TW201527357A - Poly(cyclohexylenedimethylene terephtalate) copolymer having advenced impact strength, discoloration resistance and reflectance, and resin molded article manufactured therefrom - Google Patents

Abstract

The present invention relates to a poly(cyclohexylenedimethylene terephthalate) copolymer, and a resin molded article manufactured therefrom. The poly(cyclohexylenedimethylene terephthalate) copolymer according to the present invention exhibits excellent intrinsic physical properties. Therefore, it is possible to provide a resin molded article having enhanced impact strength, discoloration resistance, and reflectance even without additional additives. Such a resin molded article is able to maintain excellent initial physical properties under continuous exposure to heat and light, and therefore, it can be appropriately applied to housings or reflectors for LEDs, etc.

Description

Polyparaphenylene with improved impact strength, resistance to discoloration and reflectivity Acid cyclohexane dimethanol ester copolymer and resin molded article made therefrom

The present invention relates to a poly(cyclohexylene dimethylene terephthalate) copolymer having improved impact strength, resistance to discoloration, and reflectance, and a resin molded article made therefrom.

Poly(alkylene terephthalate) materials have been widely used in fibers, dies, and molded articles due to their excellent physical properties such as abrasion resistance, high durability, and thermal stability. Molded article) and other items. Commercially available polyalkylene terephthalate materials include poly(ethylene terephthalate), PET, poly(butylene terephthalate), PBT And poly(1,4-cyclohexylene dimethylene terephthalate), PCT, and the like.

Among them, PCT is regarded as a new material that can overcome some problems of polyester materials such as PET and PBT. A problem with the above materials is that the moldability is lowered due to its slower crystallization rate, and application is also limited due to having a lower heat deflection temperature.

PCT is a crystalline polyester with very high melting point and very fast crystallization rate, which can be made by esterification reaction, or via terephthalic acid (TPA) or dimethyl terephthalate. , DMT) is prepared by transesterification and polycondensation reaction with 1,4-cyclohexanedimethanol (CHDM).

Compared with general polyester materials such as PET and PBT, PCT has better heat resistance, chemical resistance, hygroscopic resistance and fluidity, and in particular, the heat deflection temperature of PCT is between Between 245 ° C and 260 ° C, and the continuous-use temperature is between 130 ° C and 150 ° C. Commercially, in addition to liquid crystalline polyester, only the PCT system in non-wholly aromatic polyester can be called super-engineering plastic like polydecylamine ( Polyamide), polyphenylene sulfide, liquid crystal polymer, etc., can be used to replace metals.

PCT can be used in electronic equipment that performs surface mounting technology at high temperatures, or for continuous exposure to light and thermal emitting diodes (LEDs) in use (housing) ) or reflector.

As the range of applications for PCT continues to expand, many are suggested to improve the color and crystalline quality of PCT in the form of additives such as stabilizers or fiberglass. However, most of the methods are only related to compounds with PCT, and cannot be considered as a way to improve the physical properties of the PCT itself.

The invention provides a poly(cyclohexylene dimethylene terephthalate) copolymer, which can provide a tree made therefrom The resin molded article has improved impact strength, excellent resistance to discoloration, and reflectivity.

Further, the present invention provides a resin molded article made of a poly(cyclohexylene dimethylene terephthalate) copolymer.

The method of the present invention to achieve the above object is described below.

The present invention provides a poly(cyclohexylene dimethylene terephthalate) copolymer comprising: one repeating unit represented by the following Chemical Formula 1; and a polyoxyalkylene (polysiloxane) represented by the following Chemical Formula 2 Another repeating unit of compound formation.

In Chemical Formula 2, R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or 6 to 18 independently substituted or unsubstituted. An aromatic group of carbon atoms. D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbyl group having 4 to 10 carbon atoms. L ¹ and L ² are each independently a hydroxyl group or a hydroxy phenyl group, and n and m are each independently an integer of 5 to 300.

In the present invention, the weight percentage of the repeating unit formed of the polyoxyalkylene compound in the poly(cyclohexanedimethylene terephthalate) copolymer is from 0.1% to 30%.

The polybutylene terephthalate copolymer may have a weight average molecular weight of between 10,000 and 100,000, and the amount of the poly(cyclohexanedimethylene terephthalate) copolymer. The number average molecular weight can be between 10,000 and 50,000.

The present invention provides a process for preparing a polycyclohexylene dimethylene terephthalate copolymer comprising the following steps. First, a diol compound, a dicarboxylic acid compound, and a polysiloxane compound represented by Chemical Formula 2 are mixed, and an esterification reaction is carried out by a catalyst. Then, the product of the esterification reaction is subjected to a polycondensation reaction.

In the present invention, wherein the esterification reaction can be carried out as a composition based on 100 parts by weight (pbw) of the diol compound, the composition comprising the part by weight of 90 to 110 a dicarboxylic acid compound and the polyoxyalkylene compound in an amount of from 0.01 to 10, wherein the diol compound comprises 1,4-cyclohexanedimethanol, and the dicarboxylic acid The compound comprises terephthalic acid, dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate.

The composition of the esterification reaction may further comprise one or more phosphorus stabilizers in a part by weight of 0.001 to 5, based on 100 parts by weight of the diol compound. (phosphorus stabilizer), and the phosphorus stabilizer may be selected from the group consisting of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonium acetate (triethyl phosphonoacetate), phosphoric acid, and phosphorous acid.

In the present invention, the esterification reaction can be carried out at a temperature of from 230 ° C to 290 ° C and a pressure of from 0.01 kg / cm ² to 3.0 / cm ² for from 120 minutes to 600 minutes.

In the present invention, the catalyst may be one or more titanium-based catalysts selected from the group consisting of titanium oxide, titanium chelate compound, tetrapropyl titanate (tetra-n-). Propyl titanate), tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and titanyl titanate In the group consisting of butyl-isopropyl titanate.

In the present invention, the polycondensation reaction can be carried out for 60 minutes to 360 minutes at a temperature of from 290 ° C to 320 ° C and a pressure of from 0.1 torr to 2.0 Torr.

Further, the present invention provides a resin molded article made of the above-mentioned polycyclohexane dimethanol terephthalate copolymer.

In the present invention, the resin molded article may have an impact strength (tested by ASTM D256) of greater than or equal to 20 J/m, and when the thickness of the sample is 1/8 Torr at 25 °C.

Further, after being placed in an environment of 140 ° C for 48 hours, the value of the color space L*-b* of the resin molded article (color L*-b* value) may be greater than or equal to the resin molded article at room temperature. 95% of the value of the starting color space L*-b*.

Further, after 48 hours in an environment of being placed at 140 ° C, the resin molded article had a reflectance for a wavelength of 450 nm greater than or equal to 95% of the initial reflectance of the resin molded article at a wavelength of 450 nm.

The resin molded article can be used for a housing or reflector of a light-emitting diode.

Hereinafter, a method for preparing a polycyclohexylene dimethylene terephthalate copolymer, a poly(cyclohexanedimethylene terephthalate) copolymer, and a poly(p-phenylene terephthalate) copolymer of the present invention Each embodiment of a resin molded article made of a cyclohexane dimethanolate copolymer is described in detail.

Heretofore, the technical terms used herein are to be construed as limiting the specific embodiments, and the invention should not be construed as limited. As long as there is no specific anti-sense description, the singular type used herein also includes the plural form. In addition, the term "including" is used in an open-ended language to describe the features, regions, integers, steps, operations, units, and/or components, etc., but is not limited to the exclusion of additional features. Area, whole, step, operation, unit, composition, or/and group.

I. PCT copolymer

An embodiment of the present invention provides a poly(cyclohexylene dimethylene terephthalate) copolymer (abbreviated as PCT copolymer), comprising one repeating unit represented by the following Chemical Formula 1; and the following chemical formula 2 Another repeating unit formed by the polysiloxane compound.

In Chemical Formula 2, R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or 6 to 18 independently substituted or unsubstituted. An aromatic group of carbon atoms. D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbyl group having 4 to 10 carbon atoms. L ¹ and L ² are each independently a hydroxyl group or a hydroxy phenyl group, and n and m are each independently an integer of 5 to 300.

According to a continuous study by the present inventors, it was confirmed that a copolymer obtained by a polycondensation reaction of a polyoxyalkylene compound represented by Chemical Formula 2 and a product obtained by esterification of a diol compound with a dicarboxylic acid compound can be used. A resin molded article having excellent resistance to discoloration and reflectance is formed, and the resin molded article can have an improved impact strength.

The present PCT copolymer is a copolymer comprising both a PCT basic repeating unit (e.g., the structure of Chemical Formula 1) and another repeating unit formed by a polyoxyalkylene compound (e.g., the structure of Chemical Formula 2). The present PCT copolymer has improved intrinsic physical properties compared to conventional PCT. Thus, the PCT copolymers of the present invention can be made without the use of additional additives as compared to known PCT compositions, such as mixed components including PCT and other additives to improve their physical properties. The formed resin molded article has improved physical properties, particularly an improvement in properties such as impact strength, color resistance, and reflectance.

In the PCT copolymer of one embodiment, the repeating unit of Chemical Formula 1 may be represented by a diol Esterification of a compound such as 1,4-cyclohexanedimethanol with a dicarboxylic acid compound such as terephthalic acid, dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate Formed by a reaction and a polycondensation reaction.

In the repeating unit of Chemical Formula 1, n is not particularly limited. However, in accordance with an embodiment of the invention, n is greater than or equal to 5, and preferably may be between 5 and 300, between 5 and 200, between 5 and 150, or between 5 and 100, in order to enable the PCT The copolymer can have the desired physical properties.

The polyoxyalkylene compound of Chemical Formula 2 is subjected to a polycondensation reaction with the above-mentioned product obtained by esterification of a diol compound with a dicarboxylic acid compound, and the repeating unit thus produced may be included in the present PCT copolymer.

In the polyoxyalkylene compound of Chemical Formula 2, R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or independently substituted or unsubstituted. Substituting an aryl group having 6 to 18 carbon atoms. For example, R ¹ to R ⁴ may each independently be an alkyl group (eg, methyl, ethyl, propyl, butyl, etc.) or an aromatic group (eg, phenyl, naphthyl, etc.), and the alkyl group and The hydrogen atom in the aromatic group may be substituted by an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aromatic group having 6 to 10 carbon atoms, or the like. Was replaced.

In the polyoxyalkylene compound of Chemical Formula 2, D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 4 to 10 carbon atoms ( Alicyclic hydrocarbyl group). For example, D ¹ and D ² may each independently be an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aromatic group having 6 to 10 carbon atoms.

In the polyoxyalkylene compound of Chemical Formula 2, L ¹ and L ² are terminal groups including a hydroxyl group, and L ¹ and L ² may each independently be a hydroxyl group or a hydroxy phenyl group. .

In the polyoxyalkylene compound of Chemical Formula 2, m is greater than or equal to 5, and preferably may be between 5 and 300, between 5 and 200, between 5 and 150, or between 5 and 100, in order to reach The introduction effect of the repeating unit formed from the polyoxyalkylene compound and ensuring that the PCT copolymer can have the desired physical properties.

In an example not limited thereto, the polyoxyalkylene compound of Chemical Formula 2 may have a weight average molecular weight of between 500 and 15,000, and preferably between 1000 and 15,000 or Between 1000 and 12,000, in order to achieve the introduction effect of the repeating unit formed from the polyoxyalkylene compound, and to ensure that the PCT copolymer can have the desired physical properties.

Further, according to an embodiment, in the poly(cyclohexane) dimethanol terephthalate copolymer, the weight percentage of the repeating unit formed by the polyoxyalkylene compound is between 0.1% and 30%, and It may preferably be between 0.1% and 25%, between 1% and 20% or between 1% and 15%. That is to say, during the preparation process, an excess of repeating units may be discharged from the inside of the reaction tank, and the composition of the repeating unit may preferably be adjusted within the above range by introducing a repeating unit formed of a polyoxyalkylene compound. To achieve the desired effect of improving impact strength.

The polybutylene terephthalate copolymer may have a weight average molecular weight of between 10,000 and 100,000 or between 30,000 and 80,000, and the polyterephthalic acid ring The number average molecular weight of the alkane dimethanol ester copolymer may be between 10,000 and 50,000 or between 15,000 and 35,000. Between, it is beneficial to obtain the required structural characteristics.

The intrinsic viscosity of the poly(cyclohexanedimethylene terephthalate) copolymer is less than or equal to 11 dl/g, or between 0.5 dl/g and 1.0 dl/g, which is beneficial to achieve the desired Processability.

II. Method for preparing PCT copolymer

Meanwhile, another embodiment of the present invention provides a method for preparing the polycyclohexylene dimethylene terephthalate copolymer, which comprises the following steps. Mixing a diol compound, a dicarboxylic acid compound, and a polysiloxane compound represented by Chemical Formula 2, and performing an esterification reaction by a catalyst; The product of the esterification reaction undergoes a polycondensation reaction.

According to an embodiment, in the esterification reaction, a diol compound containing 1,4-cyclohexanedimethanol and terephthalic acid, terephthalic acid may be used. Dicarboxylic acid compound of dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate.

Further, in the esterification reaction, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol can also be used. (1,3-propanediol) and a glycol compound of neopentyl glycol, and, for example, isophthalic acid, 2,6-naphthalenedicarboxylic acid , dimethyl isophthalate and dicarboxylic acid compound of dimethyl 2,6-naphthalenedicarboxylate. However, in order to secure the essential physical properties of the PCT copolymer, it is preferred to use 80 mol% or more of 1,4-cyclohexanedimethanol as the diol. A compound, and a mixture of 80 mol% or more of terephthalic acid, dimethyl terephthalate or terephthalic acid and dimethyl terephthalate is used as the dicarboxylic acid compound.

Further, in order to ensure the efficiency of the correct esterification reaction, the esterification reaction is preferably carried out as a composition, and the composition is based on 100 parts by weight (pbw) of the diol compound. The dicarboxylic acid compound is contained in an amount of from 90 to 110 parts by weight, or the dicarboxylic acid compound is contained in an amount of from 80 to 100 or from 75 to 90 parts by weight.

Meanwhile, the weight fraction of the polyoxyalkylene compound may be between 0.01 and 10, or between 0.1 and 10, or based on 100 parts by weight of the diol compound used in the esterification reaction. Between 1 and 5. That is to say, in the preparation process, an excess of repeating units may be discharged from the inside of the reaction tank, and the content of the polyoxyalkylene compound may preferably be adjusted within the above range, and formed by introducing a polyoxane compound. The repeating unit is used to achieve the desired effect of improving the impact strength.

Further, the esterification reaction can be carried out by a catalyst, preferably a titanium-based catalyst. In an example not limited thereto, the titanium-based catalyst may include one or more compounds selected from the group consisting of titanium oxide, titanium chelate compound, and tetrapropyl titanate. (tetra-n-propyl titanate), tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and titanium In the group consisting of butyl-isopropyl titanate.

At this time, in the titanium-based catalyst, the content of the titanium atom is preferably adjusted to be equal to or less than 20 ppm based on the weight of the final PCT copolymer. That is, it is considered that, for example, the resin causes a problem such as yellowing (increased in color-b) due to an excessive amount of a catalyst or a side reaction caused by a decrease in molecular weight in the process, and the content of the catalyst is preferably. Can be adjusted within the above range, To cause the correct polycondensation reaction.

In the esterification reaction, a phosphorus stabilizer can be further utilized to ensure thermal stability. The phosphorus stabilizer may be one or more compounds selected from the group consisting of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonium acetate (triethyl phosphate). Triethyl phosphonoacetate), phosphoric acid, and phosphorous acid.

In order to obtain the desired effect with the added stabilizer, the weight percentage of the phosphorus stabilizer may be between 0.001 and 5, between 0.01 and 5 or 0.01 to 1 based on 100 parts by weight of the glycol compound. between. Alternatively, in the phosphorus stabilizer, the content of the phosphorus atom is preferably adjusted to be equal to or less than 30 ppm based on the weight of the final PCT copolymer. If the content of the phosphorus stabilizer exceeds 30 ppm, the color of the copolymer is deteriorated, and the catalytic activity of the polycondensation reaction is also lowered, thereby affecting the reaction time and the degree of polymerization.

This esterification reaction can be carried out under typical conditions, for example, preferably at a temperature of from 230 ° C to 290 ° C and a pressure of from 0.01 kg / cm ² to 3.0 / cm ² for from 120 minutes to 600 minutes.

Further, after the esterification reaction, the product of the esterification reaction can undergo a polycondensation reaction. According to an embodiment, the polycondensation reaction can be carried out after the esterification reaction. The polycondensation reaction can be carried out under typical conditions, for example, at a temperature of from 290 ° C to 320 ° C and a pressure of from 0.1 torr to 2.0 Torr for 60 minutes to 360 minutes.

If desired, the method of preparing a PCT copolymer of the present embodiment may comprise a typical resin preparation step, such as extruding a product of a polycondensation reaction to prepare a pellet, and The particulate matter is crystallized for solid phase polymerization.

III. resin molded article (resin molded article)

Further, still another embodiment of the present invention provides a resin molded article made of the above-mentioned poly(cyclohexanedimethylene terephthalate) copolymer.

Since the resin molded article is made of the poly(cyclohexanedimethylene terephthalate) copolymer, it is improved compared to known PCT compositions (such as mixed components including PCT and other additives). The physical properties thereof, the resin molded article of the present invention can have enhanced physical properties (especially improvement in properties such as impact strength, resistance to discoloration, and reflectance) without using additional additives.

More specifically, the resin molded article may have an impact strength (tested by ASTM D256) of greater than or equal to 20 J/m, and preferably between 20 and 100 J/m or between 20 and 85 J/m. Between when the thickness of the sample is 1/8 于 at 25 °C.

Further, the resin molded article can have excellent heat resistance and discoloration resistance, so that the color space L*-b* of the resin molded article after 48 hours in an environment of being placed at 140 ° C (color L*- b* value) may be greater than or equal to 95% of the value of the starting color space L*-b* of the resin molded article at room temperature.

Further, the resin molded article can maintain excellent reflectance in a harsh environment, so that the resin molded article has a reflectance for a wavelength of 450 nm or more greater than or equal to the resin after being placed in an environment of 140 ° C for 48 hours. The molded article was 95% of the initial reflectance at a wavelength of 450 nm at room temperature.

Therefore, the resin molded article can be used for a housing of a light-emitting diode, a reflector of a light-emitting diode, or an outer cover of various other light-emitting devices, and the light-emitting device can be continuously exposed to light and heat. The resin molded article can also be used in an electronic device that can perform surface mounting technology at a high temperature.

The beneficial effects of the present invention are described below. The poly(cyclohexylene dimethylene terephthalate) copolymer of the present invention has excellent intrinsic physical properties, and thus can be provided without additional additives. The resin molded article has improved impact strength, resistance to discoloration, and reflectivity. The resin molded article can maintain the original excellent physical properties under continuous exposure to light and heat, so it is suitable for use in an object such as a cover and a reflector of a light-emitting diode.

In the following, several preferred examples will be provided to better understand the invention. However, the following examples are for illustrative purposes only, and the invention is not limited by this example.

Example 1

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, and about 0.4 g of triethyl phosphate ), about 38 g of polydimethylsiloxane (in the chemical formula 2, R ¹ to R ⁴ are each a methyl group, and D ¹ and D ² are respectively a propylene group, L ¹ and L ² are each a hydroxyl group, and the weight average molecular weight Mw is 2253] and about 0.15 g of a titanium oxide-based catalyst (Sachtleben's Hombifast PC, wherein the effective ratio of titanium to the catalyst is 15%). The mixture was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature raised to 280 °C.

Next, the product of the esterification reaction is subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 torr to obtain a poly(cyclohexylenedimethylene). Terephthalate) copolymer having a weight average molecular weight Mw of 51,000, a number average molecular weight Mn of 25,000, and an intrinsic viscosity of 0.73 dl/g.

Example 2

About 46 kg of 1,4-cyclohexanedimethanol (trans 70%), about 36 kg of terephthalic acid, about 8.7 g of triethyl phosphate, about 911 g of polydimethyl decane (in In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 2253) and about 4.1 g of titanium oxide. The base catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature of 280 ° C. .

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 53,225, the number average molecular weight Mn was 23,945, and the intrinsic viscosity was 0.68 dl/g).

Example 3

About 732 kg of 1,4-cyclohexanedimethanol (trans 70%), about 600 kg of terephthalic acid, about 108 g of triethyl phosphate, and about 15.2 kg of polydimethyl decane ( In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 2253) and an oxidation of about 35.8 g. A titanium-based catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and at a temperature of 280 ° C. hour.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 47,168, the number average molecular weight Mn was 21,886, and the intrinsic viscosity was 0.64 dl/g).

Example 4

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, and about 19 g of polydimethyloxane (in In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 2253) and about 0.15 g of titanium oxide. The base catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature of 280 ° C. .

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 51,295, the number average molecular weight Mn was 24,549, and the intrinsic viscosity was 0.71 dl/g).

Example 5

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, and about 57 g of polydimethylsiloxane [polydimethylsiloxane] In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 2253] and about 0.15 g. A titanium oxide-based catalyst (Sachtleben's Hombifast PC in which the effective ratio of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and at a temperature of 280 ° C. 3 hours.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 49,985, the number average molecular weight Mn was 23,750, and the intrinsic viscosity was 0.65 dl/g).

Example 6

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethyloxane (in In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 1418) and about 0.15 g of titanium oxide. The base catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature of 280 ° C. .

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 51,769, the number average molecular weight Mn was 23,084, and the intrinsic viscosity was 0.71 dl/g).

Example 7

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethyloxane (in In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 2253) and about 0.15 g of titanium oxide. The base catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature of 280 ° C. .

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 51,622, the number average molecular weight Mn was 22,106, and the intrinsic viscosity was 0.69 dl/g).

Example 8

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethyloxane (in In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 4172) and about 0.15 g of titanium oxide. The base catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature of 280 ° C. .

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain a poly(cyclohexanedimethylene terephthalate) copolymer (the weight average molecular weight thereof). Mw was 52,551, the number average molecular weight Mn was 22,726, and the intrinsic viscosity was 0.70 dl/g).

Example 9

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethyloxane (in In Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxyl group, and a weight average molecular weight Mw is 9178) and about 0.15 g of titanium oxide. The base catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature of 280 ° C. .

Next, the product of the esterification reaction is subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain poly(cyclohexylene dimethylene terephthalate). The copolymer (having a weight average molecular weight Mw of 49,016, a number average molecular weight Mn of 21,627, and an intrinsic viscosity of 0.67 dl/g).

Comparative example 1

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, and about 0.15 g of titania-based catalyst (Sachtleben) The Hombifast PC, in which the effective ratio of titanium to the catalyst was 15%, was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature elevated to 280 °C.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain poly(cyclohexanedimethylene terephthalate) (the weight average molecular weight Mw thereof was 50,349, the number average molecular weight Mn was 23,800, and the intrinsic viscosity was 0.65 dl/g).

Comparative example 2

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, and about 38 g of polytetramethylene (polytetramethylene) Glycol) and about 0.15 grams of a titanium oxide based catalyst (Sachtleben's Hombifast PC, in which the effective ratio of titanium in the catalyst is 15%) is injected into a reactor together at atmospheric pressure. The esterification reaction was carried out for 3 hours while the temperature was raised to 280 °C.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain poly(cyclohexanedimethylene terephthalate) (the weight average molecular weight Mw thereof was 52,000, the number average molecular weight Mn was 24,500, and the intrinsic viscosity was 0.69 dl/g).

Comparative example 3

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 36 kg of terephthalic acid, about 6.5 g of triethyl phosphate, and about 4.15 g of titanium oxide based catalyst (Sachtleben) The Hombifast PC, in which the effective ratio of titanium to the catalyst was 15%, was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature elevated to 280 °C.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain poly(cyclohexanedimethylene terephthalate) (the weight average molecular weight Mw thereof was 48,637, the number average molecular weight Mn was 22,406, and the intrinsic viscosity was 0.67 dl/g).

Comparative example 4

About 732 kg of 1,4-cyclohexanedimethanol (trans 70%), about 600 kg of terephthalic acid, about 108 g of triethyl phosphate, and about 35.8 g of titanium oxide-based catalyst (Sachtleben) The Hombifast PC, in which the effective ratio of titanium to the catalyst was 15%, was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature elevated to 280 °C.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain poly(cyclohexanedimethylene terephthalate). The average molecular weight Mw was 46,708, the number average molecular weight Mn was 22,225, and the intrinsic viscosity was 0.66 dl/g.

Comparative Example 5

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 38 g of octamethylcyclotetrasiloxane, about 0.4 g of phosphoric acid Ethyl ester and about 0.15 grams of titanium oxide based catalyst (Sachtleben's Hombifast PC, where the effective ratio of titanium in the catalyst is 15%) is injected into a reactor at atmospheric pressure and the temperature is raised to 280 ° C. The esterification reaction was carried out for 3 hours.

Next, the product of the esterification reaction was subjected to a polycondensation reaction at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr for 150 minutes to obtain poly(cyclohexanedimethylene terephthalate) (the weight average molecular weight Mw thereof was 48,000, the number average molecular weight Mn was 23,000, and the intrinsic viscosity was 0.68 dl/g).

Comparative Example 6

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, and about 0.15 g of titania-based catalyst (Sachtleben) The Hombifast PC, in which the effective ratio of titanium to the catalyst was 15%, was injected into a reactor together, and the esterification reaction was carried out for 3 hours under atmospheric pressure and at a temperature elevated to 280 °C. Next, the product of the esterification reaction was subjected to a polycondensation reaction for 150 minutes at a temperature of 300 ° C and a pressure of 0.5 to 1 Torr.

Then, about 57 g of polydimethyloxane is added (in Chemical Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, and L ¹ and L ² are each a hydroxyl group, respectively. And the weight average molecular weight Mw was 2253) and stirred for 10 minutes to obtain a mixture of poly(cyclohexanedimethylene terephthalate) having a weight average molecular weight Mw of 28,158, a number average molecular weight Mn of 13,743 and an intrinsic viscosity of 0.47. Dl/g).

Experimental example 1

The PCT resin obtained in each of the examples and the comparative examples was dissolved in o-chlorophenol at a concentration of 1.2 g/dl, and then the intrinsic viscosity was measured by a Ubbelohde viscometer.

At this time, the temperature of the Ubbelode viscometer was maintained at 35 °C. When the solvent or solution flows through the ablux section of the ab section in the viscometer as t and t ₀ , respectively, the specific viscosity can be defined by the following equation 1, and the essence can be calculated by the following equation 2 Intrinsic viscosity.

In Equation 2, A represents a Huggins constant of 0.247, and c is a concentration value of 1.2 g/dl.

Experimental example 2

Each of the samples of the PCT resin obtained from each of the examples and the comparative examples was measured for the value of the initial color space L ^* -b ^* (color L*-b* value) at room temperature by the CIE LAB specification. The measured sample is placed at 140 ° C, and the color space L ^* -b ^* is measured at different time points, and the results are listed in Table 1 and Table 2 below. in.

The CIE LAB specification is used for color metrics. CIE LAB system for CIE based people The chrominance space defined by the class-aware relative color theory, such as yellow-blue and green-red. The L* value represents brightness (its value is 0 to 100, 0 is black, 100 is white), and the a* value represents green to red ([+] for red, [-] for green, and the median is close to 0), The b* value represents yellow to green ([+] stands for yellow, and [-] stands for blue, while the median is close to 0).

Experimental example 3

Each sample of the PCT resin obtained from each of the examples and the comparative examples was measured for its initial reflectance for blue light (wavelength of 450 nm). The same sample after measurement was placed at 140 ° C, and the reflectance measurement for blue light (wavelength of 450 nm) was performed at different time points, and the results are listed in Table 3 below. 4 in.

Table 4

Experimental example 4

The PCT resin obtained from each of the examples and the comparative examples was made into a sample having a thickness of 1/8 Torr, and the impact strength measurement was carried out [notched Izod] at a temperature of 25 ° C at ASTM D256. Test under the condition], and the results are listed in Table 5 below.

Referring to Tables 1 to 5, the samples prepared from the PCT copolymers of the respective examples exhibited high impact strength (higher than or equal to 20 J/m), and the results were about twice that of the comparative examples. In addition, the samples prepared from the PCT copolymers of the respective examples exhibited values and reflectances of the color space L*-b* which retained 95% or more of the initial value after deterioration, representing the relative to the comparative example. It has better resistance to discoloration and high reflectivity.

In particular, in Comparative Example 5, a siloxane compound having no terminal hydroxyl group was used without reacting with a dicarboxylic acid, so that the effect of adding oxoxane did not occur.

In Comparative Example 6, when polyfluorene oxide was added after the polycondensation reaction and physically mixed, thermal decomposition occurred in the mixing process to cause problems such as a decrease in molecular weight and color deterioration. In addition, the injection of polyoxyalkylene does not significantly enhance physical properties due to dispersion problems.

The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should be within the scope of the present invention.

Claims (15)

A poly(cyclohexylene dimethylene terephthalate) copolymer comprising: a repeating unit represented by the following Chemical Formula 1: And another repeating unit formed by a polysiloxane compound represented by the following Chemical Formula 2: Wherein in the chemical formula 2, R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or independently substituted or unsubstituted 6 An aryl group of up to 18 carbon atoms; D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic ring having 4 to 10 carbon atoms An alicyclic hydrocarbyl group; L ¹ and L ² are each independently a hydroxyl group or a hydroxy phenyl group; and n and m are each independently an integer of 5 to 300. The poly(cyclohexanedimethylene terephthalate) copolymer according to claim 1, wherein the repeating unit formed of the polyoxyalkylene compound is in the poly(cyclohexanedimethylene terephthalate) copolymer. The weight percentage is between 0.1% and 30%. The poly(cyclohexanedimethylene terephthalate) copolymer according to claim 1, wherein the polybutylene terephthalate copolymer has a weight average molecular weight of 10,000. Between 100 and 10,000, and the number average molecular weight of the poly(cyclohexanedimethylene terephthalate) copolymer is between 10,000 and 50,000. The poly(cyclohexanedimethylene terephthalate) copolymer according to claim 1, wherein the intrinsic viscosity of the poly(cyclohexanedimethylene terephthalate) copolymer is less than or equal to 11 dl/ g. A method for preparing a poly(cyclohexylene dimethylene terephthalate) copolymer according to claim 1, comprising the steps of: mixing a diol compound, a dicarboxylic acid compound and a polysiloxane compound represented by the following Chemical Formula 2, and an esterification reaction by a catalyst; and a polycondensation of the product of the esterification reaction (polycondensation) reaction: Wherein in the chemical formula 2, R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or independently substituted or unsubstituted 6 An aryl group of up to 18 carbon atoms; D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic ring having 4 to 10 carbon atoms An alicyclic hydrocarbyl group; L ¹ and L ² are each independently a hydroxyl group or a hydroxy phenyl group; and m is an integer of 5 to 300. The method of claim 5, wherein the esterification reaction is carried out as a composition based on 100 parts by weight (pbw) of the diol compound, the composition comprising parts by weight The dicarboxylic acid compound between 90 and 110 and the polyoxyalkylene compound in an amount of between 0.01 and 10, wherein the diol compound comprises 1,4-cyclohexanedimethanol (1, 4) -cyclohexanedimethanol), and the dicarboxylic acid compound comprises terephthalic acid, dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate. The method of claim 6, wherein the composition of the esterification reaction further comprises one or more phosphorus stabilizers in a part by weight of from 0.001 to 5 based on 100 parts by weight of the glycol compound. Phosphorus stabilizer, and the phosphorus stabilizer is selected from the group consisting of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonium acetate In the group consisting of triethyl phosphonoacetate, phosphoric acid, and phosphorous acid. The method of claim 5, wherein the esterification reaction is carried out for 120 minutes to 600 minutes at a temperature of from 230 ° C to 290 ° C and a pressure of from 0.01 kg / cm ² to 3.0 / cm ² . The method of claim 5, wherein the catalyst is one or more compositions selected from the group consisting of titanium oxide, titanium chelate compound, tetrapropyl titanate (tetra-). N-propyl titanate), tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl titanate four In the group consisting of butyl-isopropyl titanate. The method of claim 5, wherein the polycondensation reaction is carried out for 60 minutes to 360 minutes at a temperature of from 290 ° C to 320 ° C and a pressure of from 0.1 torr to 2.0 Torr. A resin molded article, wherein the resin molded article is made of the polycyclohexane dimethanol terephthalate copolymer as described in claim 1. The resin molded article according to claim 11, wherein the resin molded article has an impact strength (tested by ASTM D256) of 20 J/m or more, and when the thickness of the sample is 1/8 Torr at 25 ° C, . The resin molded article according to claim 11, wherein the color space L*-b* value (color L*-b* value) of the resin molded article is greater than or after being placed in an environment of 140 ° C for 48 hours. It is equal to 95% of the value of the initial color space L*-b* of the resin molded article at room temperature. The resin molded article according to claim 11, wherein the resin molded article has a reflectance for a wavelength of 450 nm greater than or equal to a wavelength of the resin molded article at room temperature for 48 hours after being placed in an environment of 140 ° C. 95% of the initial reflectance at 450 nm. The resin molded article according to claim 11, wherein the resin molded article is used for a housing or a reflector of a light-emitting diode.