KR101139137B1 - Blend of polyester and polycarbonate with good color - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to blends of polyesters and polycarbonates with excellent color, which are color and transparency compared to conventional polyester / polycarbonate blends by blending polyesters and polycarbonates prepared using specific stabilizers in polycondensation reactions. This has an excellent advantage.

Polyester, Polycarbonate, Blend, 1,4-cyclohexanedimethanol, Carboxy Phosphonic Acid Compound

Description

Blend of polyester and polycarbonate with good color

The present invention relates to a blend of polyester and polycarbonate with good color. More specifically, it relates to a blend of polyester and polycarbonate prepared by using 1,4-cyclohexanedimethanol, which is prepared using a specific stabilizer in the polycondensation reaction, as a raw material.

Generally, polyester resins represented by polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate are resins having excellent mechanical strength, heat resistance, electrical insulation, and chemical resistance, which may be used alone or in glass fiber. It is widely used as a fiber, a film, a plastic molded article, etc. by mixing or modifying a reinforcing agent and / or other additives such as, in particular, a polyester resin prepared by using 1,4-cyclohexanedimethanol as a raw material is processed, printed It has been used as an important material in the field of packaging materials, molded articles, films, etc. due to its excellent resistance to impact and impact.

However, the polyester resin prepared by using 1,4-cyclohexanedimethanol as a raw material is excellent in physical properties as described above, but lacks in heat resistance, and thus is required in fields requiring high heat resistance. Use has been limited.

On the other hand, aromatic polycarbonate resins such as bisphenol-A type have excellent thermal stability, but are poor in chemical resistance, weather resistance, processability, and printability, and have an impact strength above a critical thickness between 1/2 ＂and 1/4＂. There is a disadvantage that the sharp decrease.

In recent years, by blending a polyester resin prepared with 1,4-cyclohexanedimethanol as a raw material with polycarbonate, the defects of both resins as described above are improved, and heat resistance, impact resistance, processability, printability, and the like are improved. Research is actively underway to produce good blends and use them as commercially important materials.

However, in the case of such a conventional polyester / polycarbonate blend, heat resistance, processability and printability, etc. have been improved to some extent, but the color and transparency of the resin still have a disadvantage.

Therefore, in the present invention, in order to obtain a blend having excellent color and improved transparency, a wide range of studies on the blend of polyester resin and polycarbonate resin prepared by using 1,4-cyclohexanedimethanol polymerized by various methods as raw materials As a result, 1,4-cyclohexanedimethanol prepared using a titanium compound as a polycondensation catalyst and a carboxy phosphonic acid compound as a stabilizer was used as a raw material, and a polyester resin prepared was blended with polycarbonate. In this case, it was found that excellent color and transparency were expressed as compared to the conventional polyester / polycarbonate blend, and the present invention was completed based thereon.

Accordingly, an object of the present invention is to prepare a blend of a polycarbonate and a polyester resin prepared by using 1,4-cyclohexanedimethanol as a raw material, wherein the specified 1,4-cyclohexanedimethanol is used as a raw material. A polyester resin is used to provide a blend of polyester and polycarbonate with excellent color and transparency.

Blends of polyesters and polycarbonates according to the invention for achieving the above object are:

(a) preparing a diol component containing essentially a dicarboxylic acid component and 1,4-cyclohexanedimethanol through an esterification reaction and a polycondensation reaction, wherein a titanium compound is used as a polycondensation catalyst in the polycondensation reaction. 2 to 98 parts by weight of a polyester prepared using a carboxy phosphonic acid compound represented by the following general formula (1) as a polycondensation reaction stabilizer:

Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other hydrogen, an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R is an alkylene group or cycloalkyl having 1 to 10 carbon atoms A ylene group or an arylene group having 6 to 10 carbon atoms; And

(b) 2 to 98 parts by weight of polycarbonate having an average molecular weight (by means for measuring relative viscosity when the concentration is 0.5 parts by weight relative to dichloromethane at 25 ° C.) of 10,000 to 200,000;

Characterized in that it comprises a.

Here, the amount of the carboxy phosphonic acid-based compound is 0.1 to 500 ppm relative to the weight of the polyester based on the small amount of people.

In addition, the titanium compound is tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate , Triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide and silicon dioxide copolymers, titanium dioxide and zirconium dioxide copolymers or mixtures thereof.

Terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid or a mixture thereof in the repeating units of the dicarboxylic acid component constituting the polyester is 80 to 100 mol%, and 4 to 40 carbon atoms Other dicarboxylic acid is contained 0-20 mol%.

Also, 1 to 100 mol% of 1,4-cyclohexanedimethanol and 0 to 99 mol% of other diols having 2 to 12 carbon atoms are included in the repeating units of the diol component constituting the polyester.                         

The intrinsic viscosity of the polyester is 0.3 to 2.0 dl / g.

The blend may also further comprise at least one additive selected from the group consisting of thermal stabilizers, antioxidants, weather stabilizers, antistatic agents, pigments, phosphorus compounds, epoxy silane compounds, diimide compounds and impact modifiers.

Hereinafter, the present invention will be described in more detail.

As described above, in the present invention, 2 to 98 parts by weight of polyester and 2 to 98 parts by weight of polycarbonate prepared by using 1,4-cyclohexanedimethanol prepared as a raw material using a specific stabilizer in the polycondensation reaction Blending provides a blend of polyester and polycarbonate that is superior in color and transparency to conventional polyester / polycarbonate blends.

The method for preparing polyester prepared using 1,4-cyclohexanedimethanol used in the present invention can be broadly classified into the first step of the esterification reaction and the second step of the polycondensation reaction. Take a look at

First, as a first step, the diol component is added at a molar ratio of 1.3 to 3.0 to the dicarboxylic acid component, and the esterification reaction is carried out at a temperature of 230 to 260 ° C and a pressure condition of 0.1 to 3.0 kg / cm 2.

The dicarboxylic acid component is 80 to 100 mol% of (i) terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid or mixtures thereof in the repeating unit, and (ii) 4 to 40 carbon atoms. It contains 0-20 mol% of other dicarboxylic acids which are phosphorus.

The diol component includes (i) 1 to 100 mol% of 1,4-cyclohexanedimethanol and (ii) 0 to 99 mol% of other diols having 2 to 12 carbon atoms in the repeating unit.

As the 1,4-cyclohexanedimethanol, cis-, trans- or a mixture of two isomers can be used.

The esterification reaction is carried out at a temperature of 230 to 260 ° C and a pressure of 0.1 to 3.0 kg / cm 2. At this time, the reaction temperature is preferably 240 to 260 ° C, more preferably 245 to 255 ° C. In addition, the esterification time is usually about 100 ~ 300 minutes, which will depend on the reaction temperature, pressure, the molar ratio of the diol component to the dicarboxylic acid component.

The esterification reaction may be performed in a batch or continuous manner, or may be carried out by separately adding each raw material, but most preferably, a carboxylic acid component is added to the diol component in a slurry form. On the other hand, no catalyst is required for the esterification reaction.

After the first step of the esterification reaction as described above is completed, the second step of the polycondensation reaction is carried out. Before the start of the polycondensation reaction, the polycondensation catalyst and stabilizer are added to the esterification reaction obtained in the first step. A coloring agent etc. are added.

Generally, titanium, germanium, and antimony compounds may be used as the polycondensation catalyst. Among them, titanium compounds may be reacted even with a small amount compared to antimony compounds, and compared to germanium compounds. This is the cheapest and most desirable.

As the titanium compound used in the present invention, tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, and lac Tate titanate, triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide and silicon dioxide copolymer, titanium dioxide and zirconium dioxide copolymer, and the like. It may be used, and one or two or more of these may be mixed.

In this case, the amount of the titanium-based compound is preferably 0.1 ~ 150ppm based on the amount of titanium element relative to the weight of the final polymer, that is, polyester, but because it affects the color of the final polymer, stabilizers and colorants used in the desired color It can be used by appropriately adjusting according to the like.

Typically, as a stabilizer, phosphoric acid, trimethyl phosphate, triethyl phosphate, or the like is used. According to the present invention, it is most preferable to use a carboxy phosphonic acid-based compound of Formula 1 as a stabilizer in terms of reactivity and color.

Formula 1

Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other hydrogen, an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R is an alkylene group or cycloalkyl having 1 to 10 carbon atoms Or an arylene group having 6 to 10 carbon atoms.

Examples of the carboxy phosphonic acid-based compound represented by Formula 1 include triethylphosphonoacetate, and the like. The carboxy phosphonic acid-based compound has better stabilization performance and thermal stability for the catalyst than conventional stabilizers. And, the biggest disadvantage of the existing stabilizers has the advantage of lowering the large volatility. In addition, improved effects can be obtained in corrosion and toxicity.

At this time, the amount of the carboxy phosphonic acid-based compound used is 0.1 to 500ppm, preferably 10 to 150ppm relative to the weight of the final polymer based on the small amount of people. If the amount of the carboxyphosphonic acid-based compound is less than 0.1ppm, there is a problem that the color becomes yellow due to insufficient stabilization effect, and if it exceeds 500ppm, there is a problem that the desired high polymerization degree is not reached.

In addition, a colorant or the like for further improving the color may be further used as other additives.

Examples of the colorant include conventional colorants such as cobalt acetate and cobalt propionate, and the addition amount thereof is suitably 0 to 100 ppm relative to the final polymer weight. In addition to the colorant, an organic compound colorant may also be used.

Next, a second step of the polycondensation reaction is carried out, the polycondensation reaction is carried out under reduced pressure conditions of 250 ~ 290 ℃ and 400 ~ 0.1mmHg. The polycondensation reaction is carried out for the required time until the desired intrinsic viscosity is reached, the reaction temperature is typically 250 ~ 290 ℃, preferably 270 ~ 280 ℃. In addition, 1,4-cyclohexanedimethanol having an intrinsic viscosity of 0.3 to 2.0 dl / g, which is the object of the present invention, is used as a raw material by carrying out under reduced pressure of 400 to 0.1 mmHg to remove diols produced as a by-product. Obtained polyester resin.

The 1,4-cyclohexanedimethanol obtained therefrom is used as a raw material, and the polyester resin and the commercial polycarbonate resin, respectively, are dried and cooled to room temperature, and then fed into an extruder and blended.

Polycarbonates used in the present invention include homo polycarbonates, copolycarbonates or mixtures thereof. Preferably, polycarbonates having an average molecular weight of 10,000 to 200,000 (by means of measuring relative viscosity at a concentration of 0.5 parts by weight relative to dichloromethane at 25 ° C.) are used.

At this time, the blending ratio of the polycarbonate and the polyester resin prepared by using 1,4-cyclohexanedimethanol as a raw material is 2 to 98 parts by weight of polyester, preferably 10 to 90 parts by weight It is suitable in terms of expression.

According to the present invention, additional heat stabilizers, antioxidants, weather stabilizers, antistatic agents, pigments, phosphorus compounds, epoxy silane compounds, diimide compounds and impact modifiers may be added as necessary to blend the physical properties of the final blended resin composition. Can improve.

The extruder used in the extrusion of the blend having the composition as described above is not particularly limited to the type and type of extruder, the configuration of the screw, the length and screw width of the extruder, the rotation speed of the screw, and all extruders known in the art can be used. Can be.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

Unless stated otherwise in the following Examples and Comparative Examples, the unit "parts" means "parts by weight" and the physical properties shown were measured in the following manner.

◎ Intrinsic Viscosity (IV): After dissolving in 150 ° C ortho-chlorophenol at a concentration of 0.12%, it is measured using a Ubelrod viscometer in a 35 ° C thermostat.

◎ Pellet Color: Measured by Minolta Chroma Meter-410.

◎ Film color: Nippon Densoku Corporation measured haze meter 300 a.

Example 1

3560 parts of terephthalic acid, 1546 parts of 1,4-cyclohexanedimethanol and 1996 parts of ethylene glycol were added to a 10L reactor equipped with a stirrer and an outlet condenser, and the pressure was increased to 2.0 kg / cm 2 with nitrogen, and the temperature of the reactor was gradually raised to 245 ° C. To react. At this time, the generated water is allowed to flow out of the system for ester reaction, and when the generation and outflow of water are completed, the reactant is transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser, and a vacuum system.

Titanium dioxide and silicon dioxide copolymer are added to the esterification reaction to 40ppm of the final polymer amount based on the amount of titanium, triethyl phosphonoacetate is added to 60ppm of the final polymer amount based on the small amount of people, After adding cobalt acetate to 80ppm based on the amount of cobalt based on the amount of cobalt, ethylene glycol was removed by performing a low vacuum reaction for 40 minutes from atmospheric pressure to 50mmHg while increasing the internal temperature from 240 ° C to 275 ° C. After slowly depressurizing to 0.1mmHg and reacting under high vacuum until a desired intrinsic viscosity, it is discharged and cut into chips.

The 1,4-cyclohexanedimethanol copolyester resin thus prepared was measured by ¹ H-NMR to measure the mol ratio of the total dicarboxylic acid. As a result, 100 mol% of terephthalic acid and 49 mol of 1,4-cyclohexanedimethanol were obtained. %, 49 mol% of ethylene glycol, and 2 mol% of diethylene glycol were confirmed. On the other hand, the color and intrinsic viscosity of the 1,4-cyclohexanedimethanol copolyester resin obtained therefrom was measured by the method described above and the results are shown in Table 1 below.

Thereafter, the polyester was dried in a vacuum dryer maintained at 65 ° C and 10 mmHg or less for 18 hours to prepare pellets cooled to room temperature, and polycarbonate resin (LG-Dow, CALIBRE-301-30) was 130 ° C. After drying for 12 hours in a vacuum dryer maintained at 10 mmHg or less, the polycarbonate pellets cooled to room temperature and the polyester pellets prepared above are mixed with 30 parts by weight of polycarbonate pellets and 70 parts by weight of polyester pellets. The mixed pellet thus prepared was extruded into a 0.8 mm thick film at 270 ° C. using a Thermo Haake extruder, and the color was measured using the film colorimeter described above. The results are shown in Table 1 below.

Example 2

3417 parts of terephthalic acid, 1839 parts of 1,4-cyclohexanedimethanol and 1762 parts of ethylene glycol were added to a 10L reactor equipped with a stirrer and an outlet condenser, and the pressure was raised to 2.0 kg / cm 2 with nitrogen, and the temperature of the reactor was gradually raised to 255 ° C. To react. At this time, the generated water is allowed to flow out of the system for ester reaction, and when the generation and outflow of water are completed, the reactant is transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser, and a vacuum system.

Titanium dioxide and silicon dioxide copolymer are added to the esterification reaction to 40ppm relative to the final polymer amount, and triethylphosphonoacetate is added to 60ppm relative to the final polymer amount based on the amount of people. After adding cobalt acetate to 80ppm based on the amount of cobalt based on the amount of cobalt, ethylene glycol was removed by performing a low vacuum reaction for 40 minutes from atmospheric pressure to 50mmHg while increasing the internal temperature from 240 ° C to 275 ° C. After slowly depressurizing to 0.1mmHg and reacting under high vacuum until a desired intrinsic viscosity, it is discharged and cut into chips.

The 1,4-cyclohexanedimethanol copolyester resin thus prepared was measured by ¹ H-NMR to measure the molar ratio of the total dicarboxylic acid to 100 mol% of terephthalic acid and 61 mol of 1,4-cyclohexanedimethanol. %, 38 mol% of ethylene glycol, and 1 mol% of diethylene glycol were confirmed. On the other hand, after measuring the color and intrinsic viscosity of the 1,4-cyclohexane dimethanol copolyester resin obtained from the above method, the results are shown in Table 1 below.

Thereafter, the polyester was dried in a vacuum dryer maintained at 65 ° C and 10 mmHg or less for 18 hours to prepare pellets cooled to room temperature, and polycarbonate resin (LG-Dow, CALIBRE-301-30) was 130 ° C. After drying for 12 hours in a vacuum dryer maintained at 10mmHg or less, the polycarbonate pellets cooled to room temperature and the polyester pellets prepared above are mixed with 30 parts by weight of polycarbonate pellets and 70 parts by weight of polyester pellets. The mixed pellet thus prepared was extruded into a 0.8 mm thick film at 270 ° C. using a Thermo Haake extruder, and the color was measured using the film colorimeter described above. The results are shown in Table 1 below.

Comparative Examples 1 and 2

It was carried out in the same manner as in Example 1 except that the kind of stabilizer was changed as shown in Table 1 below, the intrinsic viscosity, pellet color and film color at this time was measured and the results are shown in Table 1 below.

Comparative Examples 3-4

It was carried out in the same manner as in Example 2, except that the type of stabilizer was changed as shown in Table 1 below, the intrinsic viscosity, pellet color and film color at this time was measured and the results are shown in Table 1 below.

As can be seen from the examples and comparative examples, 1,4-cyclohexanedimethanol prepared using a titanium compound as a polycondensation catalyst and a carboxy phosphonic acid compound as a stabilizer according to the present invention When polyester prepared as a raw material is blended with a polycarbonate, when a polyester produced by using 1,4-cyclohexanedimethanol, which is prepared using a conventional stabilizer as a raw material, is blended with a polycarbonate It was confirmed that the molded article had an excellent color. As described above, according to the present invention, yellowing is significantly reduced, thereby providing a polyester / polycarbonate blend having excellent color and transparency.

It is apparent that modifications and improvements are possible by those skilled in the art within the spirit or scope of the present invention. Accordingly, the simple modifications and variations of the present invention are all within the scope of the present invention, and the specific scope of protection of the present invention will be clarified by the appended claims and their equivalents.

Claims (7)

(a) preparing a diol component containing essentially a dicarboxylic acid component and 1,4-cyclohexanedimethanol through an esterification reaction and a polycondensation reaction, wherein a titanium compound is used as a polycondensation catalyst in the polycondensation reaction. 2 to 98 parts by weight of a polyester prepared using a carboxy phosphonic acid compound represented by the following general formula (1) as a polycondensation reaction stabilizer: Formula 1

Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other hydrogen, an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R is an alkylene group or cycloalkyl having 1 to 10 carbon atoms A ylene group or an arylene group having 6 to 10 carbon atoms; And (b) 2 to 98 parts by weight of a polycarbonate having an average molecular weight (by means of measuring a relative viscosity at a concentration of 0.5 parts by weight relative to dichloromethane at 25 ° C.) of 10,000 to 200,000. Here, the blend of the polyester and polycarbonate, characterized in that the amount of the carboxy phosphonic acid-based compound is 0.1 to 500ppm relative to the weight of the polyester based on the small amount of people. delete The method of claim 1, wherein the titanium compound is tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, Lactate titanate, triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide and silicon dioxide copolymers, titanium dioxide and zirconium dioxide copolymers or these Blend of polyester and polycarbonate, characterized in that a mixture of. The method of claim 1, wherein terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid or a mixture thereof in the repeating units of the dicarboxylic acid component constituting the polyester, 80 to 100 mol%, A blend of polyester and polycarbonate, characterized in that 0 to 20 mol% of other dicarboxylic acids having 4 to 40 carbon atoms are contained. The 1,4-cyclohexanedimethanol of 1,4 mol% of repeating units of the diol component constituting the polyester, and 0 to 99 mol% of other diols having 2 to 12 carbon atoms are included. Blend of polyester and polycarbonate, characterized in that. The blend of polyester and polycarbonate according to claim 1, wherein the intrinsic viscosity of the polyester is 0.3 to 2.0 dl / g. The method of claim 1, wherein the blend further comprises at least one additive selected from the group consisting of thermal stabilizers, antioxidants, weather stabilizers, antistatic agents, pigments, phosphorus compounds, epoxy silane compounds, diimide compounds and impact modifiers. Blend of polyester and polycarbonate, characterized in that.