KR101868990B1 - Copolymerized polyester resin and preparation method thereof - Google Patents
Copolymerized polyester resin and preparation method thereof Download PDFInfo
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- KR101868990B1 KR101868990B1 KR1020170022144A KR20170022144A KR101868990B1 KR 101868990 B1 KR101868990 B1 KR 101868990B1 KR 1020170022144 A KR1020170022144 A KR 1020170022144A KR 20170022144 A KR20170022144 A KR 20170022144A KR 101868990 B1 KR101868990 B1 KR 101868990B1
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- 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
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- 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
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- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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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
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
- C08L2666/82—Phosphorus-containing stabilizers
Abstract
Description
The examples relate to a polyester resin in which a fluorene compound is copolymerized and a method for producing the same.
In general, polyester resins are excellent in heat resistance, mechanical strength, transparency, and chemical resistance, and are used in films, fibers, containers, bottles, mechanical parts and electronic parts. This trend is continuing to expand.
A polyester resin which is a homopolymer prepared by polymerizing terephthalic acid and ethylene glycol has been unsatisfactory in moldability and a polyester resin copolymerized with various glycols or dicarboxylic acids has been proposed.
For example, Korean Patent Registration No. 10-0504063 discloses a copolymer polyester resin containing terephthalic acid, ethylene glycol and isosorbide, and the polyester resin exhibits excellent heat resistance by including isosorbide.
However, when the polyester resin contains a large amount of isosorbide, there is a problem that the color of the resin is discolored, the mechanical properties of the resin are lowered and the reactivity is lowered, making it difficult to produce a polymer having a high polymerization degree.
Therefore, the object of the examples is to provide a copolymerized polyester resin free from discoloration of the resin and excellent in impact resistance, heat resistance and chemical resistance, and a method for producing the same.
In order to achieve the above object,
(a) a dicarboxylic acid repeat unit comprising 50 to 100 mole% of a terephthalic acid (TPA) moiety; And
(b) a diol repeat unit comprising 2 to 60 mol% of a fluorene compound, 1 to 45 mol% of neopentyl glycol (NPG) and 30 to 97 mol% of an ethylene glycol (EG)
(9-bis [4- (2-hydroxyethoxy) phenyl] -Fluorene, BPEF), 9 (9-bis (4-hydroxyphenyl) fluorene, BPF) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene , 9-bis (4-glycidyloxy-3-methylphenyl) fluorene, BCFG).
Another embodiment of the present invention is a method for producing a polyester resin composition, comprising the steps of: (1) mixing a diene component containing a fluorene compound, NPG and EG with a dicarboxylic acid component containing TPA in a molar ratio of 1.05 to 3.0; And
(2) mixing the esterification reaction product, the metal catalyst, and the phosphorus stabilizer to effect a polycondensation reaction,
(9-bis [4- (2-hydroxyethoxy) phenyl] -Fluorene, BPEF), 9 (9-bis (4-hydroxyphenyl) fluorene, BPF) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene , 9-bis (4-glycidyloxy-3-methylphenyl) fluorene, BCFG).
The copolyester resin according to the embodiment has a low color-b (yellowing degree) value, is more transparent, has excellent impact resistance, chemical resistance and heat resistance, and is used in various fields requiring excellent physical properties such as foods, cosmetic containers, Can be applied.
Copolymerized polyester resin
The copolymer polyester resin of one embodiment comprises: (a) a dicarboxylic acid repeat unit comprising 50 to 100 mole% of a terephthalic acid (TPA) moiety; And (b) a diol repeat unit comprising from 2 to 60 mol% of a fluorene compound, from 1 to 45 mol% neopentyl glycol (NPG) and from 30 to 97 mol% ethylene glycol (EG)
(9-bis [4- (2-hydroxyethoxy) phenyl] -Fluorene, BPEF), 9 (9-bis (4-hydroxyphenyl) fluorene, BPF) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene , 9-bis (4-glycidyloxy-3-methylphenyl) florene, BCFG).
The dicarboxylic acid repeating unit may contain 50 to 100 mol% of TPA residues relative to the total repeating units of dicarboxylic acid. Specifically, the dicarboxylic acid repeating unit may contain 70 to 100 mol%, or 80 to 100 mol%, of the TPA residue with respect to the total repeating units of the dicarboxylic acid.
The above-mentioned dicarboxylic acid repeating unit may contain, in addition to the TPA residue, an isophthalic acid (IPA), 2,6-dimethylnaphthalene dicarboxylic acid (NDC), 1,4-cyclohexane dicarboxylic acid -CHDA), 1,3-cyclohexanedicarboxylic acid (1,3-CHDA), succinic acid, glutaric acid, adipic acid, sebacic acid, 2,5-furandicarboxylic acid, , 2,7-naphthalene dicarboxylic acid, 4,4'-dibenzoic acid, and derivatives thereof. The dicarboxylic acid may further contain at least one dicarboxylic acid. Specifically, the dicarboxylic acid repeating unit may further include a dicarboxylic acid selected from the group consisting of IPA, NDC, and combinations thereof. Further, the additional dicarboxylic acid repeating unit may be contained in an amount of 0 to 50 mol%, 0 to 25 mol%, or 0 to 20 mol% based on the total repeating units of the dicarboxylic acid.
The diol repeat unit comprises 2 to 60 mol% of a fluorene compound, 1 to 45 mol% of neopentyl glycol (NPG) and 30 to 97 mol% of an ethylene glycol (EG) moiety relative to the total diol repeat units . Specifically, the diol repeating unit may include 5 to 55 mol% of a fluorene compound and 1 to 30 mol% of an NPG residue based on the total diol repeating units. More specifically, the diol repeat unit may comprise from 5 to 55 mol% of the fluorene compound, from 1 to 30 mol% of NPG and from 35 to 94 mol% of the EG residue, based on the total diol repeat units.
When the fluorene compound residue in the above content range is contained, the heat resistance, the chemical resistance and the impact resistance of the produced polyester resin are improved, and the color-b (yellowness) value of the resin is lowered to produce a more transparent polyester resin can do.
When the NPG residues in the above content range are included, the mechanical properties of the resin are improved and the processability of the produced polyester resin chip is improved and the heat resistance is improved. Also, by including NPG residues, the reactivity is improved as compared with the copolymer containing no NPG residues, so that the produced copolyester resin is less discolored and is advantageous in terms of color improvement.
The fluorene compound serves to improve the mechanical properties of the polyester resin, and the 9,9-bis [4- (2-hydroxyethoxy) phenyl] -fluorene (9,9-bis [4- 2-hydroxyethoxy) phenyl] -Fluorene, BPEF, 9,9-bis (4-hydroxypheny) florene, BPF and 9,9- Glycidyloxy-3-methylphenyl) fluorene, and BCFG). Specifically, the fluorene compound may be BPEF.
The copolymer polyester resin may include 50 to 500 ppm of a metal catalyst based on the total weight of the resin and 3,000 ppm or less of a tripolar stabilizer. Specifically, the copolymer polyester resin may include 70 to 400 ppm of a metal catalyst based on the total weight of the resin and 10 to 3,000 ppm of a triphenylamine stabilizer.
The metal catalyst is used as a polycondensation catalyst in the production of a polyester resin. Specifically, the metal catalyst may include at least one selected from the group consisting of alkali metals, alkaline earth metals, antimony, titanium, manganese, cobalt, cerium and germanium. More specifically, the metal catalyst may include at least one selected from the group consisting of antimony, titanium, manganese, cobalt, cerium, and germanium.
The phosphorus stabilizer may include at least one member selected from the group consisting of phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, and hindered phenol.
When the metal catalyst is contained in the above-mentioned content range, the Color-b (yellowness value) of the resin is 5 or less, so that transparency is excellent and the heat resistance of the resin is improved.
When a phosphorus stabilizer is contained in the above content range, a polyester resin having a high polymerization degree can be produced.
In order to improve the color, the copolymer polyester resin may further include a coloring agent. Examples of the coloring agent include cobalt acetate, cobalt propionate, and the like. The coloring agent may be used in an amount of 5 to 100 ppm based on the total weight of the polyester resin.
The copolyester resin according to the embodiment has a glass transition temperature (Tg) of 80 DEG C or more, or 80 to 120 DEG C, and is excellent in heat resistance. The copolymer polyester resin has a color-b value of not more than 5, not more than 4.9, or not more than 4.8, and is excellent in transparency. Further, the copolymer polyester resin has an impact strength of not less than 2 J / m, not less than 3 J / m, not less than 3.5 J / m, or not less than 3.5 J / m and not more than 20 J / m.
The copolymerized polyester resin according to the embodiment has an intrinsic viscosity (IV) of 0.4 to 0.8 dl / g, or 0.42 to 0.7 dl / g. When the intrinsic viscosity is 0.4 dl / g or more, the physical properties of the product are not deteriorated even when extruded or extruded, and when the density is 0.8 dl / g or less, the process does not require much load.
Injection products prepared using the copolyester resin may be used in various organic solvents such as methanol (MeOH), tetrahydrofuran (THF), isophthalic acid (IPA), ethyl acetate (EA), hexane, heptane, Sodium hydroxide (NaOH) and the like) for 4 hours or more, the white coloration, swelling, and cracking were less likely to occur and the chemical resistance was excellent (see Experimental Example 2).
The copolyester resin according to the embodiment is transparent and has excellent impact resistance, chemical resistance and heat resistance because it has a low color-b (yellowing degree) value, and can be applied to various fields requiring excellent physical properties such as foods, cosmetic containers, have.
Process for producing copolymerized polyester resin
The process for producing the copolymer polyester resin of another embodiment
(1) mixing a diol component including a fluorene compound, NPG, and EG with a dicarboxylic acid component containing TPA in a molar ratio of 1.05 to 3.0 to perform an esterification reaction; And (2) a polycondensation reaction of an esterification reaction product, a metal catalyst and a phosphorus stabilizer,
(9-bis [4- (2-hydroxyethoxy) phenyl] -Fluorene, BPEF), 9 (9-bis (4-hydroxyphenyl) fluorene, BPF) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene , 9-bis (4-glycidyloxy-3-methylphenyl) florene, BCFG).
Step (1)
In this step, the diol component including the fluorene compound, NPG, and EG is mixed with the dicarboxylic acid component containing TPA in a molar ratio of 1.05 to 3.0, and esterified.
When the content of the diol component relative to the dicarboxylic acid component is out of the above-mentioned molar ratio, esterification or transesterification is unstable and sufficient ester oligomer can not be formed, and the problem that the characteristics of the fluorene compound is difficult to be expressed Lt; / RTI >
The dicarboxylic acid component may contain 50 to 100 mol% of TPA based on the total molar amount of the dicarboxylic acid component. Specifically, the dicarboxylic acid component may contain 70 to 100 mol%, or 80 to 100 mol% of TPA based on the total molar amount of the dicarboxylic acid component.
The dicarboxylic acid component may contain, in addition to TPA, an isophthalic acid (IPA), 2,6-dimethylnaphthalene dicarboxylic acid (NDC), 1,4-cyclohexane dicarboxylic acid (1,4-CHDA ), 1,3-cyclohexanedicarboxylic acid (1,3-CHDA), succinic acid, glutaric acid, adipic acid, sebacic acid, 2,5-furandicarboxylic acid, 2,5-thiopendicarboxylic acid, 2 , 7-naphthalene dicarboxylic acid, 4,4'-dibenzoic acid, and derivatives thereof. The dicarboxylic acid may further include at least one dicarboxylic acid. Specifically, the dicarboxylic acid component may further include a dicarboxylic acid selected from the group consisting of IPA, NDC, and combinations thereof. Further, the additional dicarboxylic acid component may be contained in an amount of 0 to 50 mol%, 0 to 25 mol%, or 0 to 20 mol% based on the total molar amount of the dicarboxylic acid component.
The diol component comprises 2 to 60 mol% of a fluorene compound, 1 to 45 mol% of neopentyl glycol (NPG) and 30 to 97 mol% of ethylene glycol (EG) based on the total molar amount of the diol component. Specifically, the diol component may contain 5 to 55 mol% of a fluorene compound and 1 to 30 mol% of NPG based on the total molar amount of the diol component. More specifically, the diol component may comprise from 5 to 55 mol% of a fluorene compound, from 1 to 30 mol% of NPG and from 35 to 94 mol% of EG based on the total molar amount of the diol component.
When a fluorene compound is contained in the above content range, the produced polyester resin is improved in heat resistance, chemical resistance and impact resistance, and the color-b (yellowness degree) value of the resin is lowered to produce a polyester resin having excellent transparency can do.
When NPG is contained in the above content range, the mechanical properties of the resin are improved and the processability of the produced polyester resin chip is improved and the heat resistance is improved. Also, by including NPG, the reactivity is improved as compared with the copolymer containing no NPG, so that discoloration of the produced copolymer polyester resin is reduced, which is advantageous for color improvement.
The esterification reaction may be performed at a pressure of 0.1 to 3.0 kg / cm 2 and an average residence time of 1 to 10 hours at a temperature of 200 to 300 ° C. Specifically, the esterification reaction may be carried out at a pressure of 0.2 to 3.0 kg / cm 2 or 0.5 to 2.9 kg / cm 2 and at an average residence time of 2 to 10 hours, 1 to 8 hours, or at a temperature of 230 to 260 ° C or 235 to 255 ° C 1.5 to 7 hours. The esterification reaction time may vary depending on the reaction temperature, the pressure, and the molar ratio of the diol component to the dicarboxylic acid used, but is preferably performed under the above conditions.
Step (2)
In this step, the polycondensation reaction is carried out by mixing the esterification reaction product, the metal catalyst and the phosphorus stabilizer.
The residual amount and kind of the metal catalyst and the residual amount and kind of the phosphorus stabilizer are as described for the copolymer polyester resin.
The polycondensation reaction may be performed 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. Specifically, the polycondensation reaction may be carried out under a reduced pressure of 300 to 0.1 mmHg and an average residence time of 1 to 10 hours at a temperature of 240 to 290 ° C or 250 to 280 ° C.
Molded articles of other embodiments are made from the copolymerized polyester resin.
The molded article may be a molded article applicable to various applications by molding the copolymer polyester resin by a molding method such as injection, extrusion and compounding processes known in the art such as biaxial extrusion.
The molded article may be in various forms such as a film, a sheet, or a fiber. The molded article may be an injection molded article, an extrusion molded article, or a blow molded article.
If the molded product is a film or a sheet, it may be various films or sheets such as unstretched, uniaxially stretched, biaxially stretched, and the like. If the molded product is a fiber, it may be any of various fibers such as unstretched yarn, drawn yarn, or primary yarn, and may be used as a fabric, a knitted fabric, a nonwoven fabric (spun bond, melt blow, staple), a rope or a net.
The molded article can be used as coatings for electrical and electronic parts such as computer accessories, architectural members, automobile parts, machine parts, daily articles or chemical parts, and chemical resistance fibers for industrial use.
[ Example ]
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
In the following examples and comparative examples, TPA is terephthalic acid, NDC is 2,6-dimethylnaphthalene dicarboxylic acid, BPEF is 9,9-bis [4- ( (9,9-bis [4- (2-hydroxyethoxy) phenyl] -florene), EG means ethyleneglycol and NPG means neopentylglycol do.
Example 1 to 6 and Comparative Example 1 to 5: Preparation of copolymerized polyester resin
A copolymerized polyester resin was prepared using the components and contents shown in Table 1 below.
Specifically, a diol component and a dicarboxylic acid component were added to a 30 L reactor equipped with a stirrer and an outlet condenser, with 20 kg of the final polymer as a base. The diol component and the dicarboxylic acid component were added so that the diol component was 1.3 mol based on the dicarboxylic acid component. Then, the internal pressure of the reactor was increased to 2.0 kg / cm < 2 > using nitrogen, and the temperature of the reactor was increased to 255 < 0 > C. The reaction product was transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser and a vacuum system when the generated water was discharged out of the system and esterified.
Antimony catalyst (Sb, manufactured by Sigma-Aldrich Co., Ltd., product name: Antimony (III) oxide) was added to the obtained esterification reaction product as a metal polycondensation catalyst in terms of antimony atom content ), And triethyl phosphate (TEP) as a phosphorus stabilizer was added so as to have the content shown in the following Table 1 (based on the amount of the final polymer) based on the phosphorus content. Thereafter, the internal temperature of the reactor was increased from 240 ° C to 275 ° C, and the pressure was reduced to a low pressure of 50 mmHg for 40 minutes under atmospheric pressure. Ethylene glycol was then withdrawn from the system, and the pressure was gradually reduced to 0.1 mmHg and the reaction was continued under high vacuum to 0.36 A power. The resultant polycondensation reaction product was discharged and cut into chips to prepare a copolymer polyester resin.
(ppm)
Experimental Example 1: Measurement of physical properties of polyester resin
The properties of the polyester resins prepared in the above Examples and Comparative Examples were measured according to the following methods and are shown in Table 2 below.
(1) Intrinsic viscosity (IV)
After dissolution of o-chlorophenol at 100 ° C, the falling time of the sample was measured with an Ostwald viscosity tube in a 35 ° C thermostatic chamber and the intrinsic viscosity (IV) of the sample was measured.
(2) Glass transition temperature (heat resistance)
The polyester resin was annealed at 300 캜 for 5 minutes, cooled to room temperature, and then measured for glass-rubber transition temperature (Tg) at the time of re-scanning at a heating rate of 10 캜 / min.
(3) Color (b)
Color-b (yellowness) values were measured using a Nippon Denshoku Spectrophotometer SE6000.
(4) Impact strength
3.2 mm thick specimens were prepared using a polyester resin and notched according to ASTM D 256, and then the impact strength was measured at 23 ° C with an izod impact strength measuring instrument.
As shown in Table 2, the polyester resins of Examples 1 to 6 were compared with the polyester resins of Comparative Example 1 which did not contain a fluorene compound and Comparative Examples 2 and 3 which contained a small amount of a fluorene compound It has been found that it has a high glass transition temperature of 80 占 폚 or higher and excellent heat resistance, low color-b value of 5 or less, excellent transparency, high impact strength of 3.5 J / m or more and excellent impact resistance.
In Comparative Example 4 containing an excessive amount of fluorene compound and Comparative Example 5 containing no NPG, a large amount of gas was generated during extrusion, and the process was extremely unstable. This is presumably due to the fact that the molecular chain is decomposed and gasified by heat due to the lack of polymerization degree.
Experimental Example 2: Measurement of chemical resistance of articles using polyester resin
Under the conditions of a barrel temperature of 240 占 폚 and a pressure of 1,200 kgf / cm2 using the polyester resin prepared in the above-mentioned Examples and Comparative Examples, heat treatment was carried out under conditions of a mold temperature of 30 占 폚, an injection time of 10 seconds, To prepare an injection specimen of 3 cm x 12 cm x 0.3 cm (width x length x thickness).
The injection specimens were precipitated in the organic solvents listed in Table 3 for 4 hours or 24 hours, respectively, and the changes were observed. The results are shown in Table 3 below. Concretely, ◯ indicates no change, H indicates haze change, W indicates whiteness, S indicates swelling, and M indicates dissolution. Numbers indicate the degree of each phenomenon, and the larger the number, the greater the degree of change.
In Table 3 below, MeOH is methanol, THF is tetrahydrofuran, IPA is isophthalic acid, EA is ethyl acetate, and NaOH is sodium hydroxide.
As shown in Table 3, the molded articles prepared from the polyester resins of Examples 4 and 5 had significantly superior chemical resistance to the organic solvents as compared with the molded articles produced from the polyester resin of Comparative Example 2. [
Claims (9)
(b) a diol repeat unit comprising 5 to 55 mol% of a fluorene compound, 1 to 30 mol% of neopentyl glycol (NPG) and 35 to 94 mol% of an ethylene glycol (EG)
Lt; / RTI >
(9-bis [4- (2-hydroxyethoxy) phenyl] -Fluorene, BPEF), 9 (9-bis (4-hydroxyphenyl) fluorene, BPF) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene , 9-bis (4-glycidyloxy-3-methylphenyl) florene, BCFG)
A color-b value of 5 or less, an impact strength of 3 J / m or more, and an intrinsic viscosity (IV) of 0.42 to 0.7 dl / g in a 3.2 mm thick test piece.
Wherein the dicarboxylic acid repeating unit is selected from the group consisting of isophthalic acid (IPA), 2,6-dimethylnaphthalene dicarboxylic acid (NDC), 1,4-cyclohexane dicarboxylic acid (1,4-CHDA) (1,3-CHDA), succinic acid, glutaric acid, adipic acid, sebacic acid, 2,5-furandicarboxylic acid, 2,5-thiopendicarboxylic acid, 2,7-naphthalenedicarboxylic acid , 4,4'-dibenzoic acid, and derivatives thereof. The copolymer polyester resin according to claim 1, wherein the dicarboxylic acid is a dicarboxylic acid.
Wherein the copolymer polyester resin comprises 50 to 500 ppm of a metal catalyst based on the total weight of the resin and 3,000 ppm or less of a triphenylamine stabilizer.
Wherein the copolymerized polyester resin has a glass transition temperature (Tg) of 80 DEG C or more.
(2) mixing the esterification reaction product, the metal catalyst, and the phosphorus stabilizer to effect a polycondensation reaction,
(9-bis [4- (2-hydroxyethoxy) phenyl] -Fluorene, BPEF), 9 (9-bis (4-hydroxyphenyl) fluorene, BPF) and 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene , 9-bis (4-glycidyloxy-3-methylphenyl) florene, BCFG)
The method according to claim 1, wherein the diol repeat unit comprises from 5 to 55 mol% of a fluorene compound, from 1 to 30 mol% neopentyl glycol (NPG) and from 35 to 94 mol% ethylene glycol (EG) A method for producing a copolymer polyester resin.
Wherein the dicarboxylic acid component comprises 50 to 100 mol% of TPA.
Wherein the esterification reaction is carried out at a pressure of 0.1 to 3.0 kg / cm 2 and an average residence time of 1 to 10 hours at a temperature of 200 to 300 ° C.
Wherein the polycondensation reaction is carried out 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 占 폚.
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| KR20210057849A (en) * | 2019-11-12 | 2021-05-24 | 에스케이씨 주식회사 | Thermosetting resin composition and decoration sheet using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210057849A (en) * | 2019-11-12 | 2021-05-24 | 에스케이씨 주식회사 | Thermosetting resin composition and decoration sheet using same |
| KR102374568B1 (en) * | 2019-11-12 | 2022-03-16 | 에스케이씨 주식회사 | Thermosetting resin composition and decoration sheet using same |
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