TWI653260B - Polybutylene terephthalate dimethanol ester copolymer having improved impact strength, color resistance and reflectivity, and resin molded article made therefrom - Google Patents

Abstract

The invention relates to a poly (cyclohexylenedimethylene terephthalate) copolymer and a resin molded product made therefrom. The copolymer of the present invention has excellent intrinsic physical properties. Therefore, even without additional additives, the resulting resin molded product can have improved impact strength, discoloration resistance, and reflectivity. Under continuous exposure to high temperature and light, the resin molded product can still maintain excellent initial physical properties, and the resin molded product is therefore suitable for use in objects such as light-emitting diode covers or reflectors.

Description

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

The invention relates to a poly (cyclohexylenedimethylene terephthalate) copolymer with improved impact strength, anti-tarnishing ability and reflectivity, and a resin molded product made therefrom.

Due to excellent physical properties such as wear resistance, high durability, and thermal stability, polyalkylene terephthalate [poly (alkylene terephthalate)] materials have been widely used in fibers, molds, and molded products ( molded article) and other items. Commercially available polyalkylene terephthalate materials include polyethylene terephthalate [poly (ethylene terephthalate), PET], polybutylene terephthalate [poly (butylene terephthalate), PBT ] And poly (1,4-cyclohexylenedimethylene terephthalate), PCT], etc.

Among them, PCT has attracted more attention and is regarded as a new material that can overcome the problems of some polyester materials such as PET and PBT. The problem with the above-mentioned materials is that the moldability is lowered due to the slower crystallization rate, and the application is limited due to the lower heat deflection temperature.

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

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

PCT can be used in electronic devices that will perform surface mounting technology at high temperatures, or for housings that will be continuously exposed to light and thermal emitting diodes (LEDs) during use ) Or reflector.

As the application range of PCT continues to expand, many additives such as stabilizers or glass fibers are proposed to improve the color and crystalline quality of PCT. However, most of the methods are only related to the compounds with PCT, and cannot be regarded as ways to improve the physical properties of PCT itself.

The invention provides a poly (cyclohexylenedimethylene terephthalate) copolymer, which can provide a tree made from this Resin molded article has improved impact strength, excellent resistance to discoloration and reflectivity.

In addition, the present invention provides a resin molded product made of poly (cyclohexylenedimethylene terephthalate) copolymer.

The following describes the method of the present invention to achieve the above object.

The invention provides a poly (cyclohexylenedimethylene terephthalate) copolymer, comprising: a repeating unit represented by the following chemical formula 1; and a polysiloxane represented by the following chemical formula 2 ) Another repeating unit formed by the compound.

In Chemical Formula 2, R ¹ to R ⁴ are independently substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms or independently substituted or unsubstituted having 6 to 18 Aryl group of one carbon atom. D ¹ and D ² are 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 independently a hydroxyl group or a hydroxy phenyl group, and n and m are independently integers of 5 to 300, respectively.

In the present invention, the weight percentage of the repeating unit formed with the polysiloxane compound in the polycyclohexanedimethylene terephthalate copolymer is between 0.1% and 30%.

The weight-average molecular weight of the polycyclohexane terephthalate copolymer The average molecular weight may be between 10,000 and 100,000, and the number average molecular weight of the polycyclohexane terephthalate copolymer may be between 10,000 and 50,000.

The invention provides a method for preparing the polycyclohexylenedimethylene terephthalate copolymer (copolymer), which includes 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 performed 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 in a composition, based on 100 parts by weight (pbw) of the diol compound, the composition includes the parts by weight of 90 to 110 A dicarboxylic acid compound and the polysiloxane compound having a weight fraction of 0.01 to 10, wherein the glycol compound includes 1,4-cyclohexanedimethanol, and the dicarboxylic acid The compound contains terephthalic acid, dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate.

Based on 100 parts by weight of the diol compound, if necessary, the composition of the esterification reaction may further include one or more phosphorus stabilizers in parts by weight of 0.001 to 5 (phosphorus stabilizer), and the phosphorus stabilizer can be selected from trimethyl phosphate (trimethyl phosphate), triethyl phosphate (triethyl phosphate), triphenyl phosphate (triphenyl phosphate), triethylphosphonoacetate (triethyl phosphonoacetate), phosphoric acid and phosphorous acid.

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

In the present invention, the catalyst may be one or more of the catalysts selected from a 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 tetra-isobutyl titanate Propyl (butyl-isopropyl titanate) in the group.

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

In addition, the present invention provides a resin molded article made of the polycyclohexane terephthalate copolymer described above.

In the present invention, the impact strength (impact strength, the ASTM D256 test) can be greater than or equal to 20J / m, when the thickness of the sample is 1/8 inch at 25 ℃.

In addition, the color space L * -b * value (color L * -b * value) of the resin molded product may be greater than or equal to the room temperature of the resin molded product after being placed in a 140 ° C environment for 48 hours 95% of the value of the initial color space L * -b *.

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

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

In the following, the preparation method of the polycyclohexylenedimethylene terephthalate copolymer and the polycyclohexylenedimethylene terephthalate copolymer of the present invention and the polyterephthalate Each example of a resin molded article made of cyclohexane dimethanol formate copolymer will be described in detail.

Before that, it must be explained that the technical terminology used here is to illustrate specific embodiments, and unless specifically stated otherwise, the present invention should not be limited thereby. As long as there is no special antisense, the singular form used here also means the form including the plural form. In addition, "including (including)" as used herein is an open-ended term that describes the features, regions, wholes, steps, operations, units, and / or components described, but is not limited to the exclusion of additional features, Region, whole, step, operation, unit, composition or / and group.

I. PCT copolymer

An embodiment of the present invention provides a poly (cyclohexylenedimethylene terephthalate) copolymer (referred to as PCT copolymer for short) including a repeating unit represented by the following chemical formula 1; and the following chemical formula 2 Another repeating unit formed by the polysiloxane compound presented.

In Chemical Formula 2, R ¹ to R ⁴ are independently substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms or independently substituted or unsubstituted having 6 to 18 Aryl group of one carbon atom. D ¹ and D ² are 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 independently a hydroxyl group or a hydroxy phenyl group, and n and m are independently integers of 5 to 300, respectively.

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

The PCT copolymer is a copolymer that includes a PCT basic repeating unit (such as the structure of Chemical Formula 1) and another repeating unit formed with a polysiloxane compound (such as the structure of Chemical Formula 2). Compared with traditional PCT, this PCT copolymer has improved essential physical properties. Therefore, compared with the known PCT composition (such as a mixed component including PCT and other additives to improve its physical properties), the PCT copolymer of the present invention can be used without additional additives. The formed resin molded product has improved physical properties, especially the improvement of properties such as impact strength, color resistance and reflectivity.

In one embodiment of the PCT copolymer, the repeating unit of Chemical Formula 1 can be Esterification of compounds (eg 1,4-cyclohexanedimethanol) with dicarboxylic acid compounds (eg terephthalic acid, dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate) Chemical reaction and polycondensation reaction.

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

The polysiloxane compound of Chemical Formula 2 undergoes a polycondensation reaction with the product of the above-mentioned esterification reaction of the diol compound and the dicarboxylic acid compound, and the repeating unit generated thereby may be included in the present PCT copolymer.

In the polysiloxane compound of Chemical Formula 2, R ¹ to R ⁴ are independently substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms or independently substituted or unsubstituted Substitute an aryl group having 6 to 18 carbon atoms. For example, R ¹ to R ⁴ may independently be an alkyl group (such as methyl, ethyl, propyl, butyl, etc.) or an aromatic group (such as phenyl, naphthyl, etc.), and the alkyl group may be The hydrogen atom in the aromatic group may be substituted or unsubstituted 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, etc. Was replaced.

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

In the polysiloxane compound of Chemical Formula 2, m is greater than or equal to 5, and preferably may be between 5 to 300, 5 to 200, 5 to 150, or 5 to 100, in order to achieve The introduction of repeating units formed from polysiloxane compounds ensures that the PCT copolymer can have the required physical properties.

In an example not limited to this, the weight average molecular weight of the polysiloxane compound of Chemical Formula 2 may be between 500 and 15,000, and preferably between 1000 and 15,000 or Between 1000 and 12,000 in order to achieve the effect of introducing repeating units formed from polysiloxane compounds and to ensure that the PCT copolymer can have the required physical properties.

In addition, according to an embodiment, in the polycyclohexanedimethylene terephthalate copolymer, the weight percentage of the repeating unit formed with a polysiloxane compound is between 0.1% and 30%, and Preferably, it may be between 0.1% to 25%, 1% to 20%, or 1% to 15%. That is to say, during the preparation process, excess repeating units can be discharged from the reaction tank, and the composition of the repeating unit can preferably be adjusted within the above range, by introducing the repeating unit formed of polysiloxane compound , To achieve the desired effect of improving the impact strength.

The weight-average molecular weight of the polycyclohexane terephthalate copolymer The average molecular weight can be between 10,000 and 100,000 or between 30,000 and 80,000, and the number average molecular weight of the polycyclohexane terephthalate copolymer can be between 10,000 Between 50,000 and 15,000 to 35,000 Between, is conducive to obtain the required structural characteristics.

The intrinsic viscosity of the polycyclohexane terephthalate copolymer is less than or equal to 11dl / g, or between 0.5dl / g and 1.0dl / 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 polycyclohexylenedimethylene terephthalate copolymer (copolymer), including 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 with a catalyst; and 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 and terephthalic acid can be used Dicarboxylic acid compound of dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate.

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

In addition, in order to ensure the efficiency of performing the correct esterification reaction, the esterification reaction is preferably carried out with a composition, and based on 100 parts by weight (pbw) of the diol compound, the composition The dicarboxylic acid compound is included in 90 to 110 parts by weight, or the dicarboxylic acid compound is 80 to 100 or 75 to 90 parts by weight.

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

In addition, the esterification reaction can be carried out by a catalyst (preferably a titanium-based catalyst). In an example not limited to this, the titanium-based catalyst may include one or more compounds selected from a 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 formed by butyl-isopropyl titanate.

At this time, in the titanium-based catalyst, based on the weight of the final PCT copolymer, the content of titanium atoms is preferably adjustable to be equal to or less than 20 ppm. That is to say, considering that the resin (resin) causes problems such as yellowing (increased in color-b) due to side reactions caused by excessive catalyst or molecular weight reduction in the process, the content of the catalyst is preferably It can be adjusted within the above range, In order to cause the correct polycondensation reaction.

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

In order to obtain the desired effect with the added stabilizer, based on 100 parts by weight of the glycol compound, the weight parts of the phosphorus stabilizer may be between 0.001 to 5, 0.01 to 5, or 0.01 to 1. between. Alternatively, in the phosphorus stabilizer, based on the weight of the final PCT copolymer, the content of phosphorus atoms is preferably adjustable to be equal to or less than 30 ppm. If the content of the phosphorus stabilizer exceeds 30 ppm, the color of the copolymer will deteriorate, and the catalytic activity of the polycondensation reaction will also decrease, which will affect the reaction time and the degree of polymerization.

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

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

If necessary, the method for preparing a PCT copolymer in this embodiment may include a typical resin manufacturing step, such as extruding the product of the polycondensation reaction to prepare a pellet, and The particulate matter is crystallized to perform solid-phase polymerization.

III. Resin molded article

In addition, another embodiment of the present invention provides a resin molded article made of the above-mentioned polycyclohexane terephthalate copolymer.

Since the resin molded product is made of the polycyclohexanedimethylene terephthalate copolymer, compared with the known PCT composition (such as the mixed components including PCT and other additives to improve Its physical properties), the resin molded article of the present invention can have enhanced physical properties (especially the improvement of impact strength, discoloration resistance, reflectivity and other properties) without using additional additives.

More specifically, the impact strength of the resin molded product (ASTM (D256 test) can be greater than or equal to 20J / m, and preferably between 20-100J / m or between 20-85J / m, when the thickness of the sample is 1/8 inch at 25 ° C.

In addition, the resin molded product can have excellent heat resistance and resistance to discoloration, so that the color space L * -b * value of the resin molded product (color L *- b * value) may be greater than or equal to 95% of the initial color space L * -b * value of the resin molded product at room temperature.

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

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

The beneficial effects of the present invention are described below. The poly (cyclohexylenedimethylene terephthalate) copolymer (copolymer) of the present invention has excellent intrinsic physical properties, and therefore can be provided in the absence of additional additives. The resin molded article has improved impact strength, resistance to discoloration and reflectivity. Under continuous exposure to light and heat, this resin molded product can still maintain its original excellent physical properties, so it is suitable for applications such as light-emitting diode covers and reflectors.

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

Example 1

Approximately 1.7 kg of 1,4-cyclohexanedimethanol (70% trans), approximately 1.5 kg of terephthalic acid, and approximately 0.4 g of triethyl phosphate (triethyl phosphate) ), About 38 grams of polydimethylsiloxane [polydimethylsiloxane, in Chemical Formula 2, R ¹ to R ⁴ are respectively methyl group (methyl group), D ¹ and D ² are respectively propylene group (propylene group), L ¹ and L ² are hydroxyl groups, respectively, and the weight-average molecular weight Mw is 2253] and about 0.15 g of titanium oxide-based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15% ) It is injected into a reactor together, and the esterification reaction is carried out for 3 hours under the condition of atmospheric pressure and temperature rising 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 for 150 minutes to obtain poly (cyclohexylenedimethylene terephthalate) terephthalate)] copolymer (its weight average molecular weight Mw is 51,000, number average molecular weight Mn is 25,000, and intrinsic viscosity is 0.73dl / g).

Example 2

About 46 kg of 1,4-cyclohexane dimethanol (trans 70%), about 36 kg of terephthalic acid, about 8.7 g of triethyl phosphate, and about 911 g of polydimethylsiloxane (in In Chemical Formula 2, R ¹ to R ⁴ are respectively methyl groups, D ¹ and D ² are respectively propylene groups, L ¹ and L ² are respectively hydroxyl groups, and the weight average molecular weight Mw is 2253) and about 4.1 g of titanium oxide Based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 280 ° C 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 a poly (cyclohexanedimethylene terephthalate) copolymer (whose weight average molecular weight Mw is 53,225, the number average molecular weight Mn is 23,945, and the intrinsic viscosity is 0.68dl / g).

Example 3

Approximately 732 kg of 1,4-cyclohexanedimethanol (trans 70%), approximately 600 kg of terephthalic acid, approximately 108 g of triethyl phosphate, and approximately 15.2 kg of polydimethylsiloxane ( In Chemical Formula 2, R ¹ to R ⁴ are methyl groups, D ¹ and D ² are propylene groups, L ¹ and L ² are hydroxyl groups, and the weight average molecular weight (Mw is 2253) and about 35.8 grams of oxidation Titanium-based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 280 ° C3 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 (whose weight average molecular weight Mw is 47,168, the number average molecular weight Mn is 21,886, and the intrinsic viscosity is 0.64dl / g).

Example 4

Approximately 1.7 kg of 1,4-cyclohexane dimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 19 g of polydimethylsiloxane (in In Chemical Formula 2, R ¹ to R ⁴ are methyl groups, D ¹ and D ² are propylene groups, L ¹ and L ² are hydroxyl groups, and the weight average molecular weight Mw is 2253) and about 0.15 g of titanium oxide Based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 280 ° C 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 a poly (cyclohexanedimethylene terephthalate) copolymer (whose weight average molecular weight Mw is 51,295, the number average molecular weight Mn is 24,549, and the intrinsic viscosity is 0.71dl / g).

Example 5

Approximately 1.7 kg of 1,4-cyclohexane dimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 57 g of polydimethylsiloxane In Chemical Formula 2, R ¹ to R ⁴ are methyl groups, D ¹ and D ² are propylene groups, L ¹ and L ² are hydroxyl groups, and the weight average molecular weight Mw is 2253] and about 0.15 g Titanium oxide-based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 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 Mw is 49,985, the number average molecular weight Mn is 23,750, and the intrinsic viscosity is 0.65dl / g).

Example 6

Approximately 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 57 g of polydimethylsiloxane (in In Chemical Formula 2, R ¹ to R ⁴ are respectively methyl groups, D ¹ and D ² are respectively propylene groups, L ¹ and L ² are respectively hydroxyl groups, and the weight average molecular weight Mw is 1418) and about 0.15 g of titanium oxide Based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 280 ° C 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 a poly (cyclohexanedimethylene terephthalate) copolymer (whose weight average molecular weight Mw is 51,769, the number average molecular weight Mn is 23,084, and the intrinsic viscosity is 0.71dl / g).

Example 7

Approximately 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 57 g of polydimethylsiloxane (in In Chemical Formula 2, R ¹ to R ⁴ are respectively methyl groups, D ¹ and D ² are respectively propylene groups, L ¹ and L ² are respectively hydroxyl groups, and the weight average molecular weight Mw is 2253) and about 0.15 g of titanium oxide Based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 280 ° C 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 a poly (cyclohexanedimethylene terephthalate) copolymer (whose weight average molecular weight Mw is 51,622, the number average molecular weight Mn is 22,106, and the intrinsic viscosity is 0.69dl / g).

Example 8

Approximately 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 57 g of polydimethylsiloxane (in In Chemical Formula 2, R ¹ to R ⁴ are respectively methyl groups, D ¹ and D ² are respectively propylene groups, L ¹ and L ² are respectively hydroxyl groups, and the weight average molecular weight Mw is 4172) and about 0.15 g of titanium oxide Based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out under atmospheric pressure and the temperature is raised to 280 ° C 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 a poly (cyclohexanedimethylene terephthalate) copolymer (whose weight average molecular weight Mw is 52,551, number average molecular weight Mn is 22,726, and intrinsic viscosity is 0.70dl / g).

Example 9

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

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 (cyclohexylenedimethylene terephthalate)] Copolymer (its weight average molecular weight Mw is 49,016, number average molecular weight Mn is 21,627, and intrinsic viscosity is 0.67dl / g).

Comparative example 1

Approximately 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 0.15 g of titanium oxide-based catalyst (Sachtleben Corporation Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out at atmospheric pressure and the temperature is raised to 280 ° C for 3 hours.

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 polycyclohexanedimethylene terephthalate (whose weight average molecular weight Mw is 50,349, the number average molecular weight Mn is 23,800, and the intrinsic viscosity is 0.65dl / g).

Comparative example 2

Approximately 1.7 kg of 1,4-cyclohexane dimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 38 g of polytetramethylene glycol glycol) and about 0.15 grams of titanium oxide-based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and under 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 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 polycyclohexanedimethylene terephthalate (whose weight average molecular weight Mw is 52,000, the number average molecular weight Mn is 24,500, and the intrinsic viscosity is 0.69dl / g).

Comparative Example 3

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

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 polycyclohexanedimethylene terephthalate (whose weight average molecular weight Mw is 48,637, the number average molecular weight Mn is 22,406, and the intrinsic viscosity is 0.67dl / g).

Comparative Example 4

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

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

Comparative Example 5

Approximately 1.7 kg of 1,4-cyclohexane dimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 38 g of octamethylcyclotetrasiloxane, and approximately 0.4 g of triphosphate Ethyl acetate and about 0.15 grams of titanium oxide-based catalyst (Sachtleben's Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) are injected into a reactor together, and the temperature is increased to 280 ° C under atmospheric pressure The esterification reaction was carried out for 3 hours.

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 polycyclohexanedimethylene terephthalate (whose weight average molecular weight Mw is 48,000, the number average molecular weight Mn is 23,000, and the intrinsic viscosity is 0.68 dl / g).

Comparative Example 6

Approximately 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), approximately 1.5 kg of terephthalic acid, approximately 0.4 g of triethyl phosphate, and approximately 0.15 g of titanium oxide-based catalyst (Sachtleben Corporation Hombifast PC, in which the effective proportion of titanium in the catalyst is 15%) is injected into a reactor together, and the esterification reaction is carried out at atmospheric pressure and the temperature is raised to 280 ° C 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.

Then, add about 57 grams of polydimethylsiloxane (in Chemical Formula 2, R ¹ to R ⁴ are respectively methyl groups, D ¹ and D ² are respectively propylene groups, L ¹ and L ² are respectively hydroxyl groups, And the weight average molecular weight Mw is 2253) and stirred for 10 minutes to obtain a polycyclohexane terephthalate dimethanol ester resin mixture (the weight average molecular weight Mw is 28,158, the number average molecular weight Mn is 13,743, and the intrinsic viscosity is 0.47dl / g).

Experimental Example 1

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

At this time, the temperature of the Ubierod viscometer was maintained at 35 ° C. When the flow time (efflux time) of the solvent or solution flowing through the ab section in the viscometer is regarded 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 the Huggins constant and is 0.247, and c is the concentration value and is 1.2 g / dl.

Experimental Example 2

Each sample of the PCT resin obtained from each example and the comparative example was measured for the initial color space L ^* -b ^* value (color L * -b * value) according to the CIE LAB specification at room temperature. The same sample after measurement is placed at 140 ℃, 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 measurement. The CIE LAB system is based on CIE The color space defined by the relative color theory of class perception, such as yellow-blue and green-red. The L * value represents the brightness (its value is 0 to 100, 0 is black, 100 is white), the a * value represents green to red ([+] represents red, [-] represents green, and the intermediate value is close to 0), The b * value represents yellow to green ([+] represents yellow, and [-] represents blue, and the intermediate value is close to 0).

Experimental Example 3

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

Table 4

Experimental Example 4

The PCT resin obtained from each example and comparative example was made into a sample with a thickness of 1/8 inch, The impact strength measurement [notched Izod, tested with ASTM D256 at a temperature of 25 [deg.] C.] is then performed, and the results are listed in Table 5 below.

Please refer to Tables 1 to 5, the samples prepared from the PCT copolymers of the examples show high impact strength (higher than or equal to 20 J / m), and this result is about twice that of the samples of the comparative example. In addition, the samples prepared from the PCT copolymers of each example show that they retain the color space L * -b * value and reflectance of 95% or more of the initial value after degradation, representing relative to the comparative example Can have better resistance to discoloration and high reflectivity.

In particular, in Comparative Example 5, a terminal hydroxyl group (terminal hydroxyl group) was used The siloxane compound of the group does not react with the dicarboxylic acid, so the addition effect of the siloxane is not produced.

In Comparative Example 6, when polysiloxane is added after the polycondensation reaction and physically mixed, thermal decomposition may occur during the mixing process, resulting in problems such as a decrease in molecular weight and color deterioration. In addition, due to the problem of dispersion, the injection of polysiloxane does not significantly improve the physical properties.

The above are only the preferred embodiments of the present invention. Equal changes and modifications made shall fall within the scope of the present invention.

Claims (14)

A poly (cyclohexylenedimethylene terephthalate) copolymer (copolymer), including: 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 the weight percentage of the repeating unit formed by the polysiloxane compound in the polycyclohexanedimethylene terephthalate copolymer is between 0.1% and 30%, wherein in the chemical formula 2, R ¹ to R ⁴ are independently substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms or independently substituted or unsubstituted aromatic groups having 6 to 18 carbon atoms Aryl group; D ¹ and D ² are 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 independently a hydroxyl group (hydroxyl group) or hydroxyphenyl group (hydroxy phenyl group); and n and m are independently integers of 5 to 300. The polycyclohexane terephthalate copolymer according to claim 1, wherein the weight average molecular weight of the polycyclohexane terephthalate copolymer is between 10,000 Between 100,000 and 100,000, and the number average molecular weight of the poly (cyclohexanedimethylene terephthalate) copolymer is between 10,000 and 50,000. The polycyclohexane terephthalate copolymer according to claim 1, wherein the intrinsic viscosity of the polycyclohexane terephthalate copolymer is less than or equal to 11dl / g. A method for preparing a poly (cyclohexylenedimethylene terephthalate) copolymer as described in claim 1 includes the following steps: mixing a diol compound, a A dicarboxylic acid compound and a polysiloxane compound represented by the following chemical formula 2, and performing an esterification reaction with a catalyst; and performing a polycondensation on the product of the esterification reaction (polycondensation) reaction:

Wherein in the chemical formula 2, R ¹ to R ⁴ are independently substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms or independently substituted or unsubstituted with 6 Aromatic groups (aryl group) of up to 18 carbon atoms; D ¹ and D ² are independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic ring having 4 to 10 carbon atoms A hydrocarbon group (alicyclic ydrocarbyl group); L ¹ and L ² are independently a hydroxyl group or a hydroxy phenyl group; and m is an integer of 5 to 300. The method according to claim 4, wherein the esterification reaction is carried out in a composition based on 100 parts by weight (pbw) of the diol compound, the composition comprising parts by weight between The dicarboxylic acid compound between 90 and 110 and the polysiloxane compound between 0.01 and 10 parts by weight, wherein the glycol compound includes 1,4-cyclohexanedimethanol (1,4 -cyclohexanedimethanol), and the dicarboxylic acid compound contains terephthalic acid, dimethyl terephthalate or a mixture of terephthalic acid and dimethyl terephthalate. The method of claim 5, wherein based on 100 parts by weight of the glycol compound, the composition of the esterification reaction further includes one or more phosphorus stabilization between 0.001 and 5 parts by weight (Phosphorus stabilizer), and the phosphorus stabilizer is selected from trimethyl phosphate (trimethyl phosphate), triethyl phosphate (triethyl phosphate), triphenyl phosphate (triphenyl phosphate), triethylphosphonoacetate In the group consisting of triethyl phosphonoacetate, phosphoric acid and phosphorous acid. The method according to claim 4, wherein the esterification reaction is carried out at a temperature of 230 ° C to 290 ° C and a pressure of 0.01 kg / cm ² to 3.0 / cm ² for 120 minutes to 600 minutes. The method according to claim 4, wherein the catalyst is one or more compounds selected from the group consisting of titanium oxide, titanium chelate compound, and tetrapropyl titanate. n-propyl titanate), tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl titanate In the group consisting of butyl-isopropyl titanate. The method according to claim 4, wherein the polycondensation reaction is carried out at a temperature ranging from 290 ° C to 320 ° C and a pressure ranging from 0.1 torr to 2.0 Torr for 60 minutes to 360 minutes. A resin molded article, wherein the resin molded article is made of the polycyclohexanedimethylene terephthalate copolymer described in claim 1. The resin molded product according to claim 10, wherein the impact strength (tested by ASTM D256) of the resin molded product is greater than or equal to 20 J / m, when the thickness of the sample is 1/8 inch at 25 ° C . The resin molded product according to claim 10, wherein the color space L * -b * value (color L * -b * value) of the resin molded product is greater than or after being placed in an environment of 140 ° C for 48 hours It is equal to 95% of the initial color space L * -b * of the resin molded product at room temperature. The resin molded article according to claim 10, wherein after being placed in an environment of 140 ° C. for 48 hours, the reflectance of the resin molded article to a wavelength of 450 nm is greater than or equal to that of the resin molded article at room temperature. 95% of the initial reflectance at 450nm. The resin molded article according to claim 10, wherein the resin molded article is used for a housing or a reflector of the light emitting diode.