KR101801704B1 - Blend of polyester and polycarbonate - Google Patents
Blend of polyester and polycarbonate Download PDFInfo
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- KR101801704B1 KR101801704B1 KR1020110109189A KR20110109189A KR101801704B1 KR 101801704 B1 KR101801704 B1 KR 101801704B1 KR 1020110109189 A KR1020110109189 A KR 1020110109189A KR 20110109189 A KR20110109189 A KR 20110109189A KR 101801704 B1 KR101801704 B1 KR 101801704B1
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- dicarboxylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
Disclosed is a polyester / polycarbonate blend which is excellent in thermal stability and color stability, has high transparency, and is excellent in flame retardancy and compatibility among compositions. The polyester / polycarbonate blend comprises (a) a dicarboxylic acid component comprising 50 to 100 mole% of a terephthalic acid moiety, and a diol component comprising 40 to 90 mole% of a 1,4-cyclohexanedimethanol moiety, 10 to 50% by weight of a first polyester comprising; (b) a dicarboxylic acid component comprising 50 to 100 mol% of a terephthalic acid moiety, and a diol component comprising 1 to 80 mol% of a cyclohexanedimethanol moiety and 1 to 60 mol% of an isosorbide moiety 3 to 30% by weight of a second polyester; And (c) from 20 to 87% by weight of the polycarbonate.
Description
The present invention relates to a polyester / polycarbonate blend, and more particularly, to a polyester / polycarbonate blend having excellent thermal stability and color stability, high transparency, flame retardancy and compatibility among compositions.
Since polyester is excellent in mechanical strength, heat resistance, transparency and gas barrier property, it is most suitable as a container for beverage filling such as juice, soft drink and carbonated beverage, packaging film, audio and video film, It is being used in large quantities. The sheet or plate of polyester has good transparency and excellent mechanical strength and is widely used as materials for cases, boxes, partitions, store shelves, protective panels, blister packaging, building materials, interior and exterior materials. As an application of a new polyester which has recently attracted attention, an example in which a thick plastic sheet is molded and used as a building interior material, a molded signboard, and the like is increasing. However, the polyester has a lower heat resistance than acryl (PMMA) or polycarbonate (PC), which is another competitive resin used for a sheet, and is sometimes unsuitable for use as an outdoor exterior material having a severe temperature change depending on the season. Therefore, various technical attempts have been made to improve the heat resistance of the polyester, and among them, a blending technique with a polycarbonate (PC) is a representative method.
However, since polyethylene terephthalate (PET) and polycarbonate, which are typical examples of polyester, have different melt viscosity and molecular structure, it is difficult to improve heat resistance by simply blending them. PET, which is a typical crystalline polymer, increases the mechanical strength in the blend by its crystal structure and imparts toughness to the entire polymer backbone. Among the crystalline PET, the homopolyester exhibits a relatively high crystallization rate as compared with the copolyester, and thus exhibits a high heat distortion temperature (HDT). In the blend matrix, the PET is distributed in a domain of several tens to several hundreds of nanometers Thereby improving the heat resistance of the blend. At this time, reducing the size of the domain and increasing the distribution improves the transparency as well as the heat resistance of the blend, and the heat resistance is more influenced by the distribution of the domains.
Techniques using copolymers or various complex catalysts to solve the heat resistance problem of polyester / polycarbonate blends are known. U.S. Patent No. 3,864,428 discloses a blend composition of a polyester, a polycarbonate and a graft copolymer (butadiene polymer-vinyl monomer), and U.S. Patent No. 4,879,355 discloses a copolymer of PET and bisphenol-A in a blend of PET and PC Discloses a technique for improving transparency and heat resistance, and U.S. Patent No. 5,942,585 discloses a technique for blending a polyester copolymerized with PC and 1,4-cyclohexane dimethanol. In addition, U.S. Patent No. 6,723,768 discloses that the color stability of a polyester / PC blend is improved when the titanium content is within 30 ppm, and the yellowing problem of the blend is closely related to the titanium content contained in each polymer.
The 1,4-cyclohexane dimethanol-copolymerized polyester is a copolyester having a basic structure of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol (CHDM), and glycol-modified poly 1,4-cyclohexylenedimethylene terephthalate (PETG), or CHDM-modified polyethylene terephthalate (see U.S. Patent No. 7,964,258). The PCTG does not contain harmful substances in the human body and is environmentally friendly and has excellent moldability, processability and transparency The PCTG can be produced by using various catalysts, but commercially produced titanium catalysts. The titanium-based catalysts have better polymerization reactivity than other catalysts, but depending on the content thereof, the color stability (Blunting yellowing problem).
With regard to the blend of polyester / polycarbonate (PC) copolymerized with 1,4-cyclohexanedimethanol, studies have been actively made since the 1980s to improve the compatibility between the two resins. The polyester / PC blend copolymerized with 1,4-cyclohexanedimethanol can exhibit complementary new physical properties depending on the composition of each component, but the heat resistance increases proportionally as the content of the polyester increases And the heat resistance (thermal stability) increases in proportion to the content only in the region where the content of the polyester is small. Further, when the content of the polyester is increased, the color of the polyester and the PC blend is changed by the titanium catalyst, and the use of the polyester is limited. On the other hand, when using an excess amount of 1,4-cyclohexanedimethanol-copolymerized polyester, it is necessary to use an additive that inhibits the activity of the catalyst. That is, in addition to improving the heat resistance, there is a limitation in terms of complementing the physical properties.
Accordingly, an object of the present invention is to provide a polyester / polycarbonate blend having excellent thermal stability, color stability, flame retardancy and compatibility between compositions.
In order to accomplish the above object, the present invention provides a process for producing a dicarboxylic acid comprising (a) a dicarboxylic acid component comprising 50 to 100 mol% of terephthalic acid moieties and 40 to 90 mol% From 10 to 50% by weight of a first polyester comprising a diol component; (b) a dicarboxylic acid component comprising 50 to 100 mol% of a terephthalic acid moiety, and a diol component comprising 1 to 80 mol% of a cyclohexanedimethanol moiety and 1 to 60 mol% of an isosorbide moiety 3 to 30% by weight of a second polyester; And (c) from 20 to 87% by weight of polycarbonate, based on the total weight of the polycarbonate blend.
The polyester / polycarbonate blend according to the present invention is a polyester / polycarbonate blend comprising 1,4-cyclohexanedimethanol copolymerized with 40 to 90% by mole of a first polyester, cyclohexanedimethanol and isosorbide 2 polyester and a polycarbonate (PC), the second polyester enhances compatibility of the first polyester and the polycarbonate, and improves the flame retardancy of the entire blend. The polyester / polycarbonate blend of the present invention is excellent in color stability (transparency) when it contains germanium (when germanium is used as a catalyst in the production of polyester), Color-b (yellow degree) It has excellent thermal stability (heat resistance).
Hereinafter, the present invention will be described in detail.
As used herein, the term "polyester" refers to a synthetic polymer prepared by the polycondensation reaction of one or more difunctional carboxylic acids with one or more bifunctional hydroxyl compounds, including "copolyesters" do. Typically, the bifunctional carboxylic acid is a dicarboxylic acid and the bifunctional hydroxyl compound is a divalent alcohol, such as a glycol or a diol. In addition, the term "residue " means a certain moiety or unit derived from the specific compound when the particular compound participates in the chemical reaction and is included in the result of the chemical reaction. For example, each of the "dicarboxylic acid residue" and "diol (glycol) residue" is a residue derived from a dicarboxylic acid component or from a dicarboxylic acid component in a polyester formed by an esterification reaction or condensation reaction . That is, when a dicarboxylic acid component and a diol (glycol) component are subjected to a conventional polyester polymerization reaction, a hydrogen, a hydroxyl group or an alkoxy group is removed and the redisue is remained. Accordingly, the dicarboxylic acid residue may be a dicarboxylic acid monomer or an acid halide thereof, an ester (for example, a lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) , Salts, anhydrides, or mixtures thereof. Thus, in the present specification, the terms "dicarboxylic acid "," terephthalic acid ", and the like are useful for the polycondensation process with a diol for producing a polyester of high molecular weight, and include dicarboxylic acid (e.g., terephthalic acid) Esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, as well as any derivatives thereof, for example, their corresponding halides, esters,
The polyester / polycarbonate blend according to the present invention is intended to improve the thermal stability, color stability, flame retardancy and compatibility of a polyester / polycarbonate blend, and 1,4-cyclohexanedimethanol : CHDM) is a first polyester copolymerized with 40 to 90 mole% of the total diol component, cyclohexanedimethanol and a second polyester copolymerized with isosorbide as a diol component, and polycarbonate (PC) ).
The first polyester used in the present invention is a polyester in which a diol component containing a dicarboxylic acid component containing 50 to 100 mol% of terephthalic acid moiety and a 1,4-cyclohexanedimethanol moiety of 40 to 90 mol% Lt; / RTI > copolyester.
The dicarboxylic acid component of the first polyester contains 50 to 100 mol%, for example, 60 to 99.9 mol%, specifically 70 to 99.5 mol% of the terephthalic acid residue relative to the entire dicarboxylic acid component And aromatic dicarboxylic acid residues (excluding terephthalic acid residues) having 8 to 20 carbon atoms, preferably 8 to 14 carbon atoms, and aliphatic dicarboxylic acids having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, in order to improve the physical properties of the polyester resin And may contain 0 to 50 mol%, for example, 0.1 to 40 mol%, more specifically 0.5 to 30 mol%, of a dicarboxylic acid residue such as a carboxylic acid residue, a carboxylic acid residue, Examples of the aromatic dicarboxylic acid capable of forming the aromatic dicarboxylic acid residue include naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid except terephthalic acid, diphenyldicarboxylic acid , 4,4'-stilbene dicarboxylic acid, 2,5-furandicarboxylic acid, 2,5-thiopendicarboxylic acid, and the like, as well as aromatic dicarboxylic acids Examples of the aliphatic dicarboxylic acid capable of forming the aliphatic dicarboxylic acid residue include cyclohexanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid Branched, or cyclic aliphatic dicarboxylic acids or aliphatic dicarboxylic acids usually used in the production of polyester resins such as acrylic acid, maleic acid, fumaric acid, adipic acid, glutaric acid, and azelaic acid. Examples of the component Can. When the content of the dicarboxylic acid residue is too small or too large when the dicarboxylic acid residue is excluded from the terephthalic acid residue, the effect of improving the physical properties is insufficient, or the physical properties of the polyester resin are deteriorated There is a concern.
The diol component of the first polyester is present in an amount of from 40 to 90 mol%, preferably from 45 to 80 mol%, more preferably from 50 to 70 mol%, of 1,4-cyclohexanedimethanol ( 1,4-cyclohexanedimethanol: CHDM) residues and 10 to 60 mol%, preferably 20 to 55 mol%, more preferably 30 to 50 mol% of ethylene glycol residues, An aliphatic diol residue having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms (excluding a 1,4-cyclohexanedimethanol residue and an ethylene glycol residue) having 8 to 40 carbon atoms, preferably 8 to 40 carbon atoms, 0 to 50 mol%, for example, 0.1 to 40 mol%, specifically 0.5 to 30 mol%, of a diol residue group such as an aromatic diol residue of 1 to 33 carbon atoms, a mixture thereof, and the like. Examples of the diol capable of forming the aliphatic diol residue include diethylene glycol, triethylene glycol, propanediol (such as 1,2-propanediol, 1,3-propanediol), 1,4-butanediol, pentanediol, hexanediol (1,6-hexanediol and the like), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, Di-, tri-, and tetra-ethylenediamine, linear, branched or cyclic aliphatic diols such as dimethanol, 1,3-cyclohexanedimethanol and tetramethyl cyclobutanediol, and diols capable of forming the aromatic diol residues include polyoxyethylene- 2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- - (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3) -2,2- , 2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) ) Propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (3.0) -2,2- - (6) -2,2-bis (4-hydroxyphenyl) propane, propylene oxide-added bisphenol A derivatives (polyoxyethylene- (n) Bis (4-hydroxyphenyl) propane, polyoxypropylene- (n) -2,2-bis (4- Hydroxyphenyl) propane, etc., where n represents the number of polyoxyethylene or polyoxypropylene units), and the like. In the first polyester according to the present invention, by controlling the content of 1,4-cyclohexane dimethanol residues as described above, the impact strength increases sharply as the content of 1,4-cyclohexane dimethanol residues increases Respectively. Further, in the first polyester, the diol residue except for the 1,4-cyclohexane dimethanol residue and the ethylene glycol residue can be obtained by subjecting 1,4-cyclohexanedimethanol and ethylene glycol alone as the raw material, It is used to improve the physical properties. If the content of the 1,4-cyclohexane dimethanol residue is less than 40 mol% based on the total diol component, the impact strength may be insufficient or the transparency may be deteriorated. If the content is more than 90 mol%, the production cost may increase have. If the content of the ethylene glycol moiety is less than 10 mol% based on the total diol component, the polymerization reaction may be difficult. If the content of the ethylene glycol moiety exceeds 90 mol%, the impact strength may be lowered.
The content of the first polyester is 10 to 50% by weight, preferably 20 to 45% by weight, more preferably 30 to 40% by weight based on the total polyester / polycarbonate blend. If the content of the first polyester is less than 10% by weight based on the total blend, the transparency may be lowered. If the content of the first polyester exceeds 50% by weight, heat resistance may be lowered. The weight average molecular weight (Mw) of the first polyester is, for example, 30,000 to 70,000. If the weight average molecular weight is out of the above range, the physical properties of the blend may be deteriorated.
The second polyester used in the present invention is a polyester containing a dicarboxylic acid component such as a terephthalic acid residue and a diol containing a cyclohexanedimethanol residue and an isosorbide (1,4: 3,6-dianhydroglucitol) Component is a copolymerized copolyester. These copolyesters are currently being produced by SK Chemicals under the ECOZEN brand.
As the dicarboxylic acid component of the second polyester, the same dicarboxylic acid component as defined in the dicarboxylic acid component of the first polyester may be used. The diol component of the second polyester is present in an amount of from 1 to 80 mol%, preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, of cyclohexanedimethanol (1,2- 1 to 60% by mole, preferably 10 to 55% by mole, more preferably 20 to 50% by mole, of residues, such as cyclohexane dimethanol, 1,3-cyclohexane dimethanol, And an aliphatic diol residue having 1 to 80 mol%, preferably 5 to 60 mol%, more preferably 10 to 50 mol%, of 2 to 20, preferably 2 to 12, carbon atoms Hexanedimethanol residues and isosorbide residues), aromatic diol residues having 8 to 40, preferably 8 to 33, carbon atoms, mixtures thereof, and the like. Examples of the diol that can form the aliphatic diol residue include ethylene glycol, diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4- (1,6-hexanediol), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, tetramethylcyclo Butylene glycol, butanediol, and the like, preferably ethylene glycol, and the diol capable of forming the aromatic diol moiety is polyoxyethylene- (2.0) -2,2-bis ( (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- Bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- Bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3) -2,3-bis (4-hydroxyphenyl) propane, polyoxyethylene- (3.0) -2,2- Bis (4-hydroxyphenyl) propane; bisphenol A derivatives having a propylene oxide (polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) Polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (n) Propane, etc., where n is the number of polyoxyethylene or polyoxypropylene units), and the like. If the content of the cyclohexanedimethanol residue in the diol component of the second polyester is less than 1 mol% based on the total diol component, the impact strength may be insufficient or the transparency may be deteriorated. When the content is more than 80 mol% , There is a possibility that processing of the polyester resin becomes difficult. If the content of the isosorbide moiety is less than 1 mol% based on the total diol component, the heat resistance or chemical resistance of the produced polyester resin (second polyester) may be insufficient, and if it exceeds 60 mol% The appearance characteristics of the polyester resin may be deteriorated and yellowing phenomenon may occur. If the content of the diol residue (excluding the cyclohexanedimethanol residue and the isosobide residue) is less than 1 mol% with respect to the total diol component, there is a possibility that the property improving effect is insufficient. On the other hand, when the content exceeds the mole%, the physical properties of the polyester may be deteriorated.
The second polyester is environmentally friendly, and has excellent thermal and mechanical properties. The second polyester is capable of significantly improving the mechanical properties, heat resistance, flame retardancy, etc. of the polyester as a part of the residues of the diol component are derived from isosobide, and can be mixed with polycarbonate (PC) and the first polyester Thereby maximizing the mutual complementary effect (increased compatibility, etc.). That is, the second polyester is used as a compatibilizer of the first polyester / PC blend, and particularly improves the flame retardancy. Also, the second polyester significantly increases the impact strength as the content of cyclohexane dimethanol increases. The content of the second polyester is 3 to 30% by weight, preferably 4 to 25% by weight, more preferably 5 to 20% by weight, based on the whole polyester / polycarbonate blend. If the content of the second polyester is less than 3% by weight based on the total blend, the heat resistance, flame retardancy and compatibility of the blend may be deteriorated. If the content of the second polyester exceeds 30% by weight based on the total blend, . The weight average molecular weight (Mw) of the second polyester is, for example, 30,000 to 70,000. If the weight average molecular weight is out of the above range, the physical properties of the blend may be deteriorated.
The first and second polyesters can be produced by a conventional polyester production method, for example, by esterifying the dicarboxylic acid and the diol compound, and subjecting the esterification reaction product to polycondensation followed by poly-condensation reaction. Specifically, the esterification reaction of the dicarboxylic acid and the diol compound may be performed by esterifying the dicarboxylic acid and the diol compound at a pressure of 0 to 10.0 kg / cm 2 and a temperature of 150 to 300 ° C for 1 to 24 hours Reaction or ester exchange reaction. The esterification reaction conditions can be appropriately controlled according to the specific properties of the polyester to be produced, the molar ratio of the dicarboxylic acid component to the glycol, the process conditions, and the like. Specific examples of the esterification reaction conditions include a pressure of 0 to 5.0 kg / cm 2, more preferably a pressure of 0.1 to 3.0 kg / cm 2, a temperature of 200 to 270 ° C, more preferably a temperature of 240 to 260 ° C, a pressure of 1 To 15 hours, and more preferably from 2 to 8 hours. The molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be from 1: 1.05 to 1: 3.0. If the molar ratio of the diol component to the dicarboxylic acid component is less than 1.05, the unreacted dicarboxylic acid component may remain in the polymerization reaction, thereby lowering the transparency of the resin. When the molar ratio exceeds 3.0, Or the productivity of the resin may be lowered. In order to improve the process time and the production amount of the esterification reaction, a catalyst may be selectively used, and the esterification reaction may be carried out batchwise or continuously, and each raw material may be separately introduced, It is preferable to add the component in the form of a slurry in which a dicarboxylic acid component is mixed. In the case of the second polyester, the diol component such as isosorbide, which is solid at room temperature, may be dissolved in water or ethylene glycol, and then mixed with a dicarboxylic acid component such as terephthalic acid to form a slurry. In addition, water may be added to a slurry containing a dicarboxylic acid component, an isosorbide, and a diol component such as ethylene glycol to increase the solubility of the isosorbide. Alternatively, slurry may be prepared at a temperature of 60 ° C or higher, A slurry in which the binder is molten may be used.
The esterification reaction product of the dicarboxylic acid component and the diol component may be subjected to polycondensation reaction at a temperature of 150 to 300 ° C. and a reduced pressure of 400 to 0.01 mmHg To < / RTI > 24 hours. This polycondensation reaction can be carried out preferably at a reaction temperature of 200 to 290 DEG C, more preferably 260 to 280 DEG C, and preferably under a reduced pressure of 100 to 0.05 mmHg, more preferably 10 to 0.1 mmHg . The glycol, which is a by-product of the polycondensation reaction, can be removed by applying the reduced pressure condition of the polycondensation reaction. However, if the polycondensation reaction is outside the range of 400 to 0.01 mmHg of the reduced pressure, the removal of by-products may be insufficient. In addition, when the polycondensation reaction takes place outside the temperature range of 150 to 300 占 폚, the physical properties of the polyester resin to be produced may be deteriorated. The polycondensation reaction can be carried out for the necessary time until the intrinsic viscosity of the final reaction product reaches an appropriate level, for example for an average residence time of 1 to 24 hours. Preferably, the final vacuum degree of the polycondensation reaction is less than 2.0 mmHg, and the esterification reaction and the polycondensation reaction may be carried out under an inert gas atmosphere.
For the production of the first and second polyester, additives such as a polycondensation catalyst or a stabilizer may be used. Such an additive such as a polycondensation catalyst or a stabilizer can be added to the product of the esterification reaction or the transesterification reaction before the start of the polycondensation reaction and the mixed slurry containing the dicarboxylic acid and the diol compound And may be added during the esterification reaction step.
As the polycondensation catalyst, a titanium compound, a germanium compound, an antimony compound, an aluminum compound, a tin compound, or a mixture thereof may be used. Examples of the titanium compound include tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, Titanium dioxide / zirconium dioxide copolymer, and the like can be given as examples of the titanium dioxide / zirconium oxide / titanium dioxide / titanate / titanium dioxide / titanium dioxide / titanium dioxide / titanium dioxide / titanium dioxide / titanate / acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, titanium dioxide, Examples of the germanium-based compound include germanium dioxide (GeO 2 ), germanium tetrachloride (GeCl 4 ), germanium ethyleneglycoxide, germanium acetate, Coalesce There may be mentioned compounds and the like. Preferably, germanium dioxide can be used, and both crystalline and amorphous ones can be used, and glycol soluble ones can be used.
As the stabilizer, phosphorus compounds such as phosphoric acid, trimethyl phosphate, and triethyl phosphate may be used, and the amount thereof may be 10 to 200 ppm based on the weight of phosphorus, based on the weight of the final polymer (polyester resin). If the addition amount of the stabilizer is less than 10 ppm, the stabilizing effect may be insufficient and the appearance of the final product may turn yellow. If the addition amount of the stabilizer exceeds 200 ppm, a polymer having a desired high polymerization degree may not be obtained.
As the polycarbonate (PC) used in the present invention, conventional polycarbonate used in conventional polyester / polycarbonate blending can be used without limitation. For example, bisphenol A (Bisphenol A) And various extrusion and extruding polycarbonates prepared by polymerization in the presence of a catalyst. The polycarbonate may be produced by a phosgene method (or a solvent method) or an ester exchange method (or a melting method). The phosgene method is a production method of reacting bisphenol A with phosgene (polycondensation reaction). When methylene chloride is added as a solvent to an aqueous solution or suspension of bisphenol A sodium salt and phosgene is blown while stirring, the polycondensation reaction proceeds, The carbonate is obtained in the state of being dissolved in the solvent. Neutralizing it, washing it to remove the by-produced inorganic salts, and precipitating the polycarbonate on the flake using a petroleum-based or alcohol-based nonsolvent. The phosgene method has an advantage that a polymer having an arbitrary molecular weight can be obtained in a small amount to a high molecular weight as compared with the transesterification method, and a special apparatus is not required because the reaction conditions are smooth. However, the above-mentioned phosgene process requires a costly solvent and requires a washing process for completely removing the solvent recovery process and the inorganic salt mixed in the resin. Since the product is obtained as a powder or a flake, .
The ester exchange method is a method in which bisphenol A and diphenyl carbonate are mixed at an appropriate mixing ratio and heated and melted at a high temperature and a reduced pressure without a solvent to obtain a polycarbonate through polycondensation by an ester reaction. Here, the pressure is maintained at 20 to 30 mmHg at the beginning of the reaction and the temperature is maintained at 200 to 230 ° C. When the reaction is terminated at a pressure of 1 mmHg and the temperature is changed to 290 to 300 ° C, the melt viscosity of the system is increased, Can be obtained. Since the ester exchange method does not use a solvent, a solvent recovery step is not required, and the resulting resin is obtained as a molten phase. Thus, the resin can be pelletized in a reaction vessel with an inert gas, . However, there is a disadvantage in that a high-temperature reactor and a hermetically-sealed reactor capable of maintaining high-temperature and high-vacuum reaction conditions are high and polycarbonate having a higher molecular weight than the phosgene method can not be produced.
The content of the polycarbonate is 20 to 87% by weight, preferably 30 to 76% by weight, more preferably 40 to 65% by weight, based on the whole polyester / polycarbonate blend. If the content of the polycarbonate is less than 20% by weight based on the total blend, the heat resistance of the blend may be lowered. If the content of the polycarbonate exceeds 87% by weight based on the total blend, the transparency of the blend may deteriorate or the blend may change have. The polycarbonate may have a melt index (MI) of 5 to 40 g / 10 min (300 ° C). If the melt index of the polycarbonate is less than 5 g / 10 min (300 캜), the workability of the blend may be lowered. If it exceeds 40 g / 10 min (300 캜), the impact strength of the blend may be lowered. The weight average molecular weight (Mw) of the polycarbonate is, for example, 20,000 to 60,000, and if the weight average molecular weight is out of the above range, the physical properties of the blend may be deteriorated.
The polyester / polycarbonate blend according to the present invention may further comprise germanium in order to improve the discoloration (yellowing) of the blend that occurs when the first and second polyesters and the polycarbonate are blended. For example, the germanium may be present in an amount of from 10 to 1000 ppm (by weight), preferably from 20 to 700 ppm (by weight), more preferably from 50 to 500 ppm (by weight) 100 to 300 ppm (weight ratio). If the content of germanium is included, the color of the blend may be discolored if the content of germanium is less than 10 ppm based on the total blend. If the content of germanium exceeds 1000 ppm, there is no particular advantage, but the cost of germanium is high, So it is not economical. The germanium may be included in the form of a germanium catalyst (polycondensation catalyst, germanium compound) so that the germanium content range is included for the entire blend during the first or second polyester polymerization. For example, in order to incorporate the germanium into the polyester / polycarbonate blend of the present invention, it is preferred that (i) the dicarboxylic acid component and the diol component are added in the presence of the germanium catalyst (germanium compound) at 0.2 to 3.0 kg / Cm 2 and an average residence time of from 2 to 10 hours at a temperature of from 200 to 300 ° C, (ii) subjecting the esterification or transesterification reaction product to a reduced pressure condition of 400 to 0.1 mmHg and Germanium may be included by preparing a first or second polyester by a polycondensation reaction at a temperature of 240 to 300 DEG C for an average residence time of 1 to 10 hours and using the blend to prepare a blend.
The polyester / polycarbonate blend according to the present invention can be produced by a conventional blending method and can be molded by molding methods such as injection molding, extrusion molding and compounding. In the preparation of the blend, if necessary, conventional additives such as an antistatic agent and a stabilizer can be appropriately added. The amount of the additive to be used can be controlled to a level that is obvious to a person skilled in the art. It is not.
The polyester / polycarbonate blend of the present invention has a color-b (yellowness, yellowness degree) of 0 or less, preferably -3 to 0, on a 3 mm thick specimen after molding. The transparency of the specimen is 89% or more, preferably 89 to 92%, and the glass transition temperature (Tg) is 100 ° C or more, preferably 100 to 120 ° C.
Both the first polyester and the second polyester exhibit a glass transition temperature of less than 100 占 폚, and the blend of the two resins (two-component blend) also has a glass transition temperature of less than 100 占 폚. However, the polyester / polycarbonate blend (three-component blend) of the present invention is superior in heat resistance to the first polyester and the second polyester blend (two-component blend) with a heat resistance of 100 ° C or higher. In addition, the polyester / polycarbonate blend of the present invention has characteristics of excellent color stability as compared to the second polyester and polycarbonate blend (two-component blend). That is, if the first polyester is not blended, the Color-b value is 0 or less, or can not have transparency of 89% or more. In addition, when blending only the first polyester with polycarbonate, the compatibility between the polyester and polycarbonate is not good and the physical properties of the blend may become unstable. However, the polyester / polycarbonate blend of the present invention may contain a second polyester Thereby improving the compatibility and flame retardancy of the entire blend and exhibiting the above-mentioned stable physical properties.
Particularly, the polyester / polycarbonate blend (blend containing germanium) of the present invention using the polyester and polycarbonate produced under the germanium catalyst can be produced, for example, by using a polyester (PCTG, PETG, etc.) It has superior color stability (Color-b (yellowness), Color-L (lightness, brightness)) and transparency compared to the used polyester / polycarbonate blend (blend containing titanium). That is, the titanium-containing blend may be discolored by the titanium component to lower the overall blend color, and the polycarbonate may also be discolored due to the strong reactivity of the titanium component, thereby lowering the overall blend color. However, a germanium-containing blend may have a color-b value of about 1 to about 2 and a transparency of about 1% higher than a titanium-containing blend. Transparency is usually regarded as a property of the resin, which requires considerable effort to increase it by 1%. However, the polyester / polycarbonate blend of the present invention contains germanium, so transparency is comparable to acrylic resin, .
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The following examples illustrate the present invention, and the scope of the present invention is not limited by the following examples.
[Production Example] Production of first polyester
1,660 g of terephthalic acid, 1,760 g of 1,4-cyclohexanedimethanol (56 mol%) and 870 g of ethylene glycol (40 mol%) as a diol component were charged into a 7 L-volume reactor, And then 0.75 g of germanium catalyst (germanium dioxide) is added thereto. Thereafter, an esterification reaction or transesterification reaction is carried out at a pressure of 0.2 to 3.0 kg / cm 2 and an average residence time of 2 to 10 hours at a temperature of 200 to 300 ° C. And the esterification or transesterification reaction product was subjected to a polycondensation reaction under a reduced pressure of 400 to 0.1 mmHg and an average residence time of 1 to 10 hours at a temperature of 240 to 300 ° C to prepare 4,000 g of a first polyester.
[Examples 1 to 6 and Comparative Examples 1 to 4] Preparation and evaluation of polyester / polycarbonate blend
The content units of the polycarbonate (PC), the first polyester, the second polyester (ECOZEN) and the polyethylene terephthalate (PET) are shown in Table 1 in the following Table 1, The content of germanium (Ge) and titanium (Ti) is in a weight ratio with respect to the total blend), and the molar percentage of hexane dimethanol (CHDM) relative to the entire diol of the first polyester (Manufactured by LG-DOW, melt index (MI): 30 g / 10 min (300 ° C)), dried at 70 ° C for 6 hours, and dried at 70 ° C The second polyester (trade name: ECOZEN, manufactured by SK Chemicals Co., Ltd.) and polyethylene terephthalate (PET), which had been dried for 6 hours, were placed in a well-dehydrated container and mixed (molten compounding) by tumbling at 250 to 280 ° C for about 3 minutes. After melt compounding, the melt mixture was extruded into an extruder to obtain a polyester / polycarbonate blend in chip form. At this time, the residence time of the extruder is preferably maintained for about 2 to 30 minutes, and the screw speed is lowered, specifically about 100 to 200 rpm, so that the polyester resin and the polycarbonate resin are sufficiently mixed.
(Length) X 120 mm (length) of the same thickness as the specimen of 40 mm (width) X 40 mm (length) width of 3.0 mm thick and the specimen of cyclohexane dimethanol copolymerized with the above- (Length / diameter) of the screw was 23, and the compressive ratio was 20 mm. The specimen was injected with a thickness of 3.0 mm by using a cold runner type water- 3. The color-b (yellowing degree) and the transparency of the specimens were measured using a colorimeter (manufacturer: Konica Minolta, CM-3600d). The results are shown in Table 1 below. The glass transition temperature (Tg) of the melt-compounded chip was measured using a DSC measuring machine (manufacturer: Mettler Toledo, DSC1, star system). The results are shown in Table 1 below. Further, in the same manner as after the injection molding, the test piece of width 12mm 6.4mm (width) X 127mm (length) of thickness, pressure 0.45 Mpa, HDT measuring device (manufacturer: Mettler toledo, device name: DSC 1 Star e system was used to measure the heat deflection temperature (HDT). The results are shown in Table 1 below.
From the results, it can be seen that the cyclohexanedimethanol-copolymerized polyester / polycarbonate blend according to the present invention has Color-b in the range of -3 to 0, transparency of 89.8% or more, and excellent color stability , Tg of 109 占 폚 or higher, HDT of 101 占 폚 or higher, and excellent thermal stability. Further, when the second polyester (Ecozen) is not contained in the blend, the Ti catalyst is contained in place of the Ge catalyst, and PET or the like is used instead (Comparative Examples 1, 2 and 4) When the content of the first polyester (PCTG) is out of the range of 10 to 50% by weight based on the total blend (Comparative Example 3), the second polyester (PCTG) , Color stability, Tg, HDT and the like are deteriorated. Further, in the case of the first and second polyester blends (Comparative Example 5), Tg and HDT were less than 100 占 폚 and the heat resistance was poor. In the case of the second polyester and polycarbonate blend (Comparative Example 6) , And a color-b value of 2.3, yellowing occurs.
Claims (14)
(b) a dicarboxylic acid component comprising 50 to 100 mol% of a terephthalic acid moiety, and a diol component comprising 1 to 80 mol% of a cyclohexanedimethanol moiety and 1 to 60 mol% of an isosorbide moiety 3 to 30% by weight of a second polyester; And
(c) from 30 to 76% by weight of polycarbonate,
(Weight ratio) of germanium relative to the total polyester / polycarbonate blend.
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| KR1020110109189A KR101801704B1 (en) | 2011-10-25 | 2011-10-25 | Blend of polyester and polycarbonate |
| PCT/KR2012/008717 WO2013062286A1 (en) | 2011-10-25 | 2012-10-23 | Polyester/polycarbonate blend |
| TW101139501A TWI551650B (en) | 2011-10-25 | 2012-10-25 | Blend of polyester and polycarbonate |
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| KR102049410B1 (en) | 2013-06-11 | 2019-11-27 | 에스케이케미칼 주식회사 | Parts for vehicle, electrical/electronic instrument, home appliance, office machine, or household item |
| KR102049411B1 (en) * | 2013-06-11 | 2019-11-27 | 에스케이케미칼 주식회사 | Polymer resin composition with excellent chemical resistance |
| KR102056154B1 (en) * | 2014-02-07 | 2019-12-16 | 에스케이케미칼 주식회사 | Resin Composition for Forming Steering Wheel Remote Control Bezel |
| KR102036891B1 (en) * | 2014-05-26 | 2019-10-25 | 삼성전자주식회사 | Polymer compositions and formed article and manufacturing method of the same |
| KR102119444B1 (en) | 2014-10-31 | 2020-06-16 | 에스케이케미칼 주식회사 | Chemically resistant resin composition for center fasia |
| KR102119445B1 (en) * | 2014-10-31 | 2020-06-16 | 에스케이케미칼 주식회사 | Chemically resistant resin composition for over head console |
| KR102217754B1 (en) * | 2014-11-14 | 2021-02-18 | 에스케이케미칼 주식회사 | Polymer resin composition |
| KR20160075207A (en) * | 2014-12-19 | 2016-06-29 | 에스케이케미칼주식회사 | Polymer resin composition having excellent flame retardancy |
| CN104672880A (en) * | 2015-02-17 | 2015-06-03 | 深圳市光华伟业实业有限公司 | PC/PETG alloy material and preparation method thereof |
| KR101673109B1 (en) * | 2016-02-01 | 2016-11-04 | 쌍용자동차 주식회사 | Sunroof panel for vehicles |
| KR20180127216A (en) * | 2017-05-18 | 2018-11-28 | 에스케이케미칼 주식회사 | Polymer resin composition, 3d printing filament including the same, and method for producing 3d printer filament |
| KR102311477B1 (en) * | 2019-05-31 | 2021-10-08 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article using the same |
| JP7431862B2 (en) * | 2019-08-27 | 2024-02-15 | エスケー ケミカルズ カンパニー リミテッド | polyester resin mixture |
| KR20210039085A (en) * | 2019-10-01 | 2021-04-09 | 에스케이케미칼 주식회사 | Polyester resin blend |
| KR20230013667A (en) * | 2021-07-15 | 2023-01-27 | 주식회사 삼양사 | Polycarbonate resin composition with excellent optical properties and article comprising the same |
| CN116039198B (en) * | 2023-01-09 | 2023-10-10 | 咏麦可思(上海)智能科技有限公司 | PC/PET blend film for automobile inner and outer ornaments and preparation method thereof |
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| KR101121361B1 (en) * | 2004-12-22 | 2012-03-09 | 에스케이케미칼주식회사 | Blend of polyester copolymerized with 1,4-cyclohexanedimethanol having low oligomer content and polycarbonate, and preparing method thereof |
| KR100950932B1 (en) * | 2007-09-05 | 2010-04-01 | 웅진케미칼 주식회사 | Flame retardant polycarbonate blend sheet, its preparation and products using it |
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| TWI551650B (en) | 2016-10-01 |
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