KR20140039629A - Method of poly(1,4-cyclohexylenedimethylene terephthalate) having enhanced colors, and poly(1,4-cyclohexylenedimethylene terephthalate) manufactured by the same - Google Patents

Abstract

The present invention relates to a manufacturing method for polycyclohexylenedimethylene terephthalate resin comprising: a step of manufacturing a liquid mixture by mixing terephthalic acid (TPA) or dimethyl terephthalate (DMT) in a diol compound including cyclohexanedimethanol (CHDM) dissolved in water; and a step of performing bubbling while putting and stirring nitrogen in the liquid mixture. The manufacturing method for polycyclohexylenedimethylene terephthalate resin according to the present invention is able to produce a polycyclohexylenedimethylene terephthalate resin with excellent polymerization, color, color stability and improved thermal stability. The polycyclohexylenedimethylene terephthalate resin according to the present invention is suitable for being used as an LED housing material in which surface mounting technology (SMT) is applied.

Description

Method for preparing polycyclohexylenedimethylene terephthalate resin with excellent color and polycyclohexylenedimethylene terephthalate resin produced by this method {enhanced method of poly (1,4-cyclohexylenedimethylene terephthalate) having enhanced colors, and poly (1, 4-cyclohexylenedimethylene terephthalate) manufactured by the same}

The present invention relates to a method for preparing a polycyclohexylenedimethylene terephthalate resin, and to a polycyclohexylenedimethylene terephthalate resin produced by the present invention, and more particularly, to a polycyclohexylenedimethylene terephthalate resin It relates to a production method and a polycyclohexylenedimethylene terephthalate resin produced thereby.

Polyalkylene terephthalate (Poly (alkylene terephthalate)) has excellent physical properties such as wear resistance, durability, heat stability, and is used as a material for fibers, films, molded articles, and the like. Such polyalkylene terephthalates include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polycyclohexylenedimethylene terephthalate (PET). Poly (1,4-cyclohexylenedimethylene terephthalate), hereinafter referred to as 'PCT' is commercialized and the most widely used material is PET, which is used for fiber and bottle.

Despite the excellent physical properties, PET has relatively low crystallization rate, so in order to be used for engineering plastics where high crystallinity is required at the product stage, it needs the help of nucleating agent and crystallization accelerator, and the production speed during injection molding process is lowered or mold The temperature should be adjusted to maintain the crystallization rate high.

On the other hand, since PBT has a faster crystallization rate than PET, it has been widely used in engineering plastics applications to overcome the physical problems of PET as mentioned above, that is, the crystallization rate is slow. However, since PBT has a lower heat deflection temperature than PET, its use has been limited to applications requiring high heat resistance despite excellent moldability compared to PET.

On the other hand, PCT is attracting attention as a new material that can overcome the problems of the polyester material described above, namely, the moldability problem due to the slow crystallization rate and the limitations in the development of the application due to the low heat deformation temperature.

Such PCT is an ester of terephthalic acid (hereinafter referred to as TPA) or dimethyl terephthalate (hereinafter referred to as DMT) and 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM), or Crystalline polyesters produced by transesterification and polycondensation reactions, having very high melting points (Tm) and very fast crystallization rates. Since the development of the PCT for the first time in the 1960s, the market developed mainly for carpet use by the soft touch characteristic of PCT fibers.However, with the appearance of polyamide, the distinct use of PCT gradually disappeared. With the development of PCT compound formulations in the field of engineering plastics, they have been used only in connectors and heat-resistant parts in the electrical, electronic and automotive fields, where high heat-resistant is required.

PCT has superior heat resistance, chemical resistance, hygroscopicity, and flowability compared to general-purpose polyesters such as PET and PBT. Among them, heat deflection temperature is 245 to 260 ° C, continuous-use. The only polyamide, polyphenylene sulfide, and liquid crystalline polymer in commercialized non-wholly aromatic polyesters except liquid crystalline polyesters with temperatures of 130-150 ° C. It belongs to the group of super engineering plastics, which means metal-substituteable engineering plastics. In particular, PCT has excellent color stability and extremely low water absorption when compared to other polymer resins such as polyamide, and is used in electronic material applications or products in which surface mounting technology is performed at high temperatures. It can be usefully applied in the housing or reflector use of LED (Light Emitting Diode) which is continuously exposed to heat and light.

U.S. Patent No. 5,106,944 describes a process for producing PCT using main materials such as DMT and CHDM, titanium alkoxide and alkaline earth metal salts as catalysts, and U.S. Patent No. 5,124,388 discloses PCT copolyester and Color enhancement techniques for PCT Copolyester / Polycarbonate blends are disclosed, respectively. In addition, US Patent No. 4,972,015 discloses a thin-walled thermoformed heatset article made of PCT and PCT copolyester having an intrinsic viscosity of 0.7-1.1, and US Patent No. 5,242,967 discloses A method of adding an aliphatic polyester as a method of improving the crystallization characteristics is disclosed. In addition, US Pat. No. 4,859,732 discloses a technique for the composition of PCT compounds to which linear alcohol and glass-reinforced fibers are added as a method of improving the crystallization characteristics and strength of the PCT.

However, the prior art proposed only the composition for improving the crystallization characteristics and color in the compound step, and no manufacturing method has been reported that can fundamentally improve the color stability and thermal stability of the PCT in the PCT polymerization step.

1. US Patent No. 5,106,944 2. United States Patent No. 5,124,388 3. US Patent No. 4,972,015 4. US Patent No. 5,242,967 5. US Patent No. 4,859,732

The present invention provides a method for producing a polycyclohexylenedimethylene terephthalate resin having excellent color and improved thermal stability.

According to an aspect of the present invention, a method for preparing a polycyclohexylenedimethylene terephthalate resin includes terephthalic acid (TPA) or dimethyl terephthalic acid (DMT) in a diol compound containing cyclohexanedimethanol (CHDM) dissolved in water. Mixing dicarboxylic acids to prepare a liquid mixture; And adding nitrogen to the mixture of the liquid phase, stirring and bubbling.

In the above, the diol compound is one or more selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propane diol, and neopentyl glycol within 20 mol% with respect to the total number of moles of the diol compound. It may further include.

In the above, the dicarboxylic acid is isophthalic acid (IPA), naphthalene 2,6-dicarboxylic acid (2,6-NDA), dimethylisophthalic acid (DMI), and dimethyl naphthalene 2,6-dicarboxylic acid ( 2,6-NDC) may be further included within 20 mol% based on the total number of moles of dicarboxylic acid.

The method may further include performing an esterification reaction and a polycondensation reaction after the bubbling.

And the said polycondensation reaction can be performed at 290 degreeC or more and less than 310 degreeC.

In addition, it may further comprise the step of injecting a titanium compound as a catalyst.

And the titanium compound is titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl-isopropyl titanate It may be selected from the group consisting of.

In addition, the titanium compound may be added in an amount of 10 to 50 ppm of titanium element based on the weight of the final polycyclohexylenedimethylene terephthalate resin.

In addition, it may further comprise the step of adding a phosphorus stabilizer.

Here, the phosphorus stabilizer is triethyl phosphate (tri-ethyl phosphate), trimethyl phosphate (tri-methyl phosphate), triphenyl phosphate (tri-phenyl phosphate), triethyl phosphonoacetate (phosphoric acid) ), And phosphorous acid.

Polycyclohexylenedimethylene terephthalate resin prepared according to the production method according to another aspect of the present invention has an intrinsic viscosity of 0.50 to 1.10 dl / g, color-L value 84 or more after heat treatment at 150 ℃ 1 hour, And a Color-b value may be 4 or less.

The method for producing a polycyclohexylenedimethylene terephthalate resin according to the present invention can be produced a polycyclohexylene dimethylene terephthalate resin excellent in the degree of polymerization, color and color stability of the polymer, and significantly improved thermal stability The polycyclohexylenedimethylene terephthalate resin according to the present invention is suitable for use as an LED housing material to which SMT (surface mounting technology) is applied.

1 is a schematic diagram of some internal sections of the Ubbelodhe viscous tube used for intrinsic viscosity measurement.

The present invention is capable of various modifications and various embodiments, and specific embodiments are described in detail in the description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The present invention comprises the steps of preparing a liquid mixture by mixing dicarboxylic acid containing terephthalic acid (TPA) or dimethyl terephthalic acid (DMT) to a diol compound containing cyclohexane dimethanol (CHDM) dissolved in water; And it provides a method for producing a polycyclohexylene dimethylene terephthalate resin comprising the step of adding nitrogen to the mixture of the liquid, stirring and bubbling.

In addition, the present invention is a polycyclohexylene dimethylene terephthalate resin having an intrinsic viscosity of 0.50 to 1.10 dl / g, color-L value of 84 or more, and Color-b value of 4 or less after heat treatment at 150 ℃ 1 hour to provide.

Hereinafter, a method for preparing a polycyclohexylenedimethylene terephthalate resin according to an embodiment of the present invention will be described in more detail.

In general, partially aromatic polyester resins are usually polymerized from dicarboxylic acids and diol compounds, as known in the art. In the method for producing an aromatic polyester resin, (A) a dicarboxylic acid compound, a diol compound and a phosphorus stabilizer compound are mixed and esterified, and (B) a catalyst compound is added to the resultant obtained by the esterification reaction. After the condensation polymerization reaction, (C) comprising the step of extruding the condensation polymerization reactant to produce a pellet, if necessary (D) may be added to the step of crystallizing the pellet to perform a solid phase polymerization.

According to one embodiment of the present invention, a liquid mixture is prepared by mixing dicarboxylic acid containing terephthalic acid (TPA) or dimethyl terephthalic acid (DMT) with a diol compound containing cyclohexanedimethanol (CHDM) dissolved in water. Manufacturing step; And it provides a method for producing a polycyclohexylene dimethylene terephthalate resin comprising the step of adding nitrogen to the liquid mixture, stirring and bubbling.

The method for producing a polycyclohexylenedimethylene terephthalate resin according to the present invention is characterized by performing nitrogen bubbling using a diol compound containing cyclohexanedimethanol (CHDM) dissolved in water.

Cyclohexanedimethanol is the main raw material of polycyclohexylenedimethylene terephthalate resin together with terephthalic acid, and cyclohexanedimethanol is a waxy solid at room temperature because its melting point is higher than room temperature, and such cyclohexanedimethanol is effectively introduced into the reactor. In order to do this, it is convenient to make the liquid and then add it in terms of operation of the process. Meanwhile, the method of making cyclohexane dimethanol in a liquid phase is prepared by heating the cyclohexane dimethanol at a temperature above the melting point, for example, at about 100 ° C., and liquefying using a solvent that is well dissolved in cyclohexane dimethanol. How to put Here, when cyclohexane dimethanol is heated by heat for a long time, it is preferable to add the solution by adding a solution because it may adversely affect the color of cyclohexane dimethanol or a resin produced therefrom by side reactions such as oxidation reactions. Do.

On the other hand, the nitrogen bubbling after the reaction in the reactor is aimed to prevent the oxidation reaction by the trace amount of oxygen as much as possible.

In the above, the diol compound may include cyclohexanedimethanol (CHDM), while one selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propane diol, and neopentyl glycol It may further include the above. That is, the diol compound mainly refers to 1,4-cyclohexanedimethanol, but is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propane diol, and neopentyl glycol. More than one species may be used by further adding within 20 mol% with respect to the total number of mol of the diol compound. This is because when it is used in excess of 20 mol%, the physical properties of the polyester is very different from that of PCT, which makes it difficult to apply to applications developed for crystalline PCT resin.

On the other hand, the dicarboxylic acid may include terephthalic acid (TPA) or dimethyl terephthalic acid (DMT), while isophthalic acid (IPA), naphthalene 2,6-dicarboxylic acid (2,6-NDA), dimethylisophthalic acid (DMI), and one or more selected from the group consisting of dimethyl naphthalene 2,6-dicarboxylic acid (2,6-NDC). That is, the dicarboxylic acid and derivatives thereof mainly mean terephthalic acid (TPA) or dimethyl terephthalic acid (DMT), but isophthalic acid (IPA), naphthalene 2,6-dicarboxylic acid (2,6- naphthalenedicarboxylic acid (2,6-NDA), dimethylisophthalate (DMI), dimethyl naphthalene 2,6-dicarboxylic acid (dimethyl 2,6-naphthalenedicarboxylate; 2,6-NDC) It may further include within 20 mol% based on the number of mol. This is because when it is used in excess of 20 mol%, the physical properties of the polyester is very different from that of PCT, which makes it difficult to apply to applications developed for crystalline PCT resin.

The method may further include performing an esterification reaction and a polycondensation reaction after the bubbling. That is, nitrogen bubbling can be carried out without limitation in the step before the esterification reaction, i.e., before the elevated temperature. As described above, the nitrogen bubbling is aimed at preventing the oxidation reaction by the trace amount of oxygen as much as possible.

And the said polycondensation reaction can be performed at 290 degreeC or more and less than 310 degreeC. If the polycondensation reaction temperature is less than 290 ° C, the reaction rate is slow due to the melting point of the polycyclohexylenedimethylene terephthalate, and the polymer is solidified inside the reactor. This is because the production of polycyclohexylenedimethylene terephthalate resin having target physical properties such as target molecular weight and color becomes difficult.

In addition, the production method may further include the step of adding a titanium compound as a catalyst. In the present invention, a titanium compound is used as a catalyst, and the titanium compound is titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl tita Nate, and butyl-isopropyl titanate.

In addition, the titanium compound may be added in an amount of 10 to 50 ppm of titanium element based on the weight of the final polycyclohexylenedimethylene terephthalate resin. This content range is for controlling side reactions that cause discoloration. When the content of titanium element is less than 10 ppm, there is a problem that the reaction rate is lowered. When the content of titanium element is more than 50 ppm, the color of the polymer is deteriorated and pyrolysis is caused. This is because there is a disadvantage in causing a reaction.

In addition, the phosphorus stabilizer may be further mixed in the manufacturing method. The phosphorus stabilizer is preferably added at the beginning of the esterification reaction, more preferably in the slurry before the esterification reaction, and is preferably added so as to be within 30 ppm based on the phosphorus element content included in the stabilizer relative to the weight of the polymer. This is because if the content of the phosphorus stabilizer exceeds 30 ppm, there is a problem that the polymerization reaction rate is slow and the degree of polymerization finally reached is low.

Here, the phosphorus stabilizer is triethyl phosphate (tri-ethyl phosphate), trimethyl phosphate (tri-methyl phosphate), triphenyl phosphate (tri-phenyl phosphate), triethyl phosphonoacetate (phosphoric acid) ), And phosphorous acid.

In addition, the esterification reaction in the present invention can be carried out in the equipment and similar reaction conditions known in the art, preferably for 4 to 10 hours at a temperature of 230-290 ℃, pressure 0.5-3.0kg / ㎠ It can be carried out. It is also desirable to configure the system so that the water during the esterification reaction can be removed immediately.

On the other hand, the polycondensation reaction can be carried out for 100 to 300 minutes under the conditions of the temperature of 290-320 ℃, pressure 0.1-2.0 torr. Cyclohexanedimethanol and by-products generated by the polycondensation reaction are preferably configured to be immediately removable.

In the case of performing the solid phase polymerization reaction, the temperature is 230 to 270 ° C, and the pressure can be carried out in a vacuum degree of 0.2 to 2.0 torr or in a nitrogen atmosphere.

On the other hand, most polymers have a color after polymerization, and in particular, when exposed to excessive heat during the polymerization process, the color of the polymer material becomes dark yellow by pyrolysis and oxidative decomposition reactions. Because of this importance, the color of the polymer material becomes an important quality item.

PCT resin prepared according to the method for producing a polycyclohexylenedimethylene terephthalate resin according to the present invention has an intrinsic viscosity of 0.50 to 1.10 dl / g, color-L value of 84 or more after heat treatment at 150 ℃ 1 hour, and The color-b value may be 4 or less.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the present invention.

Example  One

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. To this, 20 g of triethyl phosphate and 20 g of Titanium oxide-based catalyst (trade name Hombifast PC, manufactured by Sachtleben) were added and stirred and mixed in a nitrogen atmosphere at 90 ° C. to form a slurry, and at a final temperature of 1.5 atm. The esterification reaction was carried out while raising the temperature to 260 ° C. for 6 hours, followed by a polyester polycondensation reaction at 295 ° C. and a vacuum degree of 0.5 to 1 torr for 200 minutes to obtain a PCT polymer.

Example  2

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. Here, 7 g of triethyl phosphate and 20 g of Titanium oxide-based catalyst (Sachtleben's brand name Hombifast PC) were added to the reactor, stirred and mixed in a nitrogen atmosphere at 90 ° C. to obtain a slurry, and a final temperature of 1.5 The esterification reaction was performed by raising the temperature to 260 ° C. for 6 hours at atmospheric pressure, followed by a polyester polycondensation reaction at 300 ° C. and a vacuum degree of 0.5 to 1 torr for 280 minutes to obtain a PCT polymer. Got it.

Example  3

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. Here, 7 g of triethyl phosphate and 20 g of Titanium oxide-based catalyst (Sachtleben's brand name Hombifast PC) were added to the reactor, stirred and mixed in a nitrogen atmosphere at 90 ° C. to obtain a slurry, and a final temperature of 1.5 The esterification reaction was performed by raising the temperature to 260 ° C. for 6 hours at atmospheric pressure, followed by polyester polycondensation reaction at 305 ° C. under a vacuum of 0.5 to 1 torr for 280 minutes. Got it.

Comparative Example  One

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. Into this, 7 g of triethyl phosphate and 20 g of Titanium oxide catalyst (Sachtleben's brand name Hombifast PC) (15% effective Ti ratio in the catalyst) were added to the reactor, stirred and mixed at 90 ° C. to a slurry state, and the final temperature was 1.5 atm. The esterification reaction was carried out while raising the temperature to 260 ° C. for 6 hours, followed by a polyester polycondensation reaction at a temperature of 310 ° C. and a vacuum degree of 0.5 to 1 torr for 280 minutes to obtain a PCT polymer. .

Comparative Example  2

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. Into this, 7 g of triethyl phosphate and 20 g of Titanium oxide catalyst (Sachtleben's brand name Hombifast PC) (15% effective Ti ratio in the catalyst) were added to the reactor, stirred and mixed at 90 ° C. to a slurry state, and the final temperature was 1.5 atm. The esterification reaction was carried out while raising the temperature to 260 ° C. for 6 hours, followed by a polyester polycondensation reaction at a temperature of 315 ° C. and a vacuum degree of 0.5 to 1 torr for 280 minutes to obtain a PCT polymer. .

Comparative Example  3

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. Here, 7 g of triethyl phosphate and 40 g of Titanium oxide catalyst (Sachtleben's brand name Hombifast PC) were added to the reactor, stirred and mixed at 90 ° C. to form a slurry, and at a final temperature of 1.5 atm. The esterification reaction was carried out while raising the temperature to 260 ° C. for 6 hours, followed by a polyester polycondensation reaction at a temperature of 300 ° C. and a vacuum degree of 0.5 to 1 torr for 280 minutes to obtain a PCT polymer. .

Comparative Example  4

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then charged into the reactor. 48 Kg of Terephthalic acid (TPA) was added thereto, followed by nitrogen for 5 hours in an aqueous solution of TPA and CHDM. TPA-CHDM slurry was prepared while bubbling by stirring. To this, 60 g of triethyl phosphate and 60 g of Titanium oxide catalyst (Sachtleben's trade name Hombifast PC) (15% effective Ti ratio in the catalyst) were added to the reactor and stirred and mixed at 90 ° C. to form a slurry, at a final temperature of 1.5 atm. The esterification reaction was carried out while raising the temperature to 260 ° C. for 6 hours, followed by a polyester polycondensation reaction at a temperature of 300 ° C. and a vacuum degree of 0.5 to 1 torr for 280 minutes to obtain a PCT polymer. .

Comparative Example  5

65 Kg of 1,4-cyclohexanedimethanol (trans 70%) was dissolved in 6.5 Kg of water, and then 20 g of Terephthalic acid, 7 g of triethyl phosphate, and 20 g of Titanium oxide-based catalyst (trade name Hombifast PC from Sachtleben) were used. A ratio of 15%) was added to the reactor, stirred and mixed at 90 ° C. to form a slurry, and the esterification reaction was performed by heating the final temperature at 1.5 atm to 260 ° C. for 6 hours, followed by 300 ° C. and 0.5 to 0.5%. A polyester polycondensation reaction was carried out at a vacuum degree of 1 torr for 280 minutes to obtain a PCT polymer.

Comparative Example  6

Terephthalic acid 48Kg, 1,4-cyclohexanedimethanol (trans 70%) 65 Kg heated at 100 ° C for at least 5 hours, triethyl phosphate 7 g, Titanium oxide catalyst (Sachtleben Corporation Hombifast PC) 20 g (effective Ti ratio in the catalyst 15 %) Was added to the reactor, stirred and mixed at 90 ° C. to a slurry state, and the esterification reaction was carried out at a final temperature of 1.5 atm for 6 hours, followed by an esterification reaction, followed by 300 ° C. and 0.5 to 1 torr. The polyester polycondensation reaction was carried out at a vacuum degree of 280 minutes to obtain a PCT polymer.

Comparative Example  7

Terephthalic acid 48 Kg, 1,4-cyclohexanedimethanol (trans 70%) 65 Kg heated at 100 ° C for at least 5 hours, triethyl phosphate 7 g, Titanium oxide based catalyst (Sachtleben brand Hombifast PC) 20 g (effective Ti ratio in the catalyst) 15%) was added to the reactor and stirred and mixed at 90 ° C. to form a slurry, and the esterification reaction was carried out at a final temperature of 1.5 atm for 6 hours, followed by an esterification reaction, followed by 300 ° C., 0.5 to 1 A polyester polycondensation reaction was performed for 280 minutes at a vacuum degree of torr to obtain a PCT polymer.

Test Example  One

The intrinsic viscosity of the PCT resins obtained in Examples 1 to 3 and Comparative Examples 1 to 7 was measured by the following method.

After dissolving PCT resin at a concentration of 1.2 g / dl in o-chlorophenol, the intrinsic viscosity was measured using a Ubbelodhe viscous tube. The temperature of the viscous tube is maintained at 35 ° C., and the time required for the solution to pass through the solution e is the time it takes for the solvent to pass between the internal sections a-b (FIG. 1). When the time taken to t ₀ is the specific viscosity is defined as

At this time, the intrinsic viscosity was calculated using the following correction equation.

At this time, A was 0.247 as Huggins constant, and c was 1.2 g / dl as the concentration value.

Test Example  2

The color of the PCT resin obtained in Examples 1 to 3 and Comparative Examples 1 to 7 was measured by the following method.

After PCT resin was crystallized for 1 hour in a 150 ℃ convection oven, the color of the PCT resin was measured using a color meter.

CIE LAB indicator was used for color measurement. The CIE LAB system is a color space coordinate defined by CIE based on the opposite color theory of yellow-blue, green-red, etc., where human senses color. L * value is brightness (0-100; 0 is black, 100 is white) , a * values are green-red (+ is red based on 0,-is green), and b * values are yellow-blue (+ is yellow based on 0,-is blue).

The conditions and physical properties of the Examples and Comparative Examples carried out above are shown in Table 1 below.

CHDM
Input type CHDM
Nitrogen bubbling time Polycondensation
Temperature Ti metal powder input Intrinsic viscosity 150 degrees
1 hours
After heat treatment
Color-L * 150 degrees
1 hours
After heat treatment
Color-b * unit - hour ℃ ppm dl / g - - Example 1 Aqueous solution 5 295 37.5 0.70 85 2 Example 2 Aqueous solution 5 300 37.5 0.69 86 1.5 Example 3 Aqueous solution 5 305 37.5 0.68 86 2.3 Comparative Example 1 Aqueous solution 5 310 37.5 0.59 79 8 Comparative Example 2 Aqueous solution 5 315 37.5 0. 51 70 12.5 Comparative Example 3 Aqueous solution 5 300 75 0.61 82 7.5 Comparative Example 4 Aqueous solution 5 300 112.5 0.59 71 11.5 Comparative Example 5 Aqueous solution 0 300 37.5 0.73 80 5.1 Comparative Example 6 100 ℃
Heating 0 300 37.5 0.71 82 8.7 Comparative Example 7 100 ℃
Heating 0 300 37.5 0.71 82 9.9

As shown in Table 1, the method for producing a polycyclohexylenedimethylene terephthalate resin according to the present invention can produce a polycyclohexylenedimethylene terephthalate resin excellent in color, the polycyclohexylene according to the present invention Dimethylene terephthalate resin was found to be suitable for use as a LED housing material to which SMT (surface mounting technology) is applied.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (12)

Preparing a liquid mixture by mixing a diol compound including cyclohexanedimethanol (CHDM) dissolved in water with a dicarboxylic acid including terephthalic acid (TPA) or dimethyl terephthalic acid (DMT); And
Adding nitrogen to the liquid mixture, stirring and bubbling;
Method for producing a polycyclohexylenedimethylene terephthalate resin comprising a. The diol compound of claim 1, wherein the diol compound is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propane diol, and neopentyl glycol, based on the total number of moles of mol of the diol compound. Method for producing a polycyclohexylene dimethylene terephthalate resin further comprising within mol%. The dicarboxylic acid of claim 1, wherein the dicarboxylic acid is isophthalic acid (IPA), naphthalene 2,6-dicarboxylic acid (2,6-NDA), dimethylisophthalic acid (DMI), and dimethyl naphthalene 2,6-dicar. A method for producing a polycyclohexylenedimethylene terephthalate resin further comprising at least one selected from the group consisting of acids (2,6-NDC) within 20 mol% based on the total number of moles of dicarboxylic acid. The method of claim 1, further comprising performing an esterification reaction and a polycondensation reaction after the bubbling. The method for producing a polycyclohexylenedimethylene terephthalate resin according to claim 4, wherein the polycondensation reaction is performed at 290 ° C or higher and lower than 310 ° C. The method of manufacturing a polycyclohexylenedimethylene terephthalate resin according to claim 1, further comprising the step of introducing a titanium compound as a catalyst. The method of claim 6, wherein the titanium compound is titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl- A method for producing a polycyclohexylenedimethylene terephthalate resin selected from the group consisting of isopropyl titanate. The method of claim 6, wherein the titanium compound is added in an amount of 10 to 50 ppm of titanium element based on the weight of the final polycyclohexylenedimethylene terephthalate resin. The method of manufacturing a polycyclohexylenedimethylene terephthalate resin according to claim 1, further comprising the step of adding a phosphorus stabilizer. 10. The method of claim 9, wherein the phosphorus stabilizer is tri-ethyl phosphate, tri-methyl phosphate, tri-phenyl phosphate, triethyl phosphonoacetate A method for producing a polycyclohexylenedimethylene terephthalate resin selected from the group consisting of phosphoric acid, phosphoric acid, and phosphoric acid. A polycyclohexylenedimethylene terephthalate resin prepared according to any one of claims 1 to 10. The method of claim 11, wherein the polycyclohexylenedimethylene terephthalate resin has an inherent viscosity of 0.50 to 1.10 dl / g, color-L value of 84 or more, and Color-b value of 4 after heat treatment at 150 ℃ 1 hour Polycyclohexylene dimethylene terephthalate resin which is the following.

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