WO2023008826A1 - 우수한 압출 가공성 및 재활용이 가능한 압출 취입 수지 및 이를 포함하는 조성물 - Google Patents
우수한 압출 가공성 및 재활용이 가능한 압출 취입 수지 및 이를 포함하는 조성물 Download PDFInfo
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-O hydridodioxygen(1+) Chemical compound [OH+]=O MYMOFIZGZYHOMD-UHFFFAOYSA-O 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MOYKHGMNXAOIAT-JGWLITMVSA-N isosorbide dinitrate Chemical compound [O-][N+](=O)O[C@H]1CO[C@@H]2[C@H](O[N+](=O)[O-])CO[C@@H]21 MOYKHGMNXAOIAT-JGWLITMVSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a recyclable extrusion blown resin having excellent extrusion processability and a composition comprising the same.
- Waste plastic which accounts for about 70% of marine pollution, has recently emerged as a serious social problem, and accordingly, countries are regulating the use of single-use plastics and at the same time promoting the reuse of waste plastics.
- waste plastics are reused as raw materials after collecting, crushing, and washing waste plastics, melt-extruding, and re-pelletizing them.
- it is very difficult to provide a product of good quality due to foreign substances in the waste plastic. Accordingly, there is an urgent need for research to produce plastic products of good quality from waste plastics.
- polyethylene terephthalate resin is widely used commercially due to its low price and excellent physical/chemical properties, but it has a relatively low viscosity compared to polyethylene or polypropylene, so it is necessary to control the molding temperature very low during extrusion blow molding. Accordingly, the use of polyethylene terephthalate has limitations in manufacturing a uniform parison in a single or multi-head method.
- polyester which is a recyclable extrusion blown resin, including isocarbide as a monomer in the polyester resin, but has excellent extrusion processability.
- the present invention is to provide a recyclable extrusion blown resin having excellent extrusion processability and a composition comprising the same.
- the extrusion blown resin may be a polyester resin containing isocarbide as a monomer and a composition containing the same.
- the present invention provides the following polyester resin:
- X is the melting point (unit: ° C) of the polyester resin
- Y is the cooling crystallization temperature (unit: ° C) of the polyester resin
- Z is the half-crystallization time (unit: minutes) of the polyester resin.
- 'residue' refers to a specific part or unit derived from a specific compound that is included in the product of a chemical reaction when a specific compound participates in a chemical reaction.
- each of the 'residue' of the dicarboxylic acid component or the 'residue' of the diol component is derived from the dicarboxylic acid component or the diol component in the polyester resin formed by esterification or condensation polymerization. refers to the part from which
- a dicarboxylic acid or a derivative thereof and a diol are polymerized, and an acid moiety derived from the dicarboxylic acid or a derivative thereof and a diol moiety derived from the diol are repeated.
- the acid moiety and the diol moiety refer to residues remaining after hydrogen, hydroxyl groups, or alkoxy groups are removed from polymerization of dicarboxylic acids or derivatives thereof and diols.
- dicarboxylic acid or its derivative and diol will be described in more detail below, but for example, the dicarboxylic acid or its derivative may be mainly terephthalic acid or its derivative, and the diol may be mainly ethylene glycol.
- the polyester resin may satisfy Equation 1 below.
- X is the melting point (unit: ° C) of the polyester resin
- Y is the cooling crystallization temperature (unit: ° C) of the polyester resin
- Z is the half-crystallization time (unit: minutes) of the polyester resin.
- [Equation 1] is greater than 20, greater than 30, greater than 40, greater than 50. greater than 60 or greater than 70, and may be less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, or less than 80.
- Equation 1 When the value of Equation 1 is 20 or less, the crystallinity of the polyester resin is low, and thus the effect of improving the crystallization rate may be inferior.
- the product thus manufactured has a Haze of 5% or more after immersion in ethanol, exhibits chemical resistance to heat, has a ⁇ Tm of 10 ° C or more and a very low draw ratio, so it may be blended with PET and cannot be recycled.
- Equation 1 when the value of Equation 1 is 160 or more, the crystallinity is excessively high, resulting in poor processability, the weight of the extruded blown product is light, and it may be difficult to mold into a thick product, and the draw ratio is excessively high. There may be a problem in which heavy-blow is impossible during EBM (extrusion blow molding). In addition, after being immersed in ethanol, haze appears to be 5% or more, which can show chemical resistance to heat.
- the melting point (T m ) of the polyester resin composition may be 200 to 230°C. Specifically, the melting point may be 200 °C or higher, 205 °C or higher, or 210 °C or higher, and 230 °C or lower, 225 °C or lower, or 220 °C or lower.
- the cooling crystallization temperature (T mc ) of the polyester resin composition may be 130 to 150 °C.
- the cooling crystallization temperature may be 130 °C or higher, 135 °C or higher, or 140 °C or higher, and may be 150 °C or lower, or 145 °C or lower.
- the half-crystallization time (T 1/2 ) of the polyester resin composition may be 1 to 15 minutes.
- the semi-crystallization time is 1 minute or more, 2 minutes or more, 3 minutes or more, or 4 minutes or more, and 15 minutes or less, 14 minutes or less, 13 minutes or less, 12 minutes or less, 11 minutes or less, 10 minutes or less, 9 minutes or less. or less, 8 minutes or less, 7 minutes or less, or 6 minutes or less.
- the melting point, cooling crystallization temperature, and semi-crystallization time may be the melting point, cooling crystallization temperature, and semi-crystallization time when the polyester resin composition has the maximum crystallinity. Specifically, through the process of kneading the crystallizer at a rate of 10 to 100 ppm at a temperature around 230 to 250 ° C. using a twin-screw extruder for the polyester resin prepared in the above Examples and Comparative Examples, It may be a melting point, cooling crystallization temperature, and half-crystallization time after pretreatment to have maximum crystallinity in the composition.
- the polyester resin includes a diol portion derived from a diol containing ethylene glycol and a comonomer in order to satisfy the above-described parameter Equation 1, and the diol portion derived from the comonomer is 9 to 9 17 mol%.
- the polyester resin of the present invention is a diol part derived from a comonomer and essentially includes a diol part derived from isocarbide. Due to this structure, it can be reused when mixed with polyethylene terephthalate, providing a continuously usable plastic can do.
- the diol portion derived from the comonomer may include a diol portion derived from isosorbide (1,4:3,6-dianhydroglucitol) and a diol portion derived from cyclohexanedimethanol.
- the total content of the diol portion derived from isosorbide and cyclohexanedimethanol in the polyester resin may be 9 to 17 mol%.
- the total content of the diol moiety derived from isocarbide and cyclohexanedimethanol is 9 mol% or more, 10 mol% or more, 11 mol% or more, or 12 mol% or more, and 17 mol% or less, 16 mol% or less , 15 mol% or less, or 14 mol% or less.
- Equation 1 the value of Equation 1 is 160 or more, and the processability is not improved due to excessive crystallinity, and after ethanol immersion Haze is more than 5%, showing chemical resistance to heat, and the stretching ratio is high, so there may be a problem that heavy-blow is impossible during EBM (extrusion blow molding).
- the crystallinity is low as the value of Equation 1 is 20 or less, and the effect of improving the crystallization rate is inferior, and the Haze is 5% or more after ethanol immersion, resulting in heat It exhibits chemical resistance characteristics for ⁇ Tm of 10 °C or more, and there may be a problem that recycling is impossible because it is blended with PET.
- the polyester resin may include 0.1 to 3 mol% of the diol part derived from isosorbide based on the total diol part.
- the diol portion derived from isosorbide is 0.1 mol% or more, 0.5 mol% or more, or 1 mol% or more, and 3 mol% or less, 2.5 mol% or less, or 2 mol% or less, based on the total diol portion. .
- the diol portion when included in an amount of more than 3 mol%, the melting point is not measured, or even if the melting point is measured, the crystallinity is low, so that the value of [Equation 1] is 20 or less, and the effect of improving the crystallization rate is inferior, and ethanol After immersion, haze appears to be 5% or more, showing chemical resistance to heat, and ⁇ Tm is 10 °C or more, so there may be a problem that recycling is impossible because it is blended with PET.
- cyclohexane dimethanol may be further included as the diol partial comonomer other than the isocarbide.
- the cyclohexanedimethanol may contain 8 to 16 mol% of the diol portion derived therefrom with respect to the total diol, thereby providing a polyester resin that satisfies Equation 1 above.
- the diol portion derived from cyclohexanedimethanol is 8 mol% or more, 9 mol% or more, or 10 mol% or more, based on the total diol portion, and 16 mol% or less, 15 mol% or less, 14 mol% or less, 13 mol% or less or 12 mol% or less.
- Equation 1 When the diol portion derived from cyclohexanedimethanol is less than 8 mol%, the value of Equation 1 is 160 or more, and the processability is not improved due to excessive crystallinity, and Haze is 5% or more after ethanol immersion. It exhibits poor chemical resistance and has a high stretching ratio, which may cause problems in that heavy-blow is impossible during EBM (extrusion blow molding).
- a catalyst may be used in the esterification reaction or transesterification reaction.
- catalysts include methylate of sodium and magnesium; acetates, borates, fatty acid salts, carbonates such as Zn, Cd, Mn, Co, Ca, and Ba; metal Mg; Oxides of Pb, Zn, Sb, Ge, and the like may be present.
- the esterification reaction or transesterification reaction may be carried out in a batch, semi-continuous or continuous manner, and each raw material may be added separately, but diol is mixed with a dicarboxylic acid or a derivative thereof. It is preferable to introduce it in the form of a slurry.
- a polycondensation catalyst, a stabilizer, a colorant, a crystallizer, an antioxidant, a branching agent, and the like may be added to the slurry before the start of the esterification reaction or the transesterification reaction or to the product after completion of the reaction.
- the timing of adding the above additives is not limited thereto, and may be added at any time during the manufacturing step of the polyester resin.
- the polycondensation catalyst one or more conventional titanium, germanium, antimony, aluminum, and tin-based compounds may be appropriately selected and used.
- Useful titanium-based catalysts include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, and lactate titanate.
- triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide/silicone dioxide copolymer, tanium dioxide/zirconium dioxide copolymer and the like can be exemplified.
- useful germanium-based catalysts include germanium dioxide and copolymers using the same.
- a phosphorus-based compound such as phosphoric acid, trimethyl phosphate, or triethyl phosphate may be generally used, and the added amount thereof is 10 to 200 ppm based on the weight of the final polymer (polyester resin) based on the amount of phosphorus element.
- the addition amount of the stabilizer is less than 10 ppm, the stabilizing effect may be insufficient and the color of the polymer may change to yellow, and if it exceeds 200 ppm, there is a fear that a polymer having a desired high polymerization degree may not be obtained.
- the colorant added to improve the color of the polymer common colorants such as cobalt acetate and cobalt propionate can be exemplified, and the amount added is the final polymer (polyester resin) based on the amount of cobalt element. 10 to 200 ppm by weight of.
- anthraquinone-based compounds, perinone-based compounds, azo-based compounds, and methine-based compounds can be used as organic colorants.
- Clarient Toners such as Polysynthren Blue RLS from Clarient or Solvaperm Red BB from Clarient can be used.
- the addition amount of the organic compound colorant may be adjusted to 0 to 50 ppm based on the weight of the final polymer. If the colorant is used in an amount outside the above range, the yellow color of the polyester resin may not be sufficiently covered or physical properties may be deteriorated.
- crystallizing agent examples include crystal nucleating agents, ultraviolet absorbers, polyolefin-based resins, and polyamide resins.
- antioxidant hindered phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants, or mixtures thereof may be exemplified.
- the esterification reaction is carried out at a temperature of 200 to 300 ° C or 230 to 280 ° C and 0 to 10.0 kgf / cm 2 (0 to 7355.6 mmHg), 0 to 5.0 kgf / cm 2 (0 to 3677.8 mmHg) or 0.1 to 3.0 kgf / It can be carried out under pressure conditions of cm 2 (73.6 to 2206.7 mmHg).
- the transesterification reaction is carried out at a temperature of 150 to 270 ° C or 180 to 260 ° C and a pressure of 0 to 5.0 kgf / cm 2 (0 to 3677.8 mmHg) or 0.1 to 3.0 kgf / cm 2 (73.6 to 2206.7 mmHg) can be carried out.
- the pressure written outside the parentheses means the gauge pressure (indicated in kgf/cm 2 units), and the pressure written in parentheses means the absolute pressure (indicated in mmHg units).
- the reaction time (average retention time) is usually 1 to 24 hours or 2 to 8 hours, and may vary depending on the reaction temperature, pressure, and the molar ratio of the dicarboxylic acid or its derivative to the diol used.
- the product obtained through the esterification or transesterification reaction may be prepared as a polyester resin having a higher degree of polymerization through a polycondensation reaction.
- the polycondensation reaction is carried out at a temperature of 150 to 300 ° C, 200 to 290 ° C or 260 to 290 ° C and a reduced pressure of 400 to 0.01 mmHg, 100 to 0.05 mmHg or 10 to 0.1 mmHg.
- the pressure means the range of absolute pressure.
- the reduced pressure condition of 400 to 0.01 mmHg is for removing glycol, which is a by-product of the polycondensation reaction, and isocarbide, which is an unreacted material.
- the reduced pressure condition is out of the above range, there is a concern that the removal of by-products and unreacted substances may be insufficient.
- the polycondensation reaction temperature is out of the above range, the physical properties of the polyester resin may be deteriorated.
- the polycondensation reaction is carried out for a required period of time, for example, an average residence time of 1 to 24 hours until a desired intrinsic viscosity is reached.
- the vacuum reaction is intentionally prolonged at the end of the esterification reaction or transesterification reaction or the beginning of the polycondensation reaction, that is, in a state where the viscosity of the resin is not sufficiently high. It is maintained so that unreacted raw materials can be discharged out of the system.
- the viscosity of the resin increases, it becomes difficult for the raw material remaining in the reactor to escape out of the system.
- the reaction product obtained through the esterification reaction or the transesterification reaction before the polycondensation reaction is left in the reduced pressure condition of about 400 to 1 mmHg or about 200 to 3 mmHg for 0.2 to 3 hours to remain in the polyester resin. Unreacted materials such as can be effectively removed.
- the temperature of the product may be adjusted to a temperature equal to or between the esterification reaction or transesterification reaction temperature and the polycondensation reaction temperature.
- the intrinsic viscosity of the polymer is 0.30 to 1.0 dl/g.
- the reaction rate in the solid phase reaction is significantly lowered, and when the intrinsic viscosity exceeds 1.0 dl/g, as the viscosity of the melt increases during melt polymerization, the reaction between the stirrer and the reactor is reduced.
- the possibility of discoloration of the polymer increases due to shear stress, and side reaction substances such as acetaldehyde also increase.
- the polyester resin according to the embodiment may have a higher degree of polymerization by additionally undergoing a solid state reaction after the polycondensation reaction, if necessary.
- the granulation method may be a strand cutting method in which strands are extruded, solidified in a cooling liquid, and then cut with a cutter, or an underwater cutting method in which a die hole is immersed in a cooling liquid, extruded directly into the cooling liquid, and cut with a cutter.
- the temperature of the coolant In general, in the strand cutting method, the temperature of the coolant must be kept low, and the strand must be well solidified to avoid cutting problems. In the underwater cutting method, it is good to keep the temperature of the cooling liquid suitable for the polymer so that the shape of the polymer is uniform. However, in the case of a crystalline polymer, the temperature of the cooling liquid may be deliberately maintained high to induce crystallization during ejection.
- the particles can be prepared to have an average weight of less than about 15 mg.
- the granulated polymer may be washed with water by leaving it for 5 minutes to 10 hours in water having a temperature equal to or about 50 to 100° C. to the glass transition temperature of the polymer.
- the granulated polymer undergoes a crystallization step to prevent fusion during the solid phase reaction. It can be carried out in air, inert gas, water vapor, in an inert gas atmosphere containing water vapor or in a solution, and crystallization is performed at 110 ° C to 210 ° C or 120 ° C to 210 ° C. If the temperature is low, the speed at which crystals are formed is too slow, and when the temperature is high, the speed at which the surface of the particles is melted faster than the speed at which crystals are formed, causing the particles to adhere to each other and cause fusion. Since the heat resistance of the particles increases as the particles crystallize, it is also possible to divide the crystallization into several steps and increase the temperature step by step to perform crystallization.
- the solid phase reaction may be carried out under an inert gas atmosphere such as nitrogen, carbon dioxide, argon, or the like, or at a reduced pressure of 400 to 0.01 mmHg and a temperature of 180 to 220° C. for an average residence time of 1 to 150 hours.
- an inert gas atmosphere such as nitrogen, carbon dioxide, argon, or the like
- a reduced pressure 400 to 0.01 mmHg and a temperature of 180 to 220° C. for an average residence time of 1 to 150 hours.
- the crystallized polymer was dissolved in orthochlorophenol at 150 °C at a concentration of 0.12% by weight, and the intrinsic viscosity measured at 35 °C was 0.65 dl/g or more, 0.70 dl/g or more, 0.75 dl/g or more, or 0.80 dl/g. Solid phase polymerization can be performed to reach the above values.
- the polyester resin according to the embodiment has a haze of 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, measured according to ASTM D1003-97 for a specimen having a thickness of 6 mm. Or less, 2.5% or less, 2% or less, or 1% or less may exhibit high transparency. Theoretically, since haze is most preferably 0%, the lower limit may be 0% or more.
- the polyester resin according to the embodiment may have a draw ratio of 1 to 5.
- the stretching ratio may be 1 or more, or 2 or more, and 5 or less, 4 or less, or 3 or less.
- EMB Extrusion Blow Molding
- polyester resin As the polyester resin satisfies Equation 1 described above, it shows improved shear fluidization properties, and can provide a high-quality molded article by an extrusion blow molding method.
- the dicarboxylic acid component used in the present invention means a main monomer constituting a polyester resin together with a diol component.
- 'dicarboxylic acid or a derivative thereof' means at least one compound selected from dicarboxylic acids and derivatives of dicarboxylic acids.
- 'derivatives of dicarboxylic acids' are alkyl esters of dicarboxylic acids (lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl esters) or anhydrides of dicarboxylic acids.
- terephthalic acid or a derivative thereof may be terephthalic acid; monoalkyl or dialkyl terephthalates; and compounds that react with diols to form a terephthaloyl moiety, such as terephthalic anhydride.
- the residue of the dicarboxylic acid component of the present invention may include at least one residue selected from the group consisting of terephthalic acid, dimethylpetephthalic acid, and derivatives thereof.
- the polyester resin may include an acid moiety derived from a comonomer other than terephthalic acid or a derivative thereof.
- the comonomer may be at least one selected from the group consisting of an aromatic dicarboxylic acid having 8 to 14 carbon atoms or a derivative thereof, and an aliphatic dicarboxylic acid having 4 to 12 carbon atoms or a derivative thereof.
- aromatic dicarboxylic acids having 8 to 14 carbon atoms or derivatives thereof include isophthalic acid, dimethyl isophthalate, phthalic acid, dimethyl phthalate, phthalic anhydride, naphthalene dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, dimethyl 2, Dialkyl naphthalene dicarboxylates such as 6-naphthalene dicarboxylate, aromatic dicarboxylic acids commonly used in the manufacture of polyester resins such as diphenyl dicarboxylic acid, or derivatives thereof may be included.
- the aliphatic dicarboxylic acids having 4 to 12 carbon atoms or derivatives thereof include cyclohexane dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid and 1,3-cyclohexane dicarboxylic acid, dimethyl 1,4- Cyclohexane dicarboxylates, such as cyclohexane dicarboxylate, dimethyl 1,3-cyclohexane dicarboxylate, sebacic acid, succinic acid, isodecylsuccinic acid, maleic acid, maleic anhydride, fumaric acid, adipic acid, gluta Linear, branched or cyclic aliphatic dicarboxylic acids or derivatives thereof commonly used in the manufacture of polyester resins such as ric acid and azelaic acid may be included.
- cyclohexane dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid and 1,3-cyclohe
- the comonomer may be used in an amount of 0 to 50 mol%, 0 mol% to 30 mol%, 0 to 20 mol%, or 0 to 10 mol% based on the total amount of the dicarboxylic acid or its derivative.
- the diol component used in the present invention means a main monomer constituting the polyester resin together with the dicarboxylic acid component described above.
- the diol component includes isocarbide and cyclohexanedimethanol as comonomers in addition to ethylene glycol.
- the child sorbide is used to improve the processability of the polyester resin to be produced.
- the transparency and impact resistance of the polyester resin are improved by the diol component of the above-mentioned cyclohexanedimethanol, but the shear fluidization property should be improved and the crystallization rate should be delayed for processability. difficult.
- the shear fluidization property is improved and the crystallization rate is delayed, thereby improving the processability of the polyester resin produced.
- the diol portion derived from isocarbide is included in an amount of 0.1 to 3 mol% with respect to the total diol portion of the polyester resin. A detailed description of the content range of the diol portion derived from isocarbide is as described in the polyester resin portion.
- the cyclohexanedimethanol (for example, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol) has a high degree of transparency and impact resistance of the polyester resin produced. It is an ingredient that contributes to improvement.
- the diol portion derived from cyclohexanedimethanol is included in an amount of 8 to 16 mol% with respect to the total diol portion of the polyester resin.
- a detailed description of the content range of the diol portion derived from cyclohexanedimethanol is the same as described in the polyester resin portion.
- the polyester resin composition includes 9 to 17 mol% of the sum of the diol portion derived from isoide and the diol portion derived from cyclohexanedimethanol with respect to the total diol portion.
- a detailed description of the total content range of the diol portion derived from the isocarbide and cyclohexanedimethanol is as described in the polyester resin portion.
- the comonomer providing the diol portion other than the ethylene glycol may include diols commonly used in the manufacture of polyester resins in addition to the above-mentioned monomers.
- diol monomers that can be used in polyethylene terephthalate.
- isosorbide or a combination of isosorbide and cyclohexanedimethanol is advantageous in satisfying the physical properties to be obtained in the present invention.
- the polyester resin of the present invention may contain residues derived from the branching agent having two or more functional groups as the branching agent having three or more functional groups is added during its polymerization.
- the branching agent having three or more functional groups introduces a side chain into the main chain of the polyester resin or graft-polymerizes the polyester resin so that the polyester resin has a complex chain structure. Equation 1 can be satisfied.
- the branching agent is a branching agent having three functional groups, for example, benzene-1,2,4-tricarboxylic acid (trimellitic acid), benzene-1,2,4-tricarboxylic acid. Examples include acid anhydride (trimellitic anhydride), benzene-1,2,3-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid anhydride or mixtures thereof. can do.
- Residues derived from the branching agent having three or more functional groups are included in an amount of 1 part by weight or less based on 100 parts by weight of the total diol portion.
- a composition comprising a polyester resin
- the polyester resin according to one embodiment of the present invention can be blended with polyethylene terephthalate to form a composition that provides high-quality extrusion blow-molded products with improved processability.
- the type of polyethylene terephthalate is not particularly limited.
- the polyethylene terephthalate is prepared by polymerization of dicarboxylic acid or a derivative thereof and a diol, the dicarboxylic acid or a derivative thereof may be mainly terephthalic acid or a derivative thereof, and the diol is mainly ethylene glycol can be
- the polyester resin according to the embodiment can supplement the physical properties of virgin polyethylene terephthalate and also compensate for the reduced physical properties of recycled polyethylene terephthalate to a very good level.
- Reusable polyethylene terephthalate may be understood as encompassing all polyethylene terephthalate collected after use or obtained therefrom. Specifically, the reused polyethylene terephthalate is obtained by separating collected waste plastics according to a certain standard, crushing and washing, then melting and extruding to re-pelletize, or after depolymerizing the collected waste plastics to a monomer level. It may be obtained by repolymerizing it. Such reused polyethylene terephthalate may be re-pelletized and then crystallized according to a processing method, or may be used after further polycondensation in a solid state after crystallization.
- Reusable polyethylene terephthalate obtained by depolymerizing and repolymerizing waste plastics at the level of monomers may exhibit good physical properties that are difficult to distinguish from virgin polyethylene terephthalate.
- re-pelletization of waste plastics has overall lower physical properties than virgin polyethylene terephthalate, making it difficult to manufacture high-quality containers using the extrusion blow molding method even when reused polyethylene terephthalate alone or mixed with virgin polyethylene terephthalate is used. difficult.
- the polyester resin according to one embodiment shows excellent miscibility with such reused polyethylene terephthalate and can improve its processability.
- the polyester resin according to one embodiment has very good miscibility with reused polyethylene terephthalate, so that a molded article without flow-marks on the surface can be provided without other additives.
- the polyester resin may be mixed with reused polyethylene terephthalate to effectively control the crystallization rate of reused polyethylene terephthalate and provide a polyester resin composition having a melting point that is easy to dissolve.
- the processability of the polyester resin satisfying Equation 1 and the composition including the same is improved, and in particular, moldability in the extrusion blow molding method can be greatly improved.
- polyester resin and the composition including the polyester resin according to the present invention are easy to recycle.
- TPA terephthalic acid
- EG ethylene glycol
- CHDM 1,4-cyclohexanedimethanol
- ISB isosorbide
- the pressure of the 7 L reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 280 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.80 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg.
- TPA 3429.9 g
- EG 1588.5 g
- CHDM 238.0 g
- ISB 90.5 g
- GeO 2 (10.6 g)
- phosphoric acid (1.46 g) as a stabilizer
- Polysynthren Blue RLS (Clarient, 0.016 g) as a blue toner
- Solvaperm Red BB (Clarient, 0.004 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 275 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.65 dl/g.
- IV intrinsic viscosity
- the mixture was discharged to the outside of the reactor to form strands, which were solidified as a cooling liquid to have an average weight of about 12 to 14 mg.
- TPA (13.1 g)
- EG 1652.5 g
- CHDM 573.9 g
- ISB 72.7 g
- the pressure of the 7 L reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 265 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.85 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. After that, it was allowed to stand at 150° C. for 1 hour to complete crystallization to prepare a polyester resin.
- TPA (3275.5 g), EG (1101.0 g), CHDM (284.1 g), and ISB (144.0 g) were put into a 10 L reactor connected to a column and a condenser capable of cooling with water, and a catalyst As a result, GeO 2 (10.2 g) was added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 285 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.75 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. After that, it was allowed to stand at 150° C. for 1 hour to complete crystallization to prepare a polyester resin.
- TPA (3062.1 g), EG (1269.5 g), CHDM (371.9 g), and ISB (134.7 g) were put into a 10 L reactor connected to a column and a condenser capable of being cooled by water, and a catalyst Into GeO 2 (9.7 g) was added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time the temperature of the reactor was raised to 270 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.80 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. After that, it was allowed to stand at 150° C. for 1 hour to complete crystallization to prepare a polyester resin.
- TPA 3439.6 g
- EG 1541.6 g
- CHDM 328.2 g
- ISB (121.0 g) were put into a 10 L reactor connected to a column and a condenser capable of being cooled by water, and a catalyst
- GeO 2 (10.8 g)
- phosphoric acid (1.46 g) as a stabilizer
- Polysynthren Blue RLS (Clarient, 0.013 g) as a blue toner
- Solvaperm Red BB (Clarient, 0.004 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 275 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.79 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. After that, it was allowed to stand at 150° C. for 1 hour to complete crystallization to prepare a polyester resin.
- DMT dimethyl terephthalate
- EG 2684.7 g
- CHDM 273.5 g
- ISB 3684.4 g
- GeO 2 9.9 g
- the pressure of the 7 L reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 265 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.82 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. After that, it was allowed to stand at 150° C. for 1 hour to complete crystallization to prepare a polyester resin.
- TPA 3232.0 g
- EG 1062.3 g
- ISB (1279.2 g)
- GeO 2 9.9 g
- Polysynthren Blue RLS (Clarient, 0.017 g) as a blue toner
- Solvaperm Red BB (Clarient, 0.006 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered to 100 mmHg at normal pressure and maintained for 1 hour. Thereafter, polycondensation was performed by lowering the pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, simultaneously raising the temperature of the reactor to 280° C. over 1 hour, and maintaining the pressure of the reactor below 1 Torr (absolute pressure: 1 mmHg). reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.75 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. Thereafter, the mixture was allowed to stand at 150° C. for 1 hour to complete crystallization, thereby preparing a polyester resin.
- TPA 2561.1 g
- EG 994.8 g
- CHDM 99.9 g
- ISB 405.5 g
- a catalyst As a GeO 2 (9.9 g), Polysynthren Blue RLS (Clarient, 0.010 g) as a blue toner, and Solvaperm Red BB (Clarient, 0.003 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time the temperature of the reactor was raised to 270 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.82 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. Thereafter, the mixture was allowed to stand at 150° C. for 1 hour to complete crystallization, thereby preparing a polyester resin.
- TPA (3260.1 g), EG (1400.3 g), CHDM (198.0 g), and ISB (86.0 g) were put into a 10 L reactor connected to a column and a condenser capable of cooling with water, and a catalyst As a result, GeO 2 (10.0 g) and phosphoric acid (1.46 g) were added as a stabilizer.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 275 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.60 dl/g.
- IV intrinsic viscosity
- the mixture was discharged out of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg.
- TPA 3118.2 g
- EG 1211.2 g
- CHDM 459.8 g
- ISB 109.7 g
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 275 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.85 dl/g.
- IV intrinsic viscosity
- the mixture is discharged to the outside of the reactor to make a strand, which is solidified with a cooling liquid and then granulated to have an average weight of about 12 to 14 mg to prepare a polyester resin did
- TPA 3238.8 g
- EG 1318.5 g
- CHDM 337.1 g
- ISB 256.4 g
- a catalyst As a GeO 2 (10.3 g), Polysynthren Blue RLS (Clarient, 0.014 g) as a blue toner, and Solvaperm Red BB (Clarient, 0.006 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 280 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction proceeds, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.82 dl/g.
- IV intrinsic viscosity
- the mixture is discharged to the outside of the reactor to make a strand, which is solidified with a cooling liquid and then granulated to have an average weight of about 12 to 14 mg to prepare a polyester resin did
- TPA 3002.1 g
- EG 997.9 g
- CHDM 468.8 g
- ISB 211.2 g
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 285 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.78 dl/g.
- IV intrinsic viscosity
- the mixture is discharged to the outside of the reactor to make a strand, which is solidified with a cooling liquid and then granulated to have an average weight of about 12 to 14 mg to prepare a polyester resin did
- TPA (3207.0 g), EG (1233.7 g), CHDM (194.7 g), and ISB (423.1 g) were put into a 10 L reactor connected to a column and a condenser capable of cooling with water, and a catalyst
- GeO 2 (10.1 g) and phosphoric acid (1.46 g) were added as a stabilizer.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time the temperature of the reactor was raised to 270 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.84 dl/g.
- IV intrinsic viscosity
- the mixture is discharged to the outside of the reactor to make a strand, which is solidified with a cooling liquid and then granulated to have an average weight of about 12 to 14 mg to prepare a polyester resin did
- TPA (3456.2 g), EG (1574.9 g), and ISB (395.2 g) were added to a 10 L reactor connected to a column and a condenser capable of being cooled by water, and GeO 2 (10.6 g) was used as a catalyst.
- Phosphoric acid (1.46 g) as a stabilizer
- Polysynthren Blue RLS (Clarient, 0.012 g) as a blue toner
- Solvaperm Red BB (Clarient, 0.004 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 275 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.75 dl/g.
- IV intrinsic viscosity
- the mixture was discharged to the outside of the reactor to form strands, which were solidified with a cooling liquid and then granulated to have an average weight of about 12 to 14 mg, to obtain a polyester resin. manufactured.
- TPA 2641.8 g
- EG 552.5 g
- CHDM 1260.4 g
- ISB 92.9 g
- GeO 2 9.7 g
- phosphoric acid 1.46 g
- Polysynthren Blue RLS (Clarient, 0.015 g) as a blue toner
- Solvaperm Red BB (Clarient, 0.003 g) as a red toner were added.
- the pressure of the 7 L reactor was lowered from normal pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 285 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction progresses, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or when the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.80 dl/g.
- IV intrinsic viscosity
- the mixture was discharged to the outside of the reactor to form strands, which were solidified with a cooling liquid and then granulated to have an average weight of about 12 to 14 mg, to obtain a polyester resin. manufactured.
- TPA 2422.3 g
- EG 389.0 g
- CHDM 1512.9 g
- ISB 106.5 g
- GeO 2 9 g
- phosphoric acid 1.46 g
- Polysynthren Blue RLS 9 g
- Solvaperm Red BB 0.005 g
- the pressure of the 7 L reactor was lowered from atmospheric pressure to 5 Torr (absolute pressure: 5 mmHg) over 30 minutes, and at the same time, the temperature of the reactor was raised to 280 ° C over 1 hour, and the pressure of the reactor was reduced to 1 Torr (absolute pressure: 5 mmHg) over 1 hour. Pressure: 1 mmHg) or less, the polycondensation reaction was carried out.
- the stirring speed is set quickly, but as the polycondensation reaction proceeds, the stirring speed is appropriately adjusted when the stirring power is weakened due to the increase in the viscosity of the reactants or the temperature of the reactants rises above the set temperature. .
- the polycondensation reaction proceeded until the intrinsic viscosity (IV) of the mixture (melt) in the reactor reached 0.80 dl/g.
- IV intrinsic viscosity
- the mixture was discharged to the outside of the reactor to form strands, which were solidified as a cooling liquid and then granulated to have an average weight of about 12 to 14 mg. Thereafter, the mixture was allowed to stand at 150° C. for 1 hour to complete crystallization, thereby preparing a polyester resin.
- polyester resins of Examples 1 to 7 and Comparative Examples 1 to 8 were measured by the following method and are shown in Table 1.
- Residue composition determination of diol residue molar ratio
- the acid and diol-derived residue composition (mol%) in the polyester resin was obtained by dissolving the sample in CDCl 3 solvent at a concentration of 3 mg/mL and then using a nuclear magnetic resonance apparatus (JEOL, 600 MHz FT-NMR) at 25 ° C. It was confirmed through 1H-NMR spectrum.
- the TMA residue was obtained by measuring the content of benzene-1,2,4-triethylcarboxylate produced by the reaction of ethanol with TMA through ethanolysis at 250 ° C using gas chromatography (Agilent Technologies, 7890B). It was confirmed through quantitative analysis, and it was confirmed by the content (mol%) compared to the number of moles of the total diol portion.
- Intrinsic viscosity was measured by dissolving a polyester resin prepared at a concentration of 0.12% in o-chlorophenol (OCP) at 150 ° C and then measuring the intrinsic viscosity using a Ubell rod-type viscometer in a constant temperature bath at 35 ° C. did Specifically, the time it takes for the solvent to pass between specific inner sections of the viscous tube (efflux time) t 0 and the time t it takes for the solution to pass through were obtained. Then, the specific viscosity was calculated by substituting the t 0 value and the t value into Equation 1, and the specific viscosity value was substituted into Equation 2 to calculate the intrinsic viscosity.
- OCP o-chlorophenol
- the melting point of the prepared polyester resin was measured through differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- Mettler Toledo's DSC1 equipment was used. Specifically, through the process of kneading the crystallizer at a rate of 10 to 100 ppm at a temperature around 230 to 250 ° C. using a twin-screw extruder for the polyester resin prepared in the above Examples and Comparative Examples, After pretreatment to have the maximum crystallinity in the corresponding composition, the melting point was measured at a heating rate of +10 ° C. per minute under nitrogen.
- the polyester copolymers prepared in Examples and Comparative Examples were pretreated as in the case of melting point and measurement so as to have the maximum crystallinity in the corresponding composition, completely melted, and then cooled and crystallized at a temperature reduction rate of -2 ° C. per minute under nitrogen. The temperature was measured.
- the semi-crystallization time was measured by using Mettler Toledo's DSC1 equipment, pre-treating the polyester copolymers prepared in Examples and Comparative Examples as in the case of melting point and measurement so as to have the maximum crystallinity in the corresponding composition, completely melting, and then under nitrogen. It was maintained at 160 ° C. for 60 minutes, and at this time, the time (minutes) at which half of the total calorific value generated during crystallization was measured.
- the injection-molded polyester specimen was placed in a container, immersed in 65% ethanol sufficient to sufficiently submerge the specimen, and then the container containing the specimen and ethanol was stored in a hot air oven at 50 degrees for 1 day. Thereafter, Haze of the specimen was measured using Minolta's CM-3600A measuring instrument in accordance with the ASTM D1003-97 measurement method. Chemical resistance is excellent when haze is less than 5%.
- the capacity of the moldable bottle was 500 mL, 1L, and 2L, and molding was performed in 2 heads. Specifically, the bottle was molded by forming a parison at a temperature around 190 to 250 ° C. in Bekum EBM equipment. The ratio of the transverse length of the molded bottle to the transverse length of the parison was defined as the stretch ratio.
- Bottle molding was performed using the polyester copolymer resin prepared in Examples and Comparative Examples. Specifically, a 500 mL bottle was produced using a parison at a temperature around 190 to 250 ° C. using Bekum EBM equipment. The weight of the manufactured 500mL bottle was measured and marked as ‘O’ if it was 20 g or more, and marked as ‘X’ if it was less than 20 g or if the bottle could not be molded.
- the molded bottle was pulverized to obtain flakes.
- the obtained flakes were blended with 25% by weight of PET flakes and kneaded using a twin-screw extruder at a temperature of about 250 to 280 ° C. to obtain pellets.
- the melting point of the pellets obtained in this way was measured by DSC (differential scanning calorimetry) at a heating rate of +10° C. per minute after completely melting under nitrogen. If the melting point difference between the pellets and PET flakes after the kneading process was less than 10 ° C, it was marked as ‘O’, and if it was greater than 10 ° C, it was marked as ‘X’.
- Examples 1 to 7 according to the present invention since the crystallinity of the resin is not too high, a thick bottle can be molded by lowering the molding temperature. In addition, it can be confirmed that Examples 1 to 7 according to the present invention do not significantly lower the melting point even when blended with PET resin because the crystallinity is not too low, and thus recycling is possible.
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Abstract
Description
ISB 유래 디올 잔기 | CHDM 유래 디올 잔기 | ISB 및 CHDM 유래 디올 잔기 | 용융물 고유점도(IV) | |
단위 | 몰% | 몰% | 몰% | dl/g |
실시예 1 | 1 | 14 | 15 | 0.80 |
실시예 2 | 1 | 8 | 9 | 0.65 |
실시예 3 | 0.5 | 16 | 16.5 | 0.85 |
실시예 4 | 3 | 10 | 13 | 0.75 |
실시예 5 | 3 | 14 | 17 | 0.80 |
실시예 6 | 2 | 11 | 13 | 0.79 |
실시예 7 | 3 | 10 | 13 | 0.82 |
비교예 1 | 0 | 7 | 7 | 0.75 |
비교예 2 | 0 | 18 | 18 | 0.82 |
비교예 3 | 1 | 7 | 8 | 0.60 |
비교예 4 | 2 | 17 | 19 | 0.85 |
비교예 5 | 5 | 12 | 17 | 0.82 |
비교예 6 | 4 | 18 | 22 | 0.78 |
비교예 7 | 8 | 7 | 15 | 0.84 |
비교예 8 | 7 | 0 | 7 | 0.75 |
비교예 9 | 2 | 55 | 57 | 0.80 |
비교예 10 | 3 | 72 | 75 | 0.80 |
연신비 | 에탄올 침지후 Haze | 용융점 | 냉각결정화온도 | 반결정화시간 | 물성 팩터1) | |
단위 | - | % | ℃ | ℃ | 분 | (없음) |
실시예 1 | 1.5 | 2 | 209 | 141 | 7.8 | 37.7 |
실시예 2 | 3.5 | 4 | 225 | 150 | 2.2 | 153.4 |
실시예 3 | 1.5 | 2 | 208 | 140 | 9.9 | 29.4 |
실시예 4 | 2 | 3 | 211 | 142 | 5.7 | 52.6 |
실시예 5 | 1.5 | 3.5 | 207 | 138 | 13.4 | 21.3 |
실시예 6 | 3 | 4 | 212 | 144 | 4.2 | 72.8 |
실시예 7 | 2 | 4.5 | 211 | 142 | 5.7 | 52.6 |
비교예 1 | 5 | 25 | 232 | 175 | 0.7 | 580.8 |
비교예 2 | 1.5 | 20 | 201 | 134 | 26.3 | 10.3 |
비교예 3 | 5 | 10 | 230 | 152 | 0.9 | 388.6 |
비교예 4 | 1.5 | 7 | 207 | 136 | 19.4 | 14.5 |
비교예 5 | 1 | 10 | - | - | - | - |
비교예 6 | 1 | 25 | - | - | - | - |
비교예 7 | 1.5 | 10 | 203 | 135 | 22.6 | 12.1 |
비교예 8 | 4.5 | 3 | 230 | 156 | 1.4 | 256.7 |
비교예 9 | 1 | 5 | - | - | - | - |
비교예 10 | 4 | 4 | 247 | 165 | 2.2 | 185.3 |
1) [수학식 1] 물성 팩터 = (용융점*냉각결정화온도)/(반결정화시간*100) |
Bottle 중량 > 20g | △Tm <10℃ | |
실시예 1 | O | O |
실시예 2 | O | O |
실시예 3 | O | O |
실시예 4 | O | O |
실시예 5 | O | O |
실시예 6 | O | O |
실시예 7 | O | O |
비교예 1 | X | O |
비교예 2 | O | X |
비교예 3 | X | O |
비교예 4 | O | X |
비교예 5 | O | X |
비교예 6 | O | X |
비교예 7 | O | X |
비교예 8 | X | O |
비교예 9 | O | X |
비교예 10 | X | X |
Claims (11)
- 디카르복실산 혹은 이의 유도체로부터 유도된 산 부분 및 디올로부터 유도된 디올 부분이 반복되는 구조를 포함하며,하기 수학식 1을 만족하는, 폴리에스테르 수지:[수학식 1]20 < (X*Y)/(Z*100) < 160상기 수학식 1에서,X는 상기 폴리에스테르 수지의 용융점(단위: ℃)이고,Y는 상기 폴리에스테르 수지의 냉각 결정화 온도 (단위: ℃)이고,Z는 상기 폴리에스테르 수지의 반-결정화 시간 (단위: 분)이다.
- 제1항에 있어서,상기 폴리에스테르 수지는 전체 디올 부분에 대하여 아이소소바이드로부터 유도된 디올 부분을 0.1 내지 3 몰%로 포함하는, 폴리에스테르 수지.
- 제1항에 있어서,상기 폴리에스테르 수지는 전체 디올 부분에 대하여 사이클로헥산디메탄올로부터 유도된 디올 부분을 8 내지 16 몰%로 포함하는, 폴리에스테르 수지.
- 제1항에 있어서,상기 폴리에스테르 수지 조성물은 전체 디올 부분에 대하여 아이소바이드로부터 유도된 디올 부분 및 사이클로헥산디메탄올로부터 유도된 디올 부분의 합을 9 내지 17 몰%로 포함하는, 폴리에스테르 수지.
- 제1항에 있어서,상기 디카르복실산 성분의 잔기는, 테레프탈산, 디메틸테레프탈산 및 이의 유도체로 구성되는 군으로부터 선택되는 어느 하나 이상의 잔기를 포함하는,폴리에스테르 수지.
- 제1항에 있어서,상기 폴리에스테르 수지는 3 이상의 관능기를 가지는 가지화제로부터 유도된 잔기를 포함하는,폴리에스테르 수지.
- 제6항에 있어서,상기 폴리에스테르 수지 조성물은 상기 3 이상의 관능기를 가지는 가지화제로부터 유도된 잔기를 전체 디올 부분 100 중량부에 대하여 1 중량부 이하로 포함하는, 폴리에스테르 수지.
- 제1항에 있어서,상기 폴리에스테르 수지 조성물의 용융점은 200 내지 230℃인,폴리에스테르 수지.
- 제1항에 있어서,상기 폴리에스테르 수지 조성물의 냉각 결정화 온도는 130 내지 150℃인,폴리에스테르 수지.
- 제1항에 있어서,상기 폴리에스테르 수지 조성물의 반 결정화 시간은 1 내지 15분인,폴리에스테르 수지.
- 제1항 내지 제10항 중 어느 하나의 항의 폴리에스테르 수지; 및폴리에틸렌 테레프탈레이트를 포함하는,폴리에스테르 수지 조성물.
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KR20210025466A (ko) * | 2019-08-27 | 2021-03-09 | 에스케이케미칼 주식회사 | 폴리에스테르 수지 혼합물 |
KR20210099148A (ko) | 2018-12-31 | 2021-08-11 | 후아웨이 테크놀러지 컴퍼니 리미티드 | 위치 의존적 예측 조합을 위한 모드 및 크기 의존적 블록 레벨 제한 방법 및 장치 |
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KR20190001551A (ko) * | 2017-06-26 | 2019-01-04 | 에스케이케미칼 주식회사 | 폴리에스테르 필름 및 이의 제조 방법 |
KR20210099148A (ko) | 2018-12-31 | 2021-08-11 | 후아웨이 테크놀러지 컴퍼니 리미티드 | 위치 의존적 예측 조합을 위한 모드 및 크기 의존적 블록 레벨 제한 방법 및 장치 |
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KR20210009844A (ko) * | 2019-07-18 | 2021-01-27 | 에스케이케미칼 주식회사 | 폴리에스테르 수지 혼합물 |
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