophthalate (DES), when a metal sulfonate-containing dialkyl isophthalate which is usually commercially used is used, it is not reacted in the TPA polymerization process and remains as an unreacted product. It will cause a fair deterioration.

In order to suppress side reaction formation such as gel formation by pyrolysis of DES, the polymerization was used with a three-tube polymerization reactor shown in FIG. In the two-pipe type (consisting of esterification and polycondensation reaction tanks) used in the TPA polymerization method, it is difficult to select the input position of the additives and the quality of the base oligomer by the additives is not suitable for the polymer to which various additives are added. . Injecting DES was added to DE-2 to inhibit long-term residence in the reactor.

In addition, polycondensation catalysts are currently used in the manufacture of most polyesters, and antimony compounds having good performance and physical properties are used for the price.

Hereinafter, with reference to FIG. 1, it demonstrates more concretely.

(a) A slurry of terephthalic acid and ethylene glycol, which are reaction raw materials, is prepared in Preparation Room 1, and the aliphatic dibasic acid in the present invention is added in this step to prepare a slurry. The molar ratio of terephthalic acid and aliphatic dibasic acid is 20:80 to 1:99.

(b) The slurry prepared in (a) is stored in storage tank 2.

(c) Slurry of the storage tank 2 to the first reactor (DE-1) 3 in which the base oligomer is maintained in the reaction tank at a constant temperature (typically 250-260 ° C.) in a semi-batch process. Maintain the internal temperature and continuously inject the reaction. The end of the esterification reaction is determined by the amount of effluent flowing out of the reactor and the reaction rate of the oligomer. The initial amount of base oligomer is left in the DE-1 reactor and the remaining amount is passed through the filter by the nitrogen pressure in the second reactor (DE-2). ) Transfer to 5.

(d) the oligomer having undergone the esterification reaction in the DE-1 reactor is transferred to the DE-2 reactor through a transfer line filter (consisting of a basket filter) 4 to further proceed with the reaction, which is represented by Chemical Formula 1 in the present invention. Inject DES.

(e) The flame-retardant oligomer in which the reaction proceeded in DE-2 is transferred to a polycondensation reactor 7 through a transfer line filter (composed of a basket filter) 6 to react the oligomer to react the flame-retardant polyester and polycondens the flame-retardant polyester.

(f) The polymer produced in the reactor 7 is discharged from the pelletizer 8 to chip.

In the TPA polymerization process, diethylene glycol ((Diethylene Glycol, hereinafter abbreviated as DEG)) is generated as a side reaction by the acid component of TPA. The content of DEG in the polymer in the present invention is 1.5 to 3.5% by weight relative to the total polymer. In the polymerization formulation according to the present invention, the content of DEG cannot be produced in less than 1.5% by weight, and when the resultant DEG is 1.5% by weight or more, the glass transition temperature of the polymer can be lowered, but the content of DEG is 3.5. When the weight percentage is exceeded, the thermal stability of the polymer is too low, and the spinning processability of the polymer is deteriorated.

The content of terminal carboxyl groups by thermal decomposition by unreacted TPA is 30 to 50 equivalents / ton in the total polymer. If the content of the carboxyl end group is less than 30 equivalents / ton, it is possible to lower the reaction temperature or increase the content of EG, but in each case, the reaction time is prolonged, resulting in deterioration of the polymer and increase of DEG, a side reaction product. Happens incidentally. In addition, when the content of the carboxyl end groups exceeds 50 equivalents / ton, most of them are terminal carboxyl groups due to pyrolysis, thereby causing problems such as gelation due to deterioration of the polymer.

The content of unreacted TPA in the polymer is 20 ppm or less. Since unreacted TPA is a material that is neither melted nor difficult to dissolve in a solvent, if it exceeds 20 ppm, TPA remaining in an unreacted state causes deterioration of fairness of spinning.

As for the melting temperature of the said polymer, 215-240 degreeC is suitable. When lower than 215 degreeC, heat resistance will fall and a spin processability will worsen, and the heat resistance of a yarn will become a problem. If the copolymerization in polyethylene terephthalate proceeds sufficiently, the melting point decreases, and it is difficult to prepare a polymer having a melting temperature higher than 240 ° C, and when the melting point is higher than 240 ° C, copolymerization monomers remain unreacted in the polymer. As a result, the quality of the polymer and yarn decreases.

Physical properties of Examples and Comparative Examples of the present invention were analyzed by the following method.

1. Ester reaction rate of terephthalic acid: The concentration of carboxylic acid was titrated using ester-reacted oligomer.

2. Intrinsic Viscosity (hereinafter abbreviated as IV): Melt the polymer in a solution containing phenol and 1,1,2,2-tetrachloroethane in a 6: 4 weight ratio and use the Uvelode tube in a 30 ℃ thermostat. It was measured by.

3. Melting temperature and glass transition temperature: Using Perkin Elmer's DSC 7 (Differential Scanning Calorimetry), the temperature was raised to 10 ℃ / min and analyzed as a peak within the melting range.

4. Content of dibasic acid and DES: analyzed using 400MHz NMR.

5. DEG content: The polymer was decomposed using ethanol amine and analyzed by Gas Chromatography.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the scope of the present invention is not limited by this embodiment.

Example 1

TPA to aliphatic dibasic acid is composed of 20:80 ~ 1:99 molar ratio, and adipic acid (hereinafter AA) was used as aliphatic dibasic acid. A slurry was prepared by mixing TPA: AA: EG at 600: 315: 50 (volume ratio). The slurry was continuously added to the DE-1 reactor of FIG. 1 in which adipic acid was mixed with 8.7 mol% of the total dibasic acid and 1.3 tons of the base oligomer was melted at 255 ° C. The slurry was added so that the polymer became 1.5 ton, and the esterification reaction was continued for 30 minutes, and then 1.5 tons of oligomer was transferred to the DE-2 reactor using a metering pump. 1.3 mol% of the DES represented by the formula (1) in the DES represented by Formula 1 (molecular weight 356 and dissolved in EG at a concentration of 35% by weight) was added to the transferred oligomer compared to the total dibasic acids (TPA, AA, DES). It was. After sufficient stirring, the polycondensation reaction tank was transferred to FIG. 1, and 250 ppm of antimony trioxide 2% EG solution was added to the antimony trioxide based on the polymer, and the reaction was performed at 285 ° C. and 1 torr or less. Physical properties of the prepared polymer are shown in Table 1.

Example 2

Table 1 shows the physical properties of the polymer prepared in the same manner as in Example 1, except that 8.5 mol% of azelaic acid (abbreviated to AZA) was added to the total dibasic acid instead of AA.

Example 3

Table 1 shows the physical properties of the polymer prepared in the same manner as in Example 1, except that M is Li in the DES represented by Chemical Formula 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Aliphatic dibasic acid content (mol%) 8.32 8.23 8.35 0 8.2 Alkali metal (M) Na Na Li Na - DES content (mol%) 1.31 1.24 1.32 1.35 0 DEG content (% by weight) 2.19 2.40 2.32 1.56 1.21 CEG (equivalent / ton) 35 33 36 31 27 Melting temperature (℃) 232 231 234 243 241 Glass transition degree (℃) 65 63 66 76 64

Comparative Example 1

Except that AA was not added, the physical properties of the polymer prepared in the same manner as in Example 1 are shown in Table 1.

Comparative Example 2

Except that DES was not added, the physical properties of the polymer prepared in the same manner as in Example 1 are shown in Table 1.

Example 4

The polymer produced in Example 1 was vacuum dried in a 140 ° C. vacuum dryer (15 ppm water content) and spun at a first high roller speed of 1750 m / min at 295 ° C. and 80 ° C., and a second high roller speed of 3700 m / min at 120 ° C. It was. It was knitted and dyed at 95 ° C. with Kayacryl dye of Nippon Gunpowder. As a result of dyeing, good dyeability was obtained.

Comparative Example 3

It carried out similarly to Example 4 except using the polymer manufactured by the comparative example 1. The staining resulted in poor staining of the contamination level.

The copolyester polymer of the present invention can provide a low pressure atmospheric cationic dye chlorinated copolyester fibers exhibiting excellent dyeing with a cationic dye at a dyeing temperature of less than 100 ℃, the production method of the present invention is an oligomer filter Good replacement cycle and good polymerization process can reduce production cost.

Claims (9)

Atmospheric pressure cationic dye chlorinated copolyoleic acid containing 1-20 mol% of aliphatic dibasic acid components and 1.0-2.0 mol% of bishydroxy ethylisophthalate containing a metal sulfonate salt, based on the total dibasic acid component. Ester Polymers: [Formula 1]

M is an alkali metal. According to claim 1, wherein the polymer is diethylene glycol is 1.5 to 3.5% by weight relative to the total polymer, unreacted terephthalic acid is 20ppm or less, characterized in that it comprises 30 to 50 equivalents / ton of carboxyl end groups Polymer. The polymer of claim 1, wherein the polymer has a melting temperature of 215 to 240 ° C. The polymer of claim 1, wherein the polymer is prepared by a terephthalic acid polymerization method.  (a) mixing terephthalic acid and ethylene glycol to prepare a slurry, and adding a aliphatic dibasic acid to the slurry to prepare a slurry; (b) adding the prepared slurry to a first reactor to perform an esterification reaction; (c) transferring the product of step (b) to a second reactor and kneading by adding bishydroxy ethylisophthalate represented by Formula 1 to a second reactor; (d) polycondensing the flame retardant polyester by transferring the product of step (c) to a polycondensation reactor; And (e) a method for preparing an atmospheric pressure cationic dye saltable copolyester polymer, comprising the step of discharging the product of step (d) from a pelletizer to chip the polymer. The method according to claim 5, wherein the production method uses a three-tube terephthalic acid polymerization reactor. The method of claim 5, wherein the aliphatic dibasic acid is adipic acid or azelaic acid. The method of claim 5, wherein the molar ratio of aliphatic dibasic acid and terephthalic acid in the step (a) is 20:80 ~ 1:99. Atmospheric pressure cationic dye saltable copolyester fiber prepared using the polymer according to any one of claims 1 to 4.

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