KR101464597B1 - Heat-resistant Co-Polymerization Polyester and Preparing thereof - Google Patents

Abstract

The present invention relates to a heat-resistant copolymer polyester and a process for producing the same. More specifically, the present invention relates to a heat-resistant copolymer polyester and a process for producing the same. More particularly, the present invention relates to a heat- Ethylene Glycol), depolymerization of polybutylene terephthalate, esterification and polycondensation, and a process for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant co-

TECHNICAL FIELD The present invention relates to a heat-resistant copolymer polyester and a method of producing the same, and more particularly, to a heat-resistant copolymer polyester used in a polyester binder fiber and a method for producing the same.

And to provide a final polyester fiber, a film and a polyester resin for injection by producing a copolymerized polyester used for polyester binder fibers.

In preparing such polyester binder fibers, terephthalic acid, isophthalic acid and ethylene glycol are generally used. These products have a low heat resistance due to a high content of isophthalic acid, so that they are deformed at a temperature lower than the melting point at a high temperature There is a problem.

In order to compensate for this, 1,4-butanediol or the like is used so as to have heat-resistant properties. However, when 1,4-butanediol is generally used and terephthalic acid is used at a low cost, 1,4-butanediol, which is excessively charged to ensure reactivity, generates a large amount of tetrahydrofuran as a by-product in the esterification step, And a cause of lowering the 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.

Korean Patent Publication No. 2002-0064111 relates to a polyester-based binder fiber. When copolymerized polyester having a low melting point is condensed with dimethyl terephthalate and polyethylene glycol by polyethylene terephthalate (DMT), a first copolymerization component Of dimethyl adipate in an amount of 2-30 mol% based on the molar amount of the ester in the final copolymerized polyester and 1,4-butanediol as the second copolymerization component in an amount of 30-50 mol% The polyester-based binder fiber having such a low-melting-point component of the copolymerized polyester prevents an increase in toughness and a decrease in cutting strength of the final product, thereby providing an excellent tensile behavior in the production of a nonwoven fabric The strength of the nonwoven fabric hardly deteriorates even at a high temperature It is characterized.

Korean Patent Laid-Open Publication No. 2004-0078991 relates to a polyester-based binder fiber, which is a polyester-based binder fiber comprising a copolymerized polyester as a sheath component and a general polyester as a core component, wherein the copolymerized polyester is a copolymer of dimethyl terephthalic acid Or terephthalic acid, and an acidic component composed of dimethyladipic acid or adipic acid and a diol component composed of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. The polyester-based binder fiber of the above patent is characterized in that the binder component for low melting point bonding is high in the crystallinity of the binder component and does not cause deformation at a temperature lower than the melting point, and maintains the bonding strength even at a high temperature.

These prior art patents have a problem in that the use of 1,4-butanediol causes a large amount of tetrahydrofuran as a by-product in the esterification reaction step, resulting in deterioration of physical properties and reactivity. In addition, the 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 incurred. In the case of 1,4-butanediol application, Process improvement such as supplementation of transfer process equipment is additionally needed.

Accordingly, it has been desired to develop a technique for producing a copolymerized polyester which is easy to ensure physical properties and reactivity and which is economical in the simplest process in producing the copolymerized polyester.

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a polyester polymerization method and a depolymerization method in which a polymer containing a composition- And an excellent polyester fiber, a film and a polyester resin for injection molding.

It is also an object of the present invention to provide an economical copolymerized polyester resin which can be easily applied to a process used for producing a general polyethylene terephthalate (PET) resin, and which can be easily applied without modification of raw materials such as dimethyl terephthalate I have to.

In order to achieve the above object, the present invention provides a process for producing a polyester resin composition, which comprises reacting an acid component of terephthalic acid (TPA), isophthalic acid (IPA), adipic acid (AA) Ethylene Glycol: EG), and depolymerizing polybutylene terephthalate (PBT) to esterify and polycondensate the copolymer.

In the present invention, it is preferable that the acid component of the heat-resistant copolymerizable polyester contains 75 to 95 mol% of terephthalic acid, 1 to 15 mol% of isophthalic acid and 1 to 10 mol% of adipic acid, And the glycol is mixed in a molar ratio of 1.0: 1.0 to 2.0.

In the present invention, the mixing ratio of the polybutylene terephthalate to the polyethylene terephthalate composition composed of terephthalic acid, isophthalic acid, adipic acid and ethylene glycol is 1.0: 0.1 to 1.4, Wherein ethylene glycol added to polyethylene terephthalate is in a ratio of 1.0: 0.1 to 1.0: 1 by weight based on the weight of ethylene glycol, and the content of butanediol in the final copolymerized polyester resin is 50 mol% or less.

Also, the present invention relates to a process for producing a polyester resin composition, which comprises mixing acidic components terephthalic acid, isophthalic acid, adipic acid and ethylene glycol among diol components having 2 to 14 carbon atoms,

The heat-resistant copolymerizable polyester acid component is a mixture of terephthalic acid, isophthalic acid and adipic acid (AA) in an amount of 75 to 95 mol%, 1 to 15 mol% of isophthalic acid and 1 to 10 mol% Mixing and polymerizing at 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 polycondensation of the oligomer. The present invention also provides a method for producing a heat-resistant co-polyester.

In the present invention, the ratio of the polybutylene terephthalate to the polyethylene terephthalate composition composed of terephthalic acid, isophthalic acid, adipic acid and ethylene glycol is in a ratio of 1.0: 0.1 to 1.4, Wherein the ethylene glycol added for the depolymerization is a mixture of ethylene glycol to polybutylene terephthalate in a weight ratio of 1.0: 0.1 to 1.0 so that the content of butanediol in the final copolymerized polyester resin is 50 mol% or less. ≪ / RTI >

The present invention also provides a process for producing a 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 a heat-resistant copolymer polyester, which comprises stirring the mixture at a temperature of 230 to 285 ° C for 90 to 200 minutes at 40 to 100 rpm in the polycondensation step.

The process for producing a heat-resistant copolymerized polyester according to the present invention has the effect of providing a heat-resistant copolymerized polyester fiber, a film and an injection resin which are stable in physical properties and reactivity, minimize generation of tetrahydrofuran as a byproduct, and have a high reaction rate.

In addition, the process for producing a heat-resistant copolymerized polyester according to the present invention has an effect of providing an economical polyester resin by using a low-priced common terephthalic acid raw material.

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 copolymer resin produced by the method for producing a copolymerized polyester according to the present invention is heat resistant and can be practically used as a polyester fiber binder.

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 method of polymerizing ethylene glycol among acidic components terephthalic acid, isophthalic acid, adipic acid and a diol component having 2 to 14 carbon atoms, depolymerizing the polybutylene terephthalate, esterifying and polycondensing the polyethylene terephthalate copolymer polyester Is produced.

First, in the terephthalic acid, the acid component is mixed with 75 to 95 mol% of terephthalic acid, 1 to 15 mol% of isophthalic acid and 1 to 10 mol% of adipic acid with respect to the heat-resistant copolymerizable polyester acid component, and the terephthalic acid, isophthalic acid, The mixing ratio of ethylglycol to be mixed may be 1.0: 1.0 to 2.0.

The use of isophthalic acid and adipic acid is used for ensuring low melting point characteristics. In the case of isophthalic acid, the crystallinity is controlled effectively by the structure of the branched molecular chain not being straight line to terephthalic acid. Characteristics can be expressed. However, when it is less than 1 mol%, desired low melting point characteristics can not be secured, and when it is more than 15 mol%, the crystallinity of the copolyester is disturbed, which may cause a decrease in heat resistance. In addition, adipic acid can exhibit low melting point properties without interfering with crystallinity due to a straight structure, and it is possible to secure an improved adhesive strength when used as a binder. In addition, a copolymerized polyester product having excellent tear strength can be obtained by a flexible molecular chain.

In addition to the above isophthalic acid and adipic acid, sebacic acid, neopentyl glycol, 1,4-cyclohexanediol, and the like can be added to effectively impart low melting point characteristics.

When the amount of ethylene glycol used is small at the time of use of the terephthalic acid, the resulting copolymer polyester resin is insufficient in reactivity to form a copolymer polyester resin, or the strength, heat resistance, dimensional stability and moldability There is a problem that the product performance is insufficient when it is applied to a resin for injection molding other than the final fiber or film.

When the amount of ethylene glycol to be used is large, the resultant copolymerized polyester resin forms a large amount of diethylene glycol as a by-product to lower the physical properties of the copolymerized polyester resin, and also raises the production cost of the copolymerized polyester.

On the other hand, in the step of polymerizing terephthalic acid, isophthalic acid, adipic acid and ethylene glycol (EG), 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 composed of terephthalic acid, isophthalic acid, adipic acid, and ethylene glycol is mixed at a ratio of 1.0: 0.1 to 1.4 by weight of polybutylene terephthalate.

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 to the esterification reaction step of terephthalic acid and ethylene glycol, Ethylene glycol to polybutylene terephthalate may be mixed at a ratio of 1.0: 1.0 by weight or less, and the mixture may be mixed at 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 ethylene glycol Component to increase the polyethylene terephthalate component, so that the desired performance can not be exhibited. Also, the content of diethylene glycol as a byproduct increases and the amount of butanediol recovered after substitution with ethylene glycol increases due to excessive ethylene glycol, and ethylene glycol and ethylene glycol, which are degraded and recovered due to an increase in the content of byproduct tetrahydrofuran The content of butanediol is increased, resulting in improvement in recovery and purification process, and excessive cost.

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 is added to effect esterification reaction. When esterification reaction is carried out by depolymerization of polybutylene terephthalate instead of butanediol, generation of by-products is reduced, and polyethylene terephthalate having excellent heat resistance and stretchability, A copolymerized polyester resin can be produced.

It is also preferable that the content of butanediol in the final polyethyleneterephthalate copolymerized polyester resin subjected to the esterification reaction by depolymerization of the polybutylene terephthalate as described above is 50 mol% 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 subjected to an esterification step and a polycondensation step in which the acidic components terephthalic acid, isophthalic acid, adipic acid, and ethylene glycol among the diol components having 2 to 14 carbon atoms are depolymerized together with the polybutylene terephthalate in the polymerization step, .

The acid component is a mixture of terephthalic acid, isophthalic acid, and adipic acid. The acid component is mixed with terephthalic acid, isophthalic acid, and adipic acid in an amount of 75 to 95 mol% of terephthalic acid, 1 to 15 mol% of isophthalic acid and 1 to 10 mol% The mixing ratio of ethylene glycol to ethylene glycol is 1.0: 1.0 to 2.0, and polybutylene terephthalate and ethylene glycol are further mixed to depolymerize the mixture 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 ratio of the polybutylene terephthalate to be mixed with the polyester composition composed of terephthalic acid, isophthalic acid, adipic acid and ethylene glycol is mixed at a ratio of 1.0: 0.1 to 1.4 by weight of 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.

A mixture of terephthalic acid, isophthalic acid and adipic acid as a 250 ml acid component with a stirrer and a condenser was mixed at a molar ratio of 75: 15: 10, and the mixture of ethylene glycol with the mixture of terephthalic acid, isophthalic acid and adipic acid was 1 : 1.2, and then 1.0: 0.8 by weight of polybutylene terephthalate was added to ethylene glycol, and ethylene glycol was added to the mixture of ethylene glycol and terephthalic acid, isophthalic acid, adipic acid, and ethylene glycol. 0.25 weight ratio, and subjected to an esterification reaction in which the depolymerization was carried out in parallel at a temperature of 250 DEG C and 1140 Torr to obtain an ester-formed product. The resulting ester reaction product was transferred to a condensation polymerization reactor, and 100 parts by weight of the ester- 0.02 parts by weight of antimony and 0.005 parts by weight of tetrabutyl titanate were charged to a final pressure of 0.5 Torr. A polyethylene terephthalate copolyester resin compositions according to the present invention to Slowly, while the temperature is raised to 280 ℃ a forward reaction was stirred for 180 minutes under reduced pressure, and then stopped stirring, and the discharge 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 polybutylene terephthalate was mixed in the same manner as in Example 1 except that terephthalic acid, isophthalic acid, adipic acid, and polybutylene terephthalate as compared with ethylene glycol were mixed at a weight ratio of 1: 1 to perform the esterification reaction.

Example  3

The polybutylene terephthalate was mixed in the same manner as in Example 1 except that terephthalic acid, isophthalic acid, adipic acid, and polybutylene terephthalate in the ratio of ethylene glycol to ethylene glycol were mixed at a weight ratio of 1: 1.2.

Example  4

Polyethylene terephthalate copolymerized polyester resin composition was obtained in the same manner as in Example 1 except that terephthalic acid, isophthalic acid, adipic acid and diol components were added at a weight ratio of ethylene glycol of 1: 1.

Comparative Example  1 ~ Comparative Example  3

Were prepared in the same manner as in Examples 1 to 3, except that butanediol 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. Melting point

(Perkin Elmer, DMA-7; TMA mode) when there is no heat absorption peak, that is, when no melting point is present, by using a thermal differential scanning calorimeter (Perkin Elmer, DSC-7) The softening behavior was measured.

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.

4. Adhesion evaluation

The prepared binder fibers were cut into 6 mm fiber filaments and mixed into the material for wood heat insulating material. After the hot-air hot-air treatment at 90 to 100 ° C for 60 seconds, : Very excellent,?: Excellent,?: Fair, and X: poor.

5. Tactile evaluation

The internal experts were compared with each other by touching with their hand to compare sensory evaluation. The results were evaluated as?: Very excellent,?: Excellent,?: Fair, and?: Poor.

division By-product generation (wt%)
(Compared to runoff) Melting point
(° C) Reaction stability
Adhesiveness
touch
THF (Tetrahydrofuran) The recovered BD Example 1 8.9 wt% 1.1 wt% 168 Great ◎ ◎ Example 2 9.8 wt% 1.2 wt% 156 Great ◎ ◎ Example 3 7.8 wt% 2.0 wt% 158 Great ◎ ◎ Example 4 8.8 wt% 1.2 wt% 162 Great ◎ ◎ Comparative Example 1 23.6 wt% 11.7 wt% 172 lowness △ ○ Comparative Example 2 26.7 wt% 13.6 wt% 174 lowness △ △ Comparative Example 3 28.7 wt% 14.5 wt% 178 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 obvious to the person.

Claims (7)

delete delete delete An acidic component of terephthalic acid, isophthalic acid, adipic acid and a diol component having 2 to 14 carbon atoms is mixed with ethylene glycol,
The heat-resistant copolymerizable polyester acid component is a mixture of terephthalic acid, isophthalic acid and adipic acid (AA) in an amount of 75 to 95 mol%, 1 to 15 mol% of isophthalic acid and 1 to 10 mol% Mixing and polymerizing at 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 polycondensing the oligomer,
Wherein the ratio of the polybutylene terephthalate to the polyethylene terephthalate composition comprising terephthalic acid, isophthalic acid, adipic acid, and ethylene glycol is from 1.0: 0.1 to 1.4,
The ethylene glycol added for easy depolymerization is a mixture of ethylene glycol to polybutylene terephthalate in a weight ratio of 1.0: 0.1 to 1.0 so that the content of butanediol in the final copolymerized polyester resin is 50 mol% or less. Gt;
delete 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,
In the polycondensation step, the mixture is stirred at a temperature of 230 to 285 DEG C for 90 to 200 minutes at a temperature of 40 to 100 rpm.