KR101201390B1 - Block copolymeric Polyester having low melting point and Manufacturing method thereof - Google Patents

Abstract

The present invention is the first esterification of terephthalic acid (TPA), ethylene glycol (ethylene glycol: EG), diethylene glycol (DEG), and then isophthalic acid (IPA), ethylene glycol ( The present invention relates to a block copolymer low melting polyester prepared by secondary esterification by adding ethylene glycol (EG).

Description

Block copolymeric polyester having low melting point and manufacturing method

The present invention relates to a block copolymer low melting point polyester and a method for producing the same, and more particularly, to a block copolymer low melting point polyester prepared by block copolymerization and melted at a low temperature to improve adhesion.

In general, synthetic fibers have a high melting point, and their use is often limited. In particular, when the fiber fabric itself is used as a wick or the like, and is used as an adhesive that is interposed between a tape-like fabric and press-bonded, the textile fabric itself may be thermally deteriorated by heating, and special equipment such as a high frequency sewing machine may be used. Because of the hassle that must be used, it is desired to adhere easily by a conventional simple hot press without using such special equipment.

BACKGROUND ART [0002] Hot melt type binder fibers have been widely used in conventional low melting point polyester fibers for the purpose of bonding different types of fibers to each other in a mattress, an automobile interior or an interwoven fiber structure used for various nonwoven fabric padding applications.

Therefore, there is a high demand for a polyester resin having a low melting point, and it is used for a binder fiber or an adhesive. Generally, a copolymerized polyester is used for such use.

For example, U.S. Patent No. 4,129,675 discloses a low melting polyester copolymerized with terephthalic acid (TPA) and isophthalic acid (IPA), but isophthalic acid (IPA) There is a problem that the low melting point polyester using a large amount of isophthalic acid as a material has a high production cost and low competitiveness.

In addition, Japanese Patent Application Laid-open No. Hei 10-298271 uses adipic acid instead of terephthalic acid in the process of polymerization to improve crystallinity and heat resistance, and 1,4-butanediol (BD) as a diol component instead of ethylene glycol. ) To improve the adhesiveness and to provide a fiber with little decrease in the strength of the fiber even at a high temperature, but low melting point polyester produced using adipic acid is a low melting point polyester having a melting point of 150 ° C. or less. There was a problem that it is difficult to prepare a low melting point polyester of lower melting point.

The present invention has been invented to solve the above problems, an object of the present invention is to provide a block copolymer low melting point polyester having a high melting point at a melting point of 150 ° C. or less and a method of producing the same.

In addition, it solves the problem of separation of adhesive sites over time with excellent solubility parameters. When applied to polyester fiber, it exhibits excellent adhesive properties and blocks copolymers that do not separate even after elapse of time. To provide a method of manufacturing.

The present invention is the first esterification of terephthalic acid (TPA), ethylene glycol (ethylene glycol: EG), diethylene glycol (DEG), isophthalic acid (IPA), ethylene glycol ( It provides a block copolymer low-melting polyester, characterized in that prepared by the second esterification by adding ethylene glycol: EG).

In addition, the low melting point polyester provides a block copolymer low melting point polyester having a degree of polymerization (Pn) of 60 to 90.

In addition, the low-melting polyester is 47 to 75 parts by weight of isophthalic acid (IPA), 67 to 74 parts by weight of ethylene glycol (EG), diethylene glycol 100 parts by weight of terephthalic acid (TPA) (diethylene glycol: DEG) is prepared by mixing 2.5 to 13 parts by weight, the ethylene glycol (ethylene glycol: EG) is 10 to 95% by weight of the addition is added in the first esterification reaction and 5 in the second esterification reaction It provides a block copolymer low melting point polyester, characterized in that ~ 90% by weight is added.

In addition, the softening point of the low-melting point polyester provides a block copolymer low-melting point polyester, characterized in that 90 ~ 110 ℃.

The present invention also provides a block copolymer low melting point polyester having a glass transition temperature (Tg) of the low melting point polyester at 60 to 70 ° C.

In addition, there is provided a block copolymer low melting polyester, characterized in that the intrinsic viscosity (IV) of the low melting polyester is 0.55 ~ 0.75.

In addition, the present invention is a method for producing a low-melting polyester, 5 to 90% by weight of 67 to 74 parts by weight of ethylene glycol (ethylene glycol: EG), diethylene glycol (100 parts by weight terephthalic acid (terephthalic acid (TPA)) diethylene glycol: DEG) 2.5 to 13 parts by weight of the first mixing step of mixing at 200 ~ 230 ℃; A primary esterification step of esterifying the mixture of the first mixing step at 240 to 260 ° C. for 2 to 4 hours at 2.0 to 2.5 kgf / cm 2 pressure; A second mixture of 5 to 90% by weight of the ethylene glycol (EG) 67 to 74 parts by weight, and 47 to 75 parts by weight of isophthalic acid (IPA) at 230 to 240 ° C. fair; A secondary esterification step of esterifying the mixture of the second mixing step at 240 to 260 ° C. for 2 to 4 hours at 2.0 to 2.5 kgf / cm 2 pressure; And a polycondensation process of polymerizing the secondary ester reactant under vacuum at 0.1 to 1 Torr for 275 to 285 ° C. for 40 to 100 minutes. .

In addition, the degree of polymerization (Pn) of the low-melting polyester in the polycondensation process provides a method for producing a block copolymer low-melting polyester, characterized in that the polymerization to 60 ~ 90.

In addition, the present invention provides a method for producing a block copolymer low melting point polyester using antimony trioxide (Sb ₂ O ₃ ) as a reaction catalyst in the polycondensation process.

The present invention also provides a method for producing a block copolymer low melting point polyester, wherein a phosphoric acid or phosphorus flame retardant is added in the polycondensation process.

The present invention also provides a method for producing a block copolymer low melting polyester, wherein TiO ₂ or SiO ₂ is added as a matting agent in the polycondensation step.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, it should be noted that, in the drawings, the same components or parts have the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

The terms "about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation of, or approximation to, the numerical values of manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The present invention is a block copolymer low melting point polyester prepared through block copolymerization.

In general, the copolymer may be divided into a random copolymer and a block copolymer.

The random copolymer is a copolymer in which monomers having different chemical structures are randomly connected to form a polymer chain, and a block copolymer is a copolymer in which several units of chemically identical monomers are arranged according to the main polymer chain. .

The block copolymer can arbitrarily control the content of each compound to be polymerized compared to the random copolymer, and has the advantage of easily controlling the molecular weight and physical properties.

The present invention is the first esterification of terephthalic acid (TPA), ethylene glycol (ethylene glycol: EG), diethylene glycol (DEG), and then isophthalic acid (IPA), ethylene glycol ( ethylene glycol: EG) is added to the secondary esterification reaction to produce a low-melting polyester by controlling the degree of polymerization of the polymer to adjust the content of terephthalic acid, ethylene glycol, diethylene glycol, isophthalic acid and molecular weight and physical properties Can be adjusted.

In addition, as a method for controlling the melting point of the polyester, isophthalic acid (IPA), adipic acid, 1, 4-butanediol (1, 4-butanediol), neopentyl glycol (Neopentyl glycol) and the like It is added to the copolymer to produce a low melting point polyester, but in the present invention by using only isophthalic acid (IPA) to control the degree of polymerization of the copolymerized polyester to produce a low melting point polyester without lowering the radioactivity It will be meaningful.

It is preferable that the degree of polymerization (Pn) of the block copolymerized low melting polyester according to the present invention is made from 60 to 90. If the polymerization degree is less than 60, the radioactivity may be deteriorated, which may cause a problem in use. When the polymerization degree exceeds 90, the melting point may be increased.

It will be preferable to produce a polymerization degree of 60 to 90 as described above to produce a softening point of low melting point polyester at 90 to 110 ° C.

Block copolymer low melting point polyester according to the present invention is 47 to 75 parts by weight of isophthalic acid (IPA), 67 to 74 parts by weight of ethylene glycol (EG), 100 parts by weight of terephthalic acid (TPA), Diethylene glycol (DEG) 2.5 to 13 parts by weight is prepared by the primary, secondary ester reaction.

When added to less than 10% by weight of the total amount of ethylene glycol in the primary esterification or less than 5% by weight of the total amount of ethylene glycol in the secondary esterification, the effect of block copolymerization is insignificant Ethylene glycol (EG) is preferably added 10 to 95% by weight of the addition amount in the first esterification reaction and 5 to 90% by weight in the second esterification reaction.

The diethylene glycol (DEG) to lower the melting point of the polyester with isophthalic acid (IPA) to lower the crystallinity of the polyester during the polymerization process to lower the melting point, low melting point polyester After the preparation, the functional group is more functionalized in ethylene glycol than the polyester produced from ethylene glycol improves the dyeability and hygroscopicity.

As described above, the low-melting polyester prepared with terephthalic acid and isophthalic acid as an acid component and ethylene glycol and diethylene glycol as a diol component should have an intrinsic viscosity (IV) of 0.55 to 0.75. If the intrinsic viscosity is less than 0.55, the physical properties of the polyester produced is poor and the heat resistance is difficult to use, and if the intrinsic viscosity exceeds 0.75, the melting point becomes high and the target melting point cannot be obtained.

Moreover, it is preferable that the glass transition temperature (Tg) of the said block copolymer low melting point polyester is 60-70 degreeC.

Block copolymer low melting point polyester production method according to the present invention as described above is a first mixing step of mixing terephthalic acid (Tephthalic acid (TPA), ethylene glycol (EG), diethylene glycol (DEG), A first esterification step of esterifying the mixture of the first mixing step, a second mixing step of mixing ethylene glycol (EG) and isophthalic acid (IPA) with the primary ester reactant, It is prepared including a secondary esterification step of esterifying the mixture of the second mixing step, and a polycondensation step of polymerizing the secondary ester reactant.

The first mixing process is 5 to 90% by weight of 67 to 74 parts by weight of ethylene glycol (EG), diethylene glycol (DEG) 2.5 to 13 parts by weight of terephthalic acid (TPA) 100 parts by weight The process of mixing the part at 200 ~ 230 ℃ should be carried out at 200 ~ 230 ℃ to smoothly proceed to the next step of the esterification process.

The first esterification step is a step of esterifying an acid component of terephthalic acid and a diol component of ethylene glycol and diethylene glycol to generate an ester reactant. The mixture of the first mixing process is 240 at a pressure of 2.0 to 2.5 kgf / cm 2. It is a process of esterifying for 260 degreeC and 2 to 4 hours.

In the second mixing process, 5 to 90% by weight of the ethylene glycol (EG) 67 to 74 parts by weight and 47 to 75 parts by weight of isophthalic acid (IPA) are 230 to 240 ° C. in the primary ester reactant. In order to proceed with the second esterification process smoothly, the mixing process should be carried out at 230 ~ 240 ℃.

The second esterification step is a step of producing an ester reactant by adding an acid component of isophthalic acid and a diol component of ethylene glycol to produce an ester reactant. The mixture of the first mixing step is 240- under a pressure of 2.0-2.5 kgf / cm 2. It is a process of esterifying at 260 degreeC for 2 to 4 hours.

The polycondensation step is a step of polymerizing a low melting point polyester by polycondensing the ester reactant produced in the secondary esterification step to polymerize for 275 ~ 285 ℃, 40 ~ 100 minutes in a vacuum of 0.1 ~ 1 Torr or less It is a process.

Polycondensation in the production of a general polyester is prepared by polymerization for 3 hours or more, but the polycondensation process of the present invention controls the degree of polymerization by polymerization for 40 to 100 minutes.

If the polymerization time is less than 40 minutes, the degree of polymerization may be lowered to less than 60, and the yield may be lowered, which may be a problem for radioactivity. If the polymerization time exceeds 100 minutes, the degree of polymerization may increase and the melting point may be increased. May exceed 90.

The most preferable heavy fusion time of the process time of the above-mentioned heavy fusion process is 55-90 minutes.

Antimony trioxide (Sb ₂ O ₃ ), titanium oxide and dibutyl tin dilaurate may be used as the reaction catalyst in the polycondensation process, it will be preferable to use antimony trioxide (Sb ₂ O ₃ ).

It is also possible to add flame retardants for the thermal stability of the ester reactants. The flame retardant may be phosphoric acid or phosphorus based flame retardant. When using the above phosphoric acid it is preferable to use H ₃ PO ₄ , it is preferable to use a phosphate ester flame retardant when using a phosphorus flame retardant.

In addition, in the polycondensation process, TiO ₂ or SiO ₂ may be added as a quencher to prepare polyester from which light is removed.

Low-melting polyester of the present invention prepared by mixing terephthalic acid (TPA), isophthalic acid (IPA), ethylene glycol (EG), diethylene glycol (DEG) as described above The isophthalic acid, the action of diethylene glycol and a polymerization point of 60 ~ 90 can produce a soft copolymerization point (SP) of 90 ~ 110 ℃ block copolymer low melting point polyester.

The block copolymerized low melting point polyester according to the present invention is effective in providing a low melting point polyester having a lower melting point than conventional low melting point polyesters using isophthalic acid and diethylene glycol.

In addition, the block copolymer low-melting polyester of the present invention has the effect of lowering the use of expensive isophthalic acid using diethylene glycol to increase the economics of low-melting polyester.

In addition, the use of diethylene glycol is excellent in the dyeability, good absorbency block copolymer low melting point polyester can be used in various business fields.

In addition, the block copolymer low-melting polyester of the present invention is excellent in spinning properties, there is an effect that can be used as a binder fiber of various functions as a short fiber.

Hereinafter, although the Example of the method for manufacturing the block copolymerization low melting point polyester of this invention is shown, it is not limited.

Example

Terephthalic acid (TPA), ethylene glycol (EG) and diethylene glycol (DEG) were mixed at 220 ° C, and 240-260 ° C for 3 hours under 2.1-2.3 kgf / cm2 pressure. After primary esterification, ethylene glycol (EG) and isophthalic acid (IPA) were mixed with the ester reactant of the primary esterification at 230 ° C., and 240 ° C under pressure of 2.1 to 2.3 kgf / cm 2. Secondary esterification for 3 h at 260 < 0 > C.

The ester reactant of the secondary esterification was polymerized at 278-283 ° C. under a vacuum of 0.3 Torr or less to prepare a low melting polyester according to the present invention.

Examples 1 to 3 were polymerized with a polymerization time of 50 minutes, and Examples 4 to 6 were polymerized with a polymerization time of 90 minutes.

Example 7 was polymerized with a polymerization time of 30 minutes at the same composition ratio as in Example 2, and Example 8 was polymerized with a polymerization time of 140 minutes at the same composition ratio as in Example 4.

The composition ratios of the terephthalic acid, isophthalic acid, ethylene glycol, and diethylene glycol are shown in Table 1 below, and the amounts of the primary and secondary mixing processes of ethylene glycol were added at half the total amount.

division
Input amount (% by weight) TPA IPA EG DEG Example 1 43.3 25.0 30.6 1.2 Example 2 39.2 28.7 30.4 1.7 Example 3 35.8 31.9 30.4 1.9 Example 4 40.1 26.4 29.8 3.6 Example 5 40.7 25.7 29.7 3.9 Example 6 40.4 25.9 29.7 4.0 Example 7 39.2 28.7 30.4 1.7 Example 8 40.1 26.4 29.8 3.6

The softening point (SP), glass transition temperature (Tg), intrinsic viscosity, and polymerization degree of the block copolymer low melting point polyester according to the present invention prepared above are shown in Table 2.

In addition, the low melting point polyester of the above embodiments were melted and spun at 240˜275 ° C. to prepare a filament through a drawing process with a drawing ratio of 3.20 to evaluate radioactivity.

SP (℃) Tg (占 폚) IV Degree of polymerization Radioactive Example 1 86 62.8 0.463 68.1 ○ Example 2 99.9 63.2 0.556 62.8 ○ Example 3 102.6 67.1 0.595 69.2 ○ Example 4 99.0 58.8 0.637 71.5 ○ Example 5 102.0 51.3 0.676 74.7 ○ Example 6 102.0 55.0 0.696 80.4 ○ Example 7 84.3 49.3 0.409 52.6 △ Example 8 162.0 79.6 0.766 94.3 ○

As shown in Table 2, it can be seen that the softening point can be melted at a low temperature of 105 ° C. or less in the case of Examples 1 to 6 polymerized with a polymerization time of 50 minutes and 90 minutes.

In the case of Example 7 having a polymerization time of 30 minutes, it can be seen that it has a lower softening point, but there is a problem in use because of poor radioactivity. The block copolymer low-melting polyester of the present invention will most preferably have a polymerization time of 40 to 100 minutes.

The present invention described above is not limited to the above-described embodiments, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention. It will be obvious to him.

Claims (11)

After terephthalic acid (TPA), ethylene glycol (EG), and diethylene glycol (DEG) are first esterified, isophthalic acid (IPA) and ethylene glycol (ethylene glycol: EG) is added to form a secondary esterification reaction,
The terephthalic acid (TPA) 100 parts by weight of isophthalic acid (isophthalic acid (IPA) 47 to 75 parts by weight, ethylene glycol (ethylene glycol (EG) 67 ~ 74 parts by weight, diethylene glycol (DEG) 2.5 It is formed to ˜13 parts by weight, the ethylene glycol (ethylene glycol (EG) is 10 to 95% by weight of the addition amount is added in the first esterification reaction and 5 to 90% by weight is added in the second esterification reaction degree of polymerization Block copolymer low melting point polyester (Pn) is 60-90. delete delete The method of claim 1,
Block copolymerization low melting point polyester, characterized in that the softening point of the low melting point polyester is 90 ~ 110 ℃. The method of claim 1,
Block copolymer low melting point polyester, characterized in that the glass transition temperature (Tg) of the low-melting point polyester is 60 ~ 70 ℃. The method of claim 1,
Block copolymer low melting point polyester, characterized in that the intrinsic viscosity (IV) of the low melting point polyester is 0.55 ~ 0.75. In the method for producing a low melting polyester,
10 to 95% by weight of 67 to 74 parts by weight of ethylene glycol (EG) and 2.5 to 13 parts by weight of diethylene glycol (DEG) at 200 to 230 ° C. in 100 parts by weight of terephthalic acid (TPA) A first mixing step of mixing;
A primary esterification step of esterifying the mixture of the first mixing step at 240 to 260 ° C. for 2 to 4 hours at 2.0 to 2.5 kgf / cm 2 pressure;
A second mixture of 5 to 90% by weight of the ethylene glycol (EG) 67 to 74 parts by weight, and 47 to 75 parts by weight of isophthalic acid (IPA) at 230 to 240 ° C. fair;
A secondary esterification step of esterifying the mixture of the second mixing step at 240 to 260 ° C. for 2 to 4 hours at 2.0 to 2.5 kgf / cm 2 pressure; And
Block copolymerization, characterized in that it comprises a polycondensation step of polymerizing the secondary ester reactants in a vacuum at 0.1 ~ 1 Torr or less for 275 ~ 285 ℃, 40 ~ 100 minutes polymerization degree (Pn) to 60 ~ 90 Process for producing low melting polyester. delete The method of claim 7, wherein
Method for producing a block copolymer low melting point polyester using antimony trioxide (Sb ₂ O ₃ ) as the reaction catalyst in the polycondensation step. The method of claim 7, wherein
Process for producing a block copolymer low-melting polyester, characterized in that the addition of phosphoric acid or phosphorus flame retardant in the polycondensation step. The method of claim 7, wherein
A method for producing a block copolymer low melting polyester, characterized in that TiO ₂ or SiO ₂ is added as a matting agent in the polycondensation step.