KR101493391B1 - Catalyst composition for polyester polymerization, and method for preparing polyester using the same - Google Patents

Abstract

The present invention relates to a catalyst composition for producing polyester, and a process for producing polyester using the same. More particularly, the present invention relates to a catalyst composition comprising a composite metal oxide and a germanium (Ge) compound in which three metals of titanium (Ti), aluminum (Al), and magnesium (Mg) Thereby producing a polyester. The catalyst composition of the present invention is very useful as an environmentally friendly next generation mixed composition catalyst which can be polyester-polymerized even by using a small amount of a composite metal oxide and a germanium-based compound. In addition, it is possible to obtain a resin having a short reaction time, high intrinsic viscosity and good color (L, a, b) values in polyester polymerization, and thus can be usefully applied to large-scale commercial production.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst composition for polyester polymerization, and a method for preparing the same,

The present invention relates to a catalyst composition for producing polyester, and a process for producing polyester using the same. More particularly, the present invention relates to a catalyst composition for the production of a polyester comprising a composite metal oxide and a germanium compound containing three kinds of metals such as titanium, aluminum and magnesium, and oxygen, and a process for producing the polyester using the same.

Polyester has excellent mechanical and chemical properties and is widely used in applications such as beverage filling containers and medical applications, packaging materials, sheets, films, and automobile molded products . Typical examples include polyethylene terephthalate, which is widely used for excellent physical and chemical properties and dimensional stability, and is mainly made of antimony (Sb) based catalyst.

However, in the case of products made of antimony catalysts, it is necessary to use a large amount of antimony in the polymerization process. Since the metal itself is toxic, antimony is released when it is used for a long period of time, (Anal. Bioanal. Chem. 2006, 385, 821). Recent research has shown that large amounts of antimony are produced in drinking water bottles and food packaging materials using antimony catalysts (Environ. Sci. Technol., 2007, 41, 1560). Thus, in some developed countries, the use of antimony catalysts is being regulated or prohibited, and environmentally friendly catalysts are being developed to replace toxic metals such as antimony.

There have been proposed methods using a titanium metal compound and a germanium compound, which are known to be eco-friendly substances which are less toxic in vivo and which can replace toxic antimony catalysts, as a polyester polymerization catalyst.

For example, U.S. Patent Publication No. 2010-0184916 discloses a polyester manufacturing method using a representative eco-friendly metal (Ti, Titanium).

However, the titanium compound catalyst itself has a high activity, but in the case of titanium metal, excessive use leads to formation of a yellow colored polymer by binding with organic matter at high temperature and high pressure. In addition, when a small amount of titanium metal is used, formation of a yellow colored polymer can be prevented, but the viscosity is not significantly increased in solid phase polymerization. Due to such disadvantages, although the titanium-based catalyst is substantially excellent in the metal self-activity, there is a problem that it is difficult to actually apply it to commercialization.

For example, U.S. Patent No. 6,365,659 discloses the production of polyester using a mixture of environmentally friendly metals (germanium, aluminum, zirconium).

However, although the germanium compound catalyst itself has a high activity, it is difficult to use the germanium catalyst due to the high price of the catalyst when the amount of the germanium catalyst used is large. Due to such disadvantages, although the germanium-based catalyst is substantially excellent in the metal self-activity, there is a problem in commercial application.

For example, U.S. Patent No. 7,153,811 discloses a polyester manufacturing method using a mixture of germanium and aluminum or germanium and molybdenum.

However, since aluminum activity is not high, a lot of germanium should be added. Due to such disadvantages, a catalyst composition using germanium and aluminum or a mixture of germanium and molybdenum has limitations that are difficult to be practically applied to commercialization.

European Patent No. 0591488, for example, discloses a polyester manufacturing method using a mixture of germanium and lithium.

However, the catalytic activity of the germanium and lithium mixed catalyst composition is excellent, but it is difficult to actually apply the germanium necessary for the production of the polyester by commercializing it.

For example, U.S. Patent No. 5,417,908 discloses a polyester manufacturing method using a mixture of germanium and manganese.

However, the catalytic activity of the germanium and manganese mixed catalyst composition is excellent, but it is difficult to actually apply the germanium to the commercialization by excessively injecting the germanium necessary for the production of the polyester.

U.S. Patent No. 6,160,085 discloses that catalyst components adversely affect the physical properties of the polyester.

Therefore, it is still required to develop a catalyst in which the catalyst activity is maintained during the reaction with water generated in the polycondensation process, and to develop a catalyst having a high activity while preventing the yellowing and pyrolysis, .

In order to solve the above problems, an object of the present invention is to provide an eco-friendly, polyester-based catalyst capable of replacing an antimony-based catalyst exhibiting a high catalytic activity, easy synthesis, And to provide a catalyst composition which can be used for the catalyst.

It is also an object of the present invention to provide a process for producing a polyester using the catalyst composition.

In order to achieve the above object, the present invention provides a catalyst composition for polyester polymerization comprising a composite metal oxide containing titanium (Ti), aluminum (Al), magnesium (Mg) and oxygen (O) to provide.

The present invention also relates to a composite metal oxide comprising titanium (Ti), aluminum (Al), magnesium (Mg) and oxygen (O); And a germanium (Ge) based compound in the presence of a catalyst composition comprising a dicarboxylic acid component and a glycol component.

The catalyst composition of the present invention is very useful as a next-generation catalyst that can be polyester-polymerized even by using a small amount of a titanium-based compound.

Also, when polyester is produced using the catalyst composition of the present invention, the germanium compound increases the catalytic activity and increases the viscosity in the liquid phase and solid phase polymerization. And it can be usefully applied to commercial production with the reduction of reaction time, high intrinsic viscosity and improvement of color value (L, b).

In addition, in the case of a polyester resin using the polyester obtained by the above-mentioned method for producing polyester, particularly polyethylene terephthalate, excellent physical properties such as transparency, viscosity, brightness, and chromaticity are excellent and can be applied to beverage and food- have.

The catalyst composition of the present invention includes a composite metal oxide and a germanium (Ge) based compound including titanium (Ti), aluminum (Al), magnesium (Mg), and oxygen (O).

The method for producing a polyester according to the present invention is also characterized by using a composite metal oxide comprising titanium (Ti), aluminum (Al), magnesium (Mg) and oxygen (O); And a germanium (Ge) based compound, in the presence of a catalyst component comprising a dicarboxylic acid component and a glycol component.

Hereinafter, the catalyst composition of the present invention and the method for producing the polyester will be described in more detail.

Catalyst composition

The catalyst composition of the present invention is a composite metal oxide comprising titanium (Ti), aluminum (Al), magnesium (Mg) and oxygen (O); And germanium (Ge) compounds.

The catalyst composition of the present invention can be used in the polymerization of a polyester, and in particular, can be used as a catalyst in the production of polyethylene terephthalate.

Composite metal oxides that can be used as catalysts for polyester polymerization or co-precipitates thereof have been proposed in U.S. Patent No. 5,684,116.

However, the known titanium and silicon or complex metal oxides of titanium and zirconium do not exhibit sufficient activity for application to the polymerization of actual polyester. In addition, in the polyester polymerization process, it is necessary to use a phosphorus compound containing phosphorus (P) serving as a heat stabilizer and an antioxidant. However, the conventional composite metal oxide catalyst has low activity when used together with phosphorus, Which is a limitation of the condensation polymerization. Therefore, there is a limit to the application because of the small amount of phosphorus, which is likely to cause thermal decomposition, oxidative decomposition, and yellowing of the polyester during melt molding.

According to one embodiment of the present invention, the composite metal oxide included in the catalyst composition of the present invention is a composite metal oxide structure in which titanium, aluminum, and magnesium react with water in the course of its production to form an oxidation bond with oxygen Lt; / RTI >

Further, the composite metal oxide contained in the catalyst composition of the present invention can be produced by reacting a titanium compound represented by the following formula (1), an aluminum compound represented by the following formula (2), and a magnesium compound represented by the following formula (3) Lt; RTI ID = 0.0 > coprecipitate < / RTI >

[Chemical Formula 1]

Ti (OR ¹⁾ ₄

(2)

Al (OR ²⁾ ₃

(3)

Mg (OR ³⁾ ₂

Wherein R ¹ , R ² and R ³ are the same or different and each is a hydrogen atom or a C ₁ to C ₂₀ alkyl group (Alkyl), a C ₂ to C ₂₀ alkenyl group (Alkenyl A C ₃ to C ₂₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, a C ₁ to C ₂₀ alkylsilyl group, a C ₇ to C ₂₀ arylalkyl group, or C ₇ - alkyl means an aryl group (alkylaryl) of C _20.

According to an embodiment of the present invention, each of R ¹ , R ² and R ³ may be the same or different from each other and may be a hydrogen atom or a C ₁ -C ₄ alkyl group.

According to one embodiment of the present invention, the amount of the titanium compound, the aluminum compound, and the magnesium compound to be used is not particularly limited, but may be, for example, about 10: 0.5: 0.5 to about 1: 1: 1.

As described above, the composite metal oxide catalyst contained in the catalyst composition of the present invention can be produced by a relatively simple method, and is stable in moisture and easy to store. Unlike the antimony-based catalyst, the metal complex oxide has a relatively low metal self-toxicity and is unlikely to cause human and environmental problems.

The catalyst composition of the present invention comprises a germanium-based compound.

The germanium compound refers to a compound containing germanium (Ge), and examples thereof include germanium oxide, germanium methoxide, germanium ethoxide, germanium isopropoxide, isopropoxide, germanium selenide, germanium sulfide, germanium iodide, germanium nitride, germanium bromide, germanium chloride, tetramethyl germanium, Germanium, tetramethyl germanium, tetraethyl germanium, germanium metal, or mixtures thereof, but the present invention is not limited thereto.

According to the present invention, the polyester polycondensation activity can be further improved by including the germanium compound.

The catalyst composition of the present invention may further comprise a phosphorus compound.

The phosphorus compound refers to a compound containing phosphorus (P), and includes, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphoric acid, , Phenylphosphine, 2-carboxyethylphenyl phosphinic acid, or a mixture thereof, but the present invention is not limited thereto.

The phosphorus compound serves to prevent the yellowing of the polyester which is formed by reducing pyrolysis during the polymerization reaction of the polyester and inhibiting the formation of a colorbody.

Unlike the antimony catalyst, the catalyst composition of the present invention has a relatively low metal toxicity and shows a low possibility of causing human and environmental problems, and exhibits high activity within a short reaction time even in a small amount. Also, the polyester produced using the catalyst composition of the present invention is excellent in physical properties such as viscosity and color. Therefore, it can be applied to commercial use in the mass production of polyester, in particular, in the production of polyethylene terephthalate.

Method for producing polyester

The method for producing a polyester according to the present invention is characterized by comprising a composite metal oxide comprising titanium (Ti), aluminum (Al), magnesium (Mg) and oxygen (O); And a germanium (Ge) -based compound in the presence of a catalyst composition comprising a dicarboxylic acid component and a glycol component.

The step of polymerizing the polyester may be carried out by liquid phase polymerization or solid phase polymerization.

According to an embodiment of the present invention, the step of polymerizing the dicarboxylic acid component and the glycol component includes a step of esterifying the dicarboxylic acid component and the glycol component, and polycondensation of the reaction product of the esterification reaction .

More specifically, first, the dicarboxylic acid component and the glycol component are esterified.

According to one embodiment of the present invention, the dicarboxylic acid component includes, for example, terephthalic acid, oxalic acid, malonic acid, azelaic acid, It is also possible to use an organic acid such as fumaric acid, pimelic acid, suberic acid, isophthalic acid, dodecane dicarboxylic acid, naphthalene dicarboxylic acid acid, biphenyldicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 2,6-naphthalene dicarboxylic acid, acid, 1,2-Norbornane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid (Dicar but are not limited to, cyclohexane dicarboxylic acid, cyclohexane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, Dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, or 2- Sodium sulfoterephthalic acid, and the like. However, the present invention is not limited thereto. Other dicarboxylic acids not exemplified in the above may be used as long as they do not impair the object of the present invention. According to one embodiment of the present invention, terephthalic acid may be used as the dicarboxylic acid component.

According to one embodiment of the present invention, the glycol component includes, for example, ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, Butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, Propylene glycol, diethylene glycol, triethylene glycol, 1,2-cyclohexane diol, 1,3-cyclohexane diol, 1,3-cyclohexane diol, diol, 1,4-cyclohexane diol, propane diol, 1,6-hexanediol, neopentyl glycol, tetramethylcyclobutane diol, , 1,4-cyclohexane diethanol, 1,10-decamethylene glycol, 1,12-dodecane But are not limited to, Dodecane diol, Polyoxyethylene glycol, Polyoxymethylene glycol, Polyoxytetramethylene glycol, Glycerol, and the like. Other glycols can be used within the scope of not impairing the object of the present invention. Preferably, ethylene glycol may be used as the glycol component.

According to one embodiment of the present invention, the step of esterifying the dicarboxylic acid component and the glycol component is carried out at a temperature of about 200 to about 300 캜, preferably about 230 to about 280 캜, at a temperature of about 1 to about 6 Hour, preferably about 2 to about 5 hours.

Next, the reaction product of the esterification reaction is polycondensed.

Polycondensation of the reactants of the esterification reaction is carried out at a temperature of from about 200 to about 300 DEG C, preferably from about 260 DEG C to about 290 DEG C and from about 0.1 to about 1 torr for from about 1 to about 3 hours, Can be carried out by reacting for about 1 hour 30 minutes to about 2 hours 30 minutes. Therefore, since the polycondensation time can be remarkably shortened compared with the case of using the conventional catalyst, the productivity is improved.

In the method for producing polyester of the present invention, a detailed description of the composite metal oxide and the germanium (Ge) compound including titanium (Ti), aluminum (Al), magnesium (Mg) and oxygen (O) same.

In the method for producing a polyester of the present invention, the composite metal oxide and the germanium-based compound can be introduced at any stage of the polyester polymerization. For example, according to one embodiment of the present invention, the composite metal oxide, germanium-based compound may be added to the esterification reaction step in the form of a composition containing both of the above two components.

In the method for producing polyester of the present invention, in the case of the composite metal compound, about 15 ppm or less, for example, about 5 ppm or less, based on the titanium element content in the composite metal compound, About 15 ppm, preferably about 8 to about 10 ppm, can be used. Or about 20 ppm or less, for example, about 5 to about 20 ppm, preferably about 8 to about 10 ppm, based on the total content of the titanium, aluminum, and magnesium elements contained in the composite metal compound may be used.

The titanium-based catalyst compound used in the conventional polyester production method generally exhibits a decrease in activity when the polycondensation is attempted using at least 15 ppm or more based on the content of the titanium element based on the final polyester, There is a problem that a polyester having a low and high viscosity is produced. In addition, when the titanium content is high, the color of the polyester product may be shifted to the yellow side, which may be inadequate for commercial use, and the catalyst activity is excessively high, so that it is difficult to stably control various physical properties including the byproduct content in the polymerization process.

In the process for producing the polyester of the present invention, the composite metal oxide has a high catalytic activity at a low content by using not more than about 15 ppm based on the titanium element content contained in the composite metal compound with respect to the weight of the final polyester And the deterioration of the physical properties such as yellowing can be reduced.

The germanium-based compound acts directly on the esterification reaction and the polycondensation as a composite metal oxide used as a catalyst in polyester polymerization. More specifically, according to the present invention, a polycondensation reaction can be performed even when a small amount of the composite metal oxide catalyst is used by using a germanium-based compound together with a composite metal oxide catalyst. It is also possible to obtain a product having a high viscosity with a short reaction time. Therefore, since the use amount of titanium can be reduced, the yellowing phenomenon of the polyester resin produced after the polymerization is low, and the low viscosity can be increased, which is industrially advantageous. In addition, the mixed metal oxide catalyst and germanium compound mixed composition does not react with other additives, and thus has an additional advantage that it can be mixed at any stage, such as other materials.

In the method for producing a polyester of the present invention, in the case of the germanium compound, the content of the germanium compound is preferably about 7 to about 28 ppm based on the content of the germanium (Ge) element contained in the germanium compound, , About 10 to about 20 ppm, and more preferably about 12 to about 16 ppm. Addition of the germanium compound in the above range is preferable from the viewpoint of producing a polyester of excellent product by decreasing the viscosity increase and the polycondensation time in the polyester polymerization. As the content of the germanium compound increases, the reaction time and viscosity increase effect may be improved. However, when the amount of germanium compound is excessively used, the cost is increased, which is not preferable.

According to one embodiment of the present invention, the polyester can be further polymerized by further containing a phosphorus compound.

The phosphorus compound refers to a compound containing phosphorus (P), and includes, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphoric acid, , Phenylphosphine, 2-carboxyethylphenyl phosphinic acid, or a mixture thereof, but the present invention is not limited thereto.

In the method for producing polyester of the present invention, in the case of the phosphorus compound, it is preferable that the content of phosphorus (P) contained in the phosphorus compound is about 5 to about 50 ppm, About 10 to about 40 ppm can be used.

The phosphorus compound serves as a heat stabilizer to reduce pyrolysis of the polyester. More specifically, the present invention relates to a process for producing a colorant, which is caused by heat applied to an esterification exchange reaction and a polycondensation reaction, a reaction heat generated additionally, and a reverse reaction or a decomposition reaction in which molecular chains are short- Or inhibits the unintended addition reaction by controlling the activity of the catalyst, and suppresses the yellowing of the finally formed polyester to make the color of the polymer transparent and close to colorless.

Further, the use of the phosphorus compound has an effect of preventing pyrolysis in a long-term solid-state polymerization such as a plant process, thereby affecting the viscosity increase of the polyester and having an important function of preventing yellowing. However, And the activity of the catalyst may be lowered. Therefore, in order to prevent this, usually the phosphorus compound and the catalyst are injected at a time interval. However, in the case of the catalyst composition of the present invention, there is an advantage that the catalytic activity is not reduced even when the mixed metal oxide and the phosphorus compound contained therein are mixed and added or the phosphorus compound is added in excess.

Further, according to an embodiment of the present invention, a coloring agent may be further added to improve color. Examples of the coloring agent include cobalt acetate, cobalt acetylacetonate, cobalt benzoylacetonate, cobalt hydroxide, cobalt bromide, cobalt chloride, cobalt acetate, Cobalt iodide, Cobalt fluoride, Cobalt cyanide, Cobalt nitrate, Cobalt sulfate, Cobalt selenide, and the like. But are not limited to, compounds including cobalt such as cobalt phosphate, cobalt oxide, cobalt thiocyanate, or cobalt propionate.

The addition amount of the coloring agent can be added in an amount of about 150 ppm or less, for example, about 30 to about 150 ppm, and preferably about 60 to about 100 ppm, based on the final polyester. It is known that the cobalt compound itself has a certain degree of catalytic activity. However, if it is added to an extent that exhibits a catalytic effect, the residual metal in the polyester increases, leading to toxicity and a decrease in brightness. Therefore, when added in the above range, coloring can be inhibited without causing deterioration of the brightness or thermal stability of the polyester.

In addition, the step of adding the cobalt compound in the present invention is not limited to the step of esterifying the dicarboxylic acid component and the glycol component during the polymerization reaction or polycondensation of the reactant of the esterification reaction, and it can be administered at any stage . In addition, other cobalt-based compounds can be used as long as they do not impair the object of the present invention.

According to the process for producing a polyester of the present invention, the polyester can be formed by liquid phase polymerization, and the formed polyester has an intrinsic viscosity From about 0.60 to about 0.68 dl / g.

According to the process for producing a polyester of the present invention, the polyester can be formed by solid-state polymerization, wherein the formed polyester has an intrinsic viscosity of about 0.70 to about 0.85 dl / g Lt; / RTI >

The polyester produced by the process for producing a polyester of the present invention may preferably be polyethylene terephthalate. In addition, although its application is not particularly limited, it can be widely used in food packaging materials, bottles, films, or fibrous plastics which require particularly excellent transparency, brightness and color conditions.

Hereinafter, the present invention will be described in more detail with reference to examples according to the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

< Example >

Experimental conditions

        In the examples, the synthesis of the composite metal oxide was carried out in a normal atmosphere and a general synthesis method was used.

As a reaction solvent for synthesis, an alcohol type solvent was used. Titanium isopropoxide, aluminum isopropoxide, magnesium methoxide, cobalt acetate, triethyl phosphate, terephthalic acid, ethylene glycol (Ethylene glycol) were used without any special purification process.

Manufacturing example  One

Manufacture of composite metal oxides

9.0 mL (30.38 mmol) of titanium isopropoxide and 1.0 g (4.89 mmol) of aluminum isopropoxide were dissolved in 100 mL of ethanol by heating. Magnesium methoxide (6-7 wt% in methanol, 5.0 mL) was slowly added thereto using a syringe. Next, distilled water and ethanol were mixed and the diluted solution was slowly added dropwise at room temperature (23 ° C).

After stirring the mixture for 1 hour, the resulting white precipitate was filtered using a glass filter, and the collected solid was taken out in air and the residue was washed with distilled water (10 mL x 2) and again with ethanol (30 mL x 2) And washed.

The product was dried under vacuum at 70-80 占 폚 for 8 hours to obtain 5.5 g of a metal oxide catalyst containing three metals of Ti, Al and Mg.

Example  1a

Terephthalic acid (19.34 Kg, 116.4 mol), monoethylene glycol (8.49 Kg, 142.56 mol) and isophthalic acid (598.07 g, 3 mol%) were placed in a reactor while stirring, mg) and germanium oxide (461 mg) were added to the reactor, and the temperature was increased from room temperature to 250 ° C. The tower temperature sensor connected to the reactor to measure the distillation water generated during the reaction was 250 to 135 C, the reaction was stopped and the oligomer (BHET) produced by the esterification reaction was transferred through the tube to the polycondensation reactor.

In this case, triethyl phosphate (1.729 g) and cobalt acetate (3.456 g) were dissolved in 100 g of monoethylene glycol, and then mixed with a color toner (Blue / Red = 0.057 g / 0.139 g) I put it. Then, the pressure of the polycondensation reactor was reduced from 28 to 0.5 torr over 60 minutes, and the temperature was raised from 250 to 285 ° C at the same time. The reaction was stopped when the internal temperature of the reactor was lowered and no further change was maintained, and when the polycondensation reaction was completed, the reaction was stopped.

The resulting polyethylene terephthalate (PET) resin had an intrinsic viscosity of 0.641 dl / g.

After completion of the reaction, the reaction product was passed through a cooling water and pulverized through a pelletizer to obtain 20 Kg of transparent polyethylene terephthalate resin in the form of a chip.

Example  1b

The polyethylene terephthalate resin obtained in the liquid phase polymerization of Example 1a was dried in air to remove water. (2 hours and 50 minutes), 170 占 폚 (2 hours), 225 占 폚 (8 hours), and cooling at a reduced pressure (0.2 to 0.5 torr) (10 hours) for 23 hours and 50 minutes.

After completion of the reaction, a PET resin having a crystalline solid structure in the form of a white solid compound and having an intrinsic viscosity of 0.762 dl / g was obtained.

Comparative Example  1a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a except that zinc acetate was used instead of germanium oxide.

Comparative Example  1b

A polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b using the liquid resin prepared in Comparative Example 1a.

Comparative Example  2a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a, except that lithium acetate was used instead of germanium oxide.

Comparative Example  2b

A polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b using the liquid resin prepared in Comparative Example 2a.

Comparative Example  3a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a, except that magnesium acetate was used instead of germanium oxide.

Comparative Example  3b

A polyethylene terephthalate solid-state resin was prepared using the liquid resin prepared in Comparative Example 3a under the same reaction conditions as in Example 1b.

Comparative Example  4a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a, except that aluminum acetate was used instead of germanium oxide.

Comparative Example  4b

A polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b using the liquid resin prepared in Comparative Example 4a.

Comparative Example  5a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a except that a Ti / Si catalyst was used in place of the Ti / Al / Mg composite metal oxide.

Comparative Example  5b

A polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b using the liquid resin prepared in Comparative Example 5a.

Comparative Example  6a

A polyethylene terephthalate resin was prepared in the same manner as in Example 1a except that Ti (OBu) ₄ catalyst was used instead of Ti / Al / Mg composite metal oxide.

Comparative Example  6b

Using the liquid resin prepared in Comparative Example 6a, a polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b.

Comparative Example  7a

A polyethylene terephthalate resin was prepared in the same manner as in Example 1a, except that germanium oxide was not used.

Comparative Example  7b

Using the liquid resin prepared in Comparative Example 7a, a polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b.

Comparative Example  8a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a except that antimony acetate was used instead of Ti / Al / Mg and germanium oxide.

Comparative Example  8b

Using the liquid resin prepared in Comparative Example 8a, a polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b.

Comparative Example  9a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a except that Ti / Al / Mg and Ti / Si catalyst were used instead of germanium oxide.

Comparative Example  9b

Using the liquid resin prepared in Comparative Example 9a, a polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b.

Comparative Example  10a

A polyethylene terephthalate liquid resin was prepared in the same manner as in Example 1a, except that Ti / Al / Mg was not used.

Comparative Example  10b

A polyethylene terephthalate solid-state resin was prepared under the same reaction conditions as in Example 1b using the liquid resin prepared in Comparative Example 10a.

The compositions and contents of the catalysts of Examples 1a to 1b and Comparative Examples 1a to 10b are shown in Table 1 below.

division Type of polymerization Catalyst composition PET reference element
Content (unit: ppm) Example 1a Liquid phase polymerization Ti / Al / Mg + GeO ₂ Ti = 10, Al = 0.5, Mg = 0.5, Ge = 14 Example 1b Solid state polymerization Ti / Al / Mg + GeO ₂ Ti = 10, Al = 0.5, Mg = 0.5, Ge = 14 Comparative Example 1a Liquid phase polymerization Ti / Al / Mg + Zn (OAc) ₂ Ti = 10, Al = 0.5, Mg = 0.5, Zn = 14 Comparative Example 1b Solid state polymerization Ti / Al / Mg + Zn (OAc) ₂ Ti = 10, Al = 0.5, Mg = 0.5, Zn = 14 Comparative Example 2a Liquid phase polymerization Ti / Al / Mg + LiOAc Ti = 10, Al = 0.5, Mg = 0.5, Li = 14 Comparative Example 2b Solid state polymerization Ti / Al / Mg + LiOAc Ti = 10, Al = 0.5, Mg = 0.5, Li = 14 Comparative Example 3a Liquid phase polymerization Ti / Al / Mg + Mg (OAc) ₂ Ti = 10, Al = 0.5, Mg = 0.5, Mg = 14 Comparative Example 3b Solid state polymerization Ti / Al / Mg + Mg (OAc) ₂ Ti = 10, Al = 0.5, Mg = 0.5, Mg = 14 Comparative Example 4a Liquid phase polymerization Ti / Al / Mg + AlOH (OAc) ₂ Ti = 10, Al = 0.5, Mg = 0.5, Al = 14 Comparative Example 4b Solid state polymerization Ti / Al / Mg + AlOH (OAc) ₂ Ti = 10, Al = 0.5, Mg = 0.5, Al = 14 Comparative Example 5a Liquid phase polymerization Ti / Si + GeO ₂ Ti = 10, Si = 0.5, Ge = 14 Comparative Example 5b Solid state polymerization Ti / Si + GeO ₂ Ti = 10, Si = 0.5, Ge = 14 Comparative Example 6a Liquid phase polymerization Ti (OBu) ₄ + GeO ₂ Ti = 10, Ge = 14 Comparative Example 6b Solid state polymerization Ti (OBu) ₄ + GeO ₂ Ti = 10, Ge = 14 Comparative Example 7a Liquid phase polymerization Ti / Al / Mg Ti = 10, Al = 0.5, Mg = 0.5 Comparative Example 7b Solid state polymerization Ti / Al / Mg Ti = 10, Al = 0.5, Mg = 0.5 Comparative Example 8a Liquid phase polymerization Sb (OAc) ₃ Sb = 253 Comparative Example 8b Solid state polymerization Sb (OAc) ₃ Sb = 253 Comparative Example 9a Liquid phase polymerization Ti / Si Ti = 10, Si = 0.5 Comparative Example 9b Solid state polymerization Ti / Si Ti = 10, Si = 0.5 Comparative Example 10a Liquid phase polymerization GeO ₂ Ge = 14 Comparative Example 10b Solid state polymerization GeO ₂ Ge = 14

< Experimental Example >

How to measure

Intrinsic viscosity ( Intrinsic Viscosity , IV )

Phenol and 1,1,2,2-tetrachloroethanol were mixed in a weight ratio of 6: 4, and 0.4 g of the polyester resin to be measured was added to 100 mL of the reagent. After dissolution for 90 minutes, Ubbelohde Transfer it to a viscometer and keep it in a 30 ° C thermostat for 10 minutes. Use a viscometer and an aspirator to determine the number of drops of solution. The number of drops of the solvent was also found by the same method, and then R.V. Value and I.V. Values were calculated. In the following equation, C represents the concentration of the sample.

[Equation 1]

R.V. = Samples falling in water / solvent drops in seconds

[Equation 2]

IV = 1/4 (RV-1) / C + 3/4 (in RV / C)

The carboxyl terminal end ( Carboxylic end group , CEG , - COOH ) Concentration

0.5 g of a polyester resin of 4 mm in size to be measured was placed in a 100 mL dissolution tube, and 25 mL of an ortho-chlorophenol solvent was added and dissolved at 100 DEG C for 1 hour to prepare a sample. The sample was titrated with 0.02 M KOH methanol solution and measured. The number of carboxyl groups is referred to as carboxylic group equivalents / 10 ⁶ g (or mmol / Kg) of polymer.

Hydroxyl end ( Diethylene glycol , DEG , - OH ) Concentration

0.5 g of a polyester resin of 4 mm in size to be measured was placed in a 100 mL dissolution tube, and 25 mL of an ortho-chlorophenol solvent was added and dissolved at 100 DEG C for 1 hour to prepare a sample. 50 mL of an excess amount of adipic acid was added to the sample, and the reaction was carried out at 100 DEG C for 1 hour to replace the terminal hydroxyl group with the terminal carboxyl group. After removing the extra adipic acid, the difference between the terminal carboxyl group amount of the substituted sample and the terminal carboxyl group amount of the non-substituted sample was calculated.

Polyethylene Terephthalate  Resin color ( Color = L, a, b)

50 g of the polyester resin to be measured was removed from the air and put in a colorimeter model SA-2000, and the color was measured 10 times, and the average value was set as a standard value.

The L, a, and b color systems are used internationally as a basis for polyester color evaluation. These color values are one of the color systems for standardizing color measurements and describe recognizable colors and color differences. In this system, L is the brightness factor and a and b are the color measurement numbers. In general, the b value indicating the yellow / blue balance is an important figure in the manufacture of drinking water containers and food packaging materials. Positive b value means yellow discoloration and negative value means blue discoloration. Positive a value means red discoloration and negative value means green discoloration. The L value is a numerical factor indicating the brightness and is a very important value such as b value in the production of drinking water containers and food packaging materials.

Experimental Example  One

The polycondensation time (time taken to complete the reaction after the start of the polycondensation reaction), solid phase polymerization time, and intrinsic viscosity of Examples 1a to 1b and Comparative Examples 1a to 10b were measured and are shown in Table 2 below.

 division The polycondensation time /
Solid phase polymerization time Intrinsic viscosity
(IV) Example 1a 2 hours 10 minutes 0.641 Example 1b 23 hours 50 minutes 0.762 Comparative Example 1a 2 hours 35 minutes 0.612 Comparative Example 1b 23 hours 50 minutes 0.711 Comparative Example 2a 2 hours 32 minutes 0.612 Comparative Example 2b 23 hours 50 minutes 0.697 Comparative Example 3a 2 hours 30 minutes 0.621 Comparative Example 3b 23 hours 50 minutes 0.691 Comparative Example 4a 2 hours and 39 minutes 0.625 Comparative Example 4b 23 hours 50 minutes 0.705 Comparative Example 5a 2 hours 34 minutes 0.610 Comparative Example 5b 23 hours 50 minutes 0.709 Comparative Example 6a 2 hours 47 minutes 0.602 Comparative Example 6b 23 hours 50 minutes 0.707 Comparative Example 7a 2 hours and 38 minutes 0.622 Comparative Example 7b 23 hours 50 minutes 0.710 Comparative Example 8a 2 hours 18 minutes 0.631 Comparative Example 8b 23 hours 50 minutes 0.742 Comparative Example 9a 2 hours and 39 minutes 0.624 Comparative Example 9b 23 hours 50 minutes 0.703 Comparative Example 10a 3 hours 05 minutes 0.590 Comparative Example 10b 23 hours 50 minutes 0.682

As shown in Table 2 above, the polyethylene terephthalate obtained in Examples 1a and 1b has excellent polycondensation time and intrinsic viscosity as compared with the polyethylene terephthalate obtained in Comparative Examples 1a to 10b. Specifically, in Example 1a prepared by liquid phase polymerization, the intrinsic viscosity value was 0.641, and in Comparative Examples 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, and 10a prepared by liquid phase polymerization 2b, 3b, 4b, 5b, 6b, 6b and 6c prepared by solid-state polymerization showed an intrinsic viscosity of 0.762 in Example 1b prepared by solid phase polymerization, 7b, 8b, 9b, and 10b. Compared with Comparative Examples 8a and 8b using Sb (OAc) ₃ catalyst in particular, it can be seen that the mixed composition of the composite metal oxide and the germanium compound of the present invention has a short polycondensation time and exhibits a high intrinsic viscosity.

Experimental Example  2

Color (L, a, b) values, CEG concentration, and DEG concentrations of Examples 1a to 1b and Comparative Examples 1a to 7b were measured and shown in Table 3 below.

division Color CEG concentration
(Unit: mmol / Kg) DEG concentration
(Unit: wt%) L a b Example 1a 45.34 0.82 -6.42 21.4 1.62 Example 1b 75.44 -0.59 -7.15 19.8 1.55 Comparative Example 1a 42.11 1.02 -3.45 23.5 2.78 Comparative Example 1b 70.89 0.05 -4.06 22.1 2.66 Comparative Example 3a 44.21 1.12 -3.25 22.6 1.98 Comparative Example 3b 71.99 0.25 -3.96 21.5 1.76 Comparative Example 5a 44.59 1.03 -3.15 24.6 1.89 Comparative Example 5b 72.21 0.06 -3.91 23.0 1.59 Comparative Example 7a 43.83 1.13 -3.78 24.6 1.89 Comparative Example 7b 71.00 -0.89 -4.52 22.0 1.95

Claims (15)

A composite metal oxide including titanium (Ti), aluminum (Al), magnesium (Mg), and oxygen (O); And
A catalyst composition for polyester polymerization comprising a germanium (Ge) compound.
2. The catalyst composition for polyester polymerization according to claim 1, wherein the composite metal oxide comprises titanium, aluminum, and magnesium elements alternately oxidized with oxygen.
The composite metal oxide according to claim 1, wherein the composite metal oxide is a catalyst for polyester polymerization which is a coprecipitate of a titanium compound represented by the following formula (1), an aluminum compound represented by the following formula (2), and a magnesium compound represented by the following formula Composition:
[Chemical Formula 1]
Ti (OR ¹⁾ ₄
(2)
Al (OR ²⁾ ₃
(3)
Mg (OR ³⁾ ₂
In the above formulas (1), (2) and (3)
R ¹ , R ² and R ³ are each independently a hydrogen atom or a C ₁ to C ₂₀ alkyl group (Alkyl), a C ₂ to C ₂₀ alkenyl group, a C ₃ to C ₂₀ cycloalkyl group _{(Cycloalkyl), C 6 ~ C} 20 aryl group (aryl), C group ₁ ~ C ₂₀ alkyl silyl (alkylsilyl), an alkyl aryl of C ₇ ~ C ₂₀ aryl group (arylalkyl) or C ₇ ~ C ₂₀ of the group (Alkylaryl).
The method of claim 1, wherein the germanium compound is at least one selected from the group consisting of germanium oxide, germanium methoxide, germanium ethoxide, germanium isopropoxide, germanium selenide, Germanium sulfide, germanium iodide, germanium nitride, germanium bromide, germanium chloride, tetramethyl germanium, tetraethyl germanium (e. G. Tetraethyl germanium), and germanium metal. The catalyst composition for polyester polymerization according to claim 1,
5. The catalyst composition for polyester polymerization according to claim 4, wherein the germanium compound is germanium oxide.
A composite metal oxide including titanium (Ti), aluminum (Al), magnesium (Mg), and oxygen (O); And a germanium (Ge) based compound in the presence of a catalyst composition comprising a dicarboxylic acid component and a glycol component.
7. The method of claim 6, wherein polymerizing the dicarboxylic acid component and the glycol component comprises the step of esterifying the dicarboxylic acid component and the glycol component, and polycondensation of the reactants of the esterification reaction A method for producing a polyester.
7. The method for producing a polyester according to claim 6, wherein the composite metal oxide and the germanium compound are added to the step of esterifying the dicarboxylic acid component and the glycol component.
7. The catalyst composition for polyester polymerization according to claim 6, wherein the composite metal oxide contains titanium (Ti) in an amount of 5 to 15 ppm based on the weight of the polyester.
7. The catalyst composition for polyester polymerization according to claim 6, wherein the germanium compound contains the germanium element in the germanium compound in an amount of 7 to 28 ppm based on the weight of the polyester.
The process for producing a polyester according to claim 6, which is carried out by liquid phase polymerization or solid phase polymerization.
12. The process according to claim 11, wherein the polyester is formed by liquid phase polymerization and has an intrinsic viscosity of 0.60 to 0.68 dl / g.
The process for producing a polyester according to claim 11, wherein the polyester is formed by solid state polymerization and has an intrinsic viscosity of 0.70 to 0.85 dl / g.
The method according to claim 6, wherein the polyester is used in food packaging materials, bottles, films or fibrous plastics.
The method for producing a polyester according to claim 6, wherein the polyester is polyethylene terephthalate.