KR101924773B1 - Manufacturing Method of Polyethylen Terephthalate Co-Polymerization Polyester - Google Patents

Abstract

The present invention relates to a polyethylene terephthalate copolymerized polyester and a method for producing the same. More specifically, the present invention relates to a polyethylene terephthalate copolymerized polyester obtained by polymerizing terephthalic acid (TPA) as an acid component and ethylene glycol as a diol component having 2 to 14 carbon atoms, And polyethylene terephthalate copolyester produced by esterification and polycondensation of polybutylene terephthalate in combination with depolymerization of polybutylene terephthalate, and a process for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyethylene terephthalate copolymerized polyester and a method for producing the same. BACKGROUND ART [0002] Polyethylene terephthalate co-

The present invention relates to a polyethylene terephthalate copolymerized polyester and a method for producing the same, and more particularly, to a polyethylene terephthalate copolymer polyester which can be spinnable and used for yarn and the like, and a method for producing the same.

Polyethylene terephthalate is a typical polyester resin and has excellent strength, heat resistance transparency, and chemical resistance, and has been used for various purposes such as fiber, bottle, and film. However, polyethylene terephthalate (PET) formed by polycondensation reaction of terephthalic acid and ethylene glycol , It is difficult to develop heat-resistant fiber and polyester film due to low crystallization speed and elongation property. Especially, there are many restrictions on the development of injection molding products.

Accordingly, in order to solve such problems, the prior art has solved the problem by applying a 1,4-butanediol raw material having a relatively high crystallization rate and stretching property to ethylene glycol in polymerization, or solving the problem by using a compounding of polyethylene terephthalate and polybutylene terephthalate As an Alloy product.

However, in the case of using the polymerization method, when 1,4-butanediol is generally used and terephthalic acid is used at a low cost, 1,4-butanediol is used excessively to ensure reactivity, and the by-product is reacted with tetrahydrofuran THF) is generated in a large amount, resulting in reduction of physical properties and reactivity. Also, ethylene glycol and 1,4-butanediol used together in the polycondensation step are recovered together, which makes it difficult to separate and purify, and a large amount of processing cost is generated. In addition, 1,4-butanediol application requires further process improvement such as storage of raw materials and by-products and supplementation of transfer process facilities.

Conventional technologies solve this problem by applying a small amount of 1,4-butanediol or dimethyl terephthalate, which is expensive but has a low occurrence of THF by-products relative to terephthalic acid.

Accordingly, it has been desired to develop a technique for producing copolymerized polyester using 1,4-butanediol, which is easy to secure physical properties and reactivity and can be economically produced by a simple process as much as possible.

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a method for producing a polyamide resin composition which is stable in physical properties and reactivity, and which is excellent in heat resistance and stretchability, in combination with a conventional polyester polymerization method and a depolymerization method in which a polymer containing a composition- Ester fiber, film and polyester resin for injection molding.

It is another object of the present invention to provide a process for producing a polyethylene terephthalate (PET) resin, which can be easily applied with little or no change, and which can be economically produced without modification of raw materials such as dimethyl terephthalate .

In order to achieve the above object, the present invention relates to a process for producing poly (ethylene terephthalate) by polymerizing terephthalic acid (TPA) as an acid component and ethylene glycol as a diol component having 2 to 14 carbon atoms, depolymerizing polybutylene terephthalate and esterifying and polycondensing And a polyethylene terephthalate copolymerized polyester.

The present invention also provides a polyethylene terephthalate copolymer polyester characterized in that the ratio of ethylene glycol to terephthalic acid (TPA) is in a range of 1.0: 1.0 to 2.0: 1.

In the present invention, the ratio of the polybutylene terephthalate to the polyethylene terephthalate composition composed of terephthalic acid and ethylene glycol is in the range of 1.0: 0.1 to 1.4 by weight and the ethylene glycol Wherein the content of butane diol in the final polyethylene terephthalate copolymerized polyester resin is 50% or less by mixing ethylene glycol at a ratio of 1.0: 0.1 to 1.0 with respect to polybutylene terephthalate.

The present invention also relates to a method for producing a polyester resin composition, which comprises polymerizing terephthalic acid (TPA) as an acid component and ethylene glycol (ethylene glycol) of a diol component having 2 to 14 carbon atoms in a molar ratio of 1.0: An esterification step in which the polymerized material is subjected to polybutylene terephthalate depolymerization to produce an oligomer; And polycondensing the oligomer. The present invention also provides a method for producing the polyethylene terephthalate copolymer polyester.

In the present invention, the ratio of the polybutylene terephthalate to the polyethylene terephthalate composition composed of terephthalic acid and ethylene glycol is in the range of 1.0: 0.1 to 1.4 by weight and the ethylene glycol Wherein the content of butane diol in the final polyethylene terephthalate copolymerized polyester resin is 50% or less by mixing ethylene glycol to polybutylene terephthalate in a ratio of 1.0: 0.1 to 1.0 .

The present invention also provides a process for producing polyethylene terephthalate copolyester, wherein the esterification is carried out at a temperature of 200 to 250 ° C for 150 to 300 minutes at a rate of 40 to 80 rpm.

The present invention also provides a method for producing polyethylene terephthalate copolyester, wherein the polycondensation step is carried out at a temperature of 230 to 285 DEG C for 90 to 200 minutes at 40 to 100 rpm.

The present invention also provides a polyester fiber produced using the polyethylene terephthalate copolymer polyester or the method for producing the polyethylene terephthalate copolymer polyester.

The method for producing a copolymerized polyester according to the present invention has the effect of providing a polyethylene terephthalate copolymerized polyester resin which is stable in physical properties and reactivity, minimizes generation of THF as a byproduct and has a high reaction rate.

In addition, the method for producing a copolymerized polyester according to the present invention has an effect of providing an economical polyester resin by using a common terephthalic acid raw material which is inexpensive.

In addition, the process for producing the copolyester according to the present invention minimizes the process change even when the raw material is changed or added, and thus a simple and economical process can be applied.

In addition, the polyethylene terephthalate copolymer resin produced by the method for producing a copolymerized polyester according to the present invention has excellent heat resistance and stretching properties, and can be practically used for extrusion of high performance fibers and films.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring 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 relates to a process for producing a polyester resin composition, which comprises polymerizing terephthalic acid (TPA) as an acid component and ethylene glycol as a diol component having 2 to 14 carbon atoms, depolymerizing the polybutylene terephthalate, esterifying and polycondensing the polyethylene terephthalate Thereby producing a copolymerized polyester.

First, the terephthalic acid and ethylene glycol are polymerized, and the polymerization ratio of ethylene glycol to terephthalic acid may be 1.0: 1.0 to 2.0.

When the use amount of the terephthalic acid is small at the time of use of the terephthalic acid, the resulting copolymerized polyester resin is insufficient in reactivity to form a copolymer polyester resin, or the strength, heat resistance, dimensional stability and molding processability of the formed copolymer polyester resin There is a problem in that the product performance is insufficient when the resin is used as a resin for extrusion of a fiber or a film.

On the contrary, when the amount of ethylene glycol to be used is large, the copolymerized polyester resin obtained forms a large amount of diethylene glycol as a by-product to lower the physical properties of the copolymerized polyester resin, and the production cost of the copolymerized polyester increases .

On the other hand, in the step of polymerizing terephthalic acid and ethylene glycol, depolymerization of the polybutylene terephthalate may be performed in parallel to cause an esterification reaction.

It is preferable that the ratio of the polybutylene terephthalate to the polyester composition comprising terephthalic acid and ethylene glycol is in the range of 1.0: 0.1 to 1.4 by weight.

The polyethylene terephthalate copolymerized polyester resin having a polybutylene terephthalate content of less than 0.1 is insufficient in heat resistance and elongation properties due to insufficient fiber and film properties during injection, .

If the content of polybutylene terephthalate is more than 1.4 wt%, the polybutylene terephthalate is more likely to be used than polyethylene terephthalate for use as a polyethylene terephthalate copolymer polyester.

On the other hand, when the polybutylene terephthalate is mixed, ethylene glycol may be added in order to smoothly depolymerize polybutylene terephthalate in the esterification reaction step between terephthalic acid and ethylene glycol. The content of ethylene glycol added is, Ethylene glycol to polybutylene terephthalate may be mixed in a ratio of 1.0: 1.0 by weight or less, preferably in a ratio of 1.0: 0.1 to 1.0 by weight.

In the case of ethylene glycol added at depolymerization, when the ratio by weight of polybutylene terephthalate is more than 1.0, the excess of ethylene glycol increases the depolymerization rate of polybutylene terephthalate, but when the butanediol component of polybutylene terephthalate is replaced by ethyleneglycol Component to increase the polyethylene terephthalate component, so that the desired performance can not be exhibited. In addition, the content of diethylene glycol as a byproduct increases due to an excessive amount of ethylene glycol, the content of butanediol recovered after substitution with ethylene glycol increases, the content of tetrahydrofuran as a byproduct increases, and the content of ethylene glycol and butanediol The recovery and purification process are improved and excessive costs are incurred.

In the present invention, depolymerization of the polybutylene terephthalate to esterification reaction results in remarkable reduction of the formation of by-products, and a polyethylene terephthalate copolymerized polyester resin having excellent heat resistance and stretching properties can be produced. Conventionally, butanediol (BD) has been added to esterify the esterification reaction of depolymerization of polybutylene terephthalate instead of butanediol (BD), which reduces the generation of by-products during the process, and has excellent heat resistance and stretching properties. A polyethylene terephthalate copolymerized polyester resin having excellent properties can be produced.

Also, it is preferable that the content of butanediol of the final polyethylene terephthalate copolymerized polyester resin subjected to the esterification reaction by polycondensation of the polybutylene terephthalate as described above is 50% or less.

The polyethylene terephthalate copolymerized polyester according to the present invention can produce a polyethylene terephthalate copolymerized polyester resin which is easy and economical without much modification of the process in the process of producing a conventional polyethylene terephthalate polyester resin. Also, since the reaction rate with other raw materials is high, there is an advantage that there is little restriction on the added raw materials.

As for the method of producing the polyester according to the present invention,

The polyester fiber composition is prepared by depolymerizing ethylene glycol (Ethylene Glycol) among the acidic terephthalic acid and the diol component having 2 to 14 carbon atoms together with the polybutylene terephthalate, followed by esterification and polycondensation.

The ratio of the ethylene glycol to the terephthalic acid (TPA), which is an acid component, is in a range of 1.0: 1.0 to 2.0 molar ratio, and then polybutylene terephthalate and ethylene glycol are further mixed and depolymerized to effect an esterification reaction. Polyethylene terephthalate copolymerized polyester resin having excellent reaction stability due to the addition of polybutylene terephthalate and having a low yield of by-products and a high reaction rate can be produced.

The mixing ratio of the polybutylene terephthalate to the polyester composition composed of terephthalic acid and ethylene glycol is in the range of 1.0: 0.1 to 1.4 by weight based on the polybutylene terephthalate.

The ethylene glycol added in the esterification reaction step is preferably 1.0: 0.1 to 1.0, and more preferably 1.0: 0.1 to 1.0, of ethylene glycol relative to polybutylene terephthalate.

Wherein the esterification reaction is carried out at a temperature of 200 to 250 DEG C for 150 to 300 minutes under stirring at a speed of 40 to 80 rpm to effect an esterification reaction to produce an oligomer.

The oligomer prepared through the esterification reaction is polycondensed at 230 to 285 DEG C for 90 to 200 minutes at 40 to 100 rpm to prepare a polyethylene terephthalate copolymerized polyester resin.

In the polycondensation process, the oligomer produced by the ester process is polycondensed at 230 to 285 DEG C for 90 to 200 minutes at 40 to 100 rpm to produce a polyester.

As the catalyst used in the polycondensation reaction in the present invention, antimony compounds and titanium compounds can be used. In order to suppress color discoloration at a high temperature, phosphorus compounds can be used. Examples of the antimony compounds include antimony trioxide, antimony tetraoxide, Antimony trioxide, antimony benzoate, antimony tristearate and the like can be used as the antimony antimony such as antimony trioxide, antimony trioxide, antimony trioxide, antimony trichloride, antimony trichloride and the like. Antimony trioxide, antimony triacetate and the like show excellent effects and it is preferable to use them. The amount of the antimony triacetate to be used is preferably 100 to 600 ppm based on the total weight of the polymer obtained after the polymerization.

The titanium compound includes titanium such as butyl titanate, isopropyl titanate, tetrabutyl titanate, and tetrafluoro titanium, and it is preferable to use at least one of them, and it is preferable to use tetrabutyl titanate . The amount of the titanium compound used is preferably 10 to 100 ppm based on the total weight of the polymer obtained after the polymerization.

As the phosphorus compound, phosphoric acid, trimethylphosphoric acid monomethylphosphoric acid, phosphoric acid such as tributylphosphoric acid, and derivatives thereof are preferably used. Of these, trimethylphosphoric acid, triethylphosphoric acid or triphenylphosphoric acid is preferable because of its excellent effect. The amount of the compound to be used is preferably 100 to 500 ppm based on the total weight of the polymer obtained after the polymerization.

The polyethylene terephthalate copolymerized polyester resin prepared as described above is preferably processed at a temperature of 170 to 300 ° C using a compounder equipped with a twin extruder to be used as a resin for injection molding of fiber and film, It can be practically used as electric / electronic products.

Hereinafter, examples of the method for producing the polyester of the present invention are shown, but the present invention is not limited thereto.

Example  One

First, the production of polyester is as follows.

250 ml of an acid component with a stirrer and a condenser was added thereto so that the weight ratio of ethylene glycol to terephthalic acid and diol component was 1: 1.2. Then, 1.0: 0.7 by weight of polybutylene terephthalate to ethylene glycol and ethylene glycol The ethylene glycol was mixed with the polybutylene terephthalate at a weight ratio of 1.0: 0.25, and esterification reaction was carried out at 250 DEG C under depolarization under a pressure of 1140 Torr to obtain an ester-formed product. 0.02 part by weight of antimony trioxide and 0.005 part by weight of tetrabutyl titanate were added to 100 parts by weight of the ester reactant, and the mixture was heated to 280 DEG C while being gradually reduced in pressure to a final pressure of 0.5 Torr, followed by stirring for 180 minutes Stirring was stopped and discharged to obtain polyethylene < RTI ID = 0.0 > Les phthalate copolymer polyester resin composition was obtained.

The reaction rate of the esterification reaction was measured, and the amount of the byproducts generated was compared with the amount of the effluent.

Example  2

The preparation of polybutylene terephthalate was carried out in the same manner as in Example 1 except that terephthalic acid and polybutylene terephthalate were mixed with ethylene glycol and esterified at a weight ratio of 1: 1.

Example  3

The preparation of polybutylene terephthalate was carried out in the same manner as in Example 1 except that terephthalic acid and polybutylene terephthalate were mixed in an amount of 1: 1.2 by weight based on ethylene glycol and esterified.

Example  4 ~ Example  6

The polyethylene terephthalate copolymerized polyester resin composition was prepared in the same manner as in Examples 1 to 3 except that the weight ratio of ethylene glycol to terephthalic acid and the diol component was 1: 1.

Comparative Example  1 ~ Comparative Example  3

Were prepared in the same manner as in Examples 1 to 3, except that butanediol (BD) was added in the same amount as polybutylene terephthalate without depolymerization of polybutylene terephthalate.

The byproducts and reaction rates of the fiber compositions prepared in the above Examples and Comparative Examples were compared, and the comparative data are shown in Table 1 below.

How to measure

1. Measurement of recovered 1,4-butanediol: Polybutylene terephthalate used in depolymerization In the esterification reaction step, 1,4-butanediol is produced by substituting ethylene glycol in the polybutylene terephthalate structure. Ethylene glycol And the weight of 1,4-butanediol produced by substitution.

2. Measurement of esterification reaction rate: Water (H2O) is produced as an effluent in the esterification reaction between the raw material of an acid component such as terephthalic acid and ethylene glycol and the diol component raw material of an alcohol system. Therefore, the esterification reaction rate can be obtained from "[theoretical effluent (water)] / [actual effluent (water)] * 100".

3. Reaction stability: The reaction stability is confirmed by three phenomena of THF content, effluent water content and bubbling phenomenon during reaction. When the above three phenomena are high, the stability of the reaction is low, and conversely, when the three phenomena are low, the reaction stability is excellent.

division By-product generation (wt%)
(Compared to runoff) Esterification reaction rate (%)

Reaction stability THF (Tetrahydrofuran) The recovered BD Example 1 8.3 wt% 1.8 wt% 96% Great Example 2 9.2 wt% 1.7 wt% 98% Great Example 3 6.9 wt% 1.5 wt% 92% Great Example 4 8.1 wt% 1.8 wt% 95% Great Example 5 8.4 wt% 1.6 wt% 95% Great Example 6 7.5 wt% 1.5 wt% 93% Great Comparative Example 1 22.4 wt% 12.1 wt% 82% lowness Comparative Example 2 24.6 wt% 13.8 wt% 85% lowness Comparative Example 3 23.2 wt% 10.6 wt% 83% lowness

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be clear to those who are.

Claims (8)

(Terephthalic acid, TPA), an ethylene glycol (ethylene glycol) among diol components having 2 to 14 carbon atoms, and depolymerizing polybutylene terephthalate to esterify and polycondensate the polybutylene terephthalate,
The mixing ratio of the polybutylene terephthalate to the polyethylene terephthalate composition composed of terephthalic acid and ethylene glycol is 1.0: 0.1 to 1.4 in weight ratio of polybutylene terephthalate, and ethylene glycol added for easy depolymerization is polybutylene Wherein ethylene glycol relative to terephthalate is mixed in a ratio of 1.0: 0.1 to 1.0: 1, and the content of butanediol in the final polyethylene terephthalate copolymerized polyester resin is 50% by weight or less.
The method according to claim 1,
Wherein the ratio of ethylene glycol to terephthalic acid (TPA) is 1.0: 1.0 to 2.0: 1.
delete Polymerizing an acidic component of terephthalic acid (TPA) and ethylene glycol (ethylene glycol) among the diol components having 2 to 14 carbon atoms in a molar ratio of 1.0: 1.0 to 2.0;
An esterification step in which the polymerized material is subjected to polybutylene terephthalate depolymerization to produce an oligomer; And
And polycondensing the oligomer. The method of producing a polyethylene terephthalate copolymerized polyester according to claim 1,
5. The method of claim 4,
The mixing ratio of the polybutylene terephthalate to the polyethylene terephthalate composition composed of terephthalic acid and ethylene glycol is 1.0: 0.1 to 1.4 in weight ratio of polybutylene terephthalate, and ethylene glycol added for easy depolymerization is polybutylene Wherein ethylene glycol to terephthalate is mixed at a ratio of 1.0: 0.1 to 1.0 by weight, and the content of butanediol in the final polyethylene terephthalate copolymerized polyester resin is 50% by weight or less.
5. The method of claim 4,
Wherein the esterification step is carried out at a temperature of 200 to 250 DEG C for 150 to 300 minutes at a rate of 40 to 80 rpm.
5. The method of claim 4,
Wherein the polycondensation step is carried out at a temperature of 230 to 285 DEG C for 90 to 200 minutes at a temperature of 40 to 100 rpm.
A polyethylene terephthalate copolymerized polyester according to any one of claims 1 to 3,
Or a polyester fiber produced by using the polyethylene terephthalate copolymer polyester produced by any one of claims 4 to 7.