WO2024085502A1 - Composition de résine comprenant une résine de polyesteramide et article moulé associé - Google Patents

Composition de résine comprenant une résine de polyesteramide et article moulé associé Download PDF

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WO2024085502A1
WO2024085502A1 PCT/KR2023/015197 KR2023015197W WO2024085502A1 WO 2024085502 A1 WO2024085502 A1 WO 2024085502A1 KR 2023015197 W KR2023015197 W KR 2023015197W WO 2024085502 A1 WO2024085502 A1 WO 2024085502A1
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resin composition
resin
weight
residue
diol
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PCT/KR2023/015197
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English (en)
Korean (ko)
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김도균
김성기
김해리
박준용
황신영
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에스케이케미칼 주식회사
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Publication of WO2024085502A1 publication Critical patent/WO2024085502A1/fr

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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to polyesteramide resin compositions and molded articles thereof.
  • Polyester resin is a material with excellent mechanical strength, heat resistance, transparency, and gas barrier properties.
  • PET polyethylene terephthalate
  • TPA terephthalic acid
  • EG ethylene glycol
  • biaxially stretched PET films are used for packaging and displays. It is used for industrial purposes, insulating materials, and in various other industrial fields.
  • PET has a low melting point (Tm) of 260°C, which limits the application of surface mount technology recently used in the industry.
  • PCT polycyclohexanedimethylene terephthalate
  • PCT has a low moisture absorption rate and excellent heat resistance and chemical resistance, but low mechanical strength.
  • the crystallization rate is faster than PET, it is still slower than other engineering plastics, resulting in longer injection times and lower productivity.
  • polyamide resins represented by nylon-6 and nylon-6,6, have properties such as mechanical strength, heat resistance, abrasion resistance, and chemical resistance, and are attracting attention as a material applicable to various industries.
  • polyamide resin has poor long-term dimensional stability and has the problem of deteriorating mechanical properties when it absorbs water. Accordingly, research is in progress to solve this problem, and for example, blending it with other polymer resins that have excellent heat resistance and show little change in physical properties even in a relatively high humidity environment is being considered.
  • polyamide resin has poor compatibility with other polymer resins, so even when blended, defects may occur in the extrusion process, and there is a high possibility that the physical properties of the produced polymer resin molded product will not meet the desired level.
  • the present disclosure seeks to provide a polyesteramide resin composition that has excellent compatibility with polyamide resin without the need for a compatibilizer in order to improve productivity and improve mechanical properties by shortening the injection time of polyester resin.
  • the present disclosure seeks to provide a polyesteramide resin composition that is based on blending polyamide resin and polyester resin and has excellent compatibility without adding a compatibilizer with an existing functional group.
  • the present disclosure seeks to provide a polyesteramide resin composition that has improved productivity by shortening the injection time and has excellent mechanical properties.
  • Embodiments of the present invention provide a polyesteramide resin copolymerized with a diacid component, a diol component, and a diamine component, a composition thereof, and a molded article containing the same.
  • the diacid component and the diol component are blended in a specific molar ratio.
  • 'moiety' refers to a certain part or unit derived from a specific compound when the specific compound participates in a chemical reaction and is included in the product of the chemical reaction.
  • the 'residue' of the diacid component, the 'residue' of the diol component, and the 'residue' of the diamine component are a portion derived from the diacid component and a portion derived from the diol component, respectively. refers to a portion derived from the diamine component and a portion derived from the diamine component.
  • One embodiment of the present disclosure includes polyesteramide resin; and polyamide, wherein the polyamide is contained in an amount of 1 part by weight to 30 parts by weight or 70 parts by weight to less than 100 parts by weight based on 100 parts by weight of the resin composition.
  • the purpose of the resin composition of the present disclosure is to have excellent compatibility without adding a compatibilizer and to maintain the excellent physical properties of each resin by blending polyamide with polyesteramide resin.
  • the polyamide is used in an amount of 1 part by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more to 30 parts by weight, 25 parts by weight or less, and 20 parts by weight.
  • it may be included in 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. If too little polyamide is included, the effect of increasing productivity and improving physical properties by shortening the injection time that is desired by blending polyamide resins cannot be obtained, and if too much polyamide is included, dimensional stability is poor. There may be a problem.
  • the polyamide may be included in an amount of 70 parts by weight or more, 75 parts by weight or more, 80 parts by weight or more, or 85 parts by weight or more but less than 100 parts by weight, 95 parts by weight or less, or 90 parts by weight or less. You can. When polyamide is the main ingredient in the resin composition, dimensional stability and moisture content can be improved.
  • the resin composition of the present invention may have a polyamide mixing amount of 1 to 30 parts by weight or 70 to less than 100 parts by weight, depending on the desired effect. If you want to improve extrusion processability and mechanical properties by improving compatibility without a compatibilizer, the polyamide mixing amount can be 1 to 30 parts by weight per 100 parts by weight of the resin composition. In order to use it even under long-term moisture absorption conditions, To ensure low moisture absorption, the mixing amount of polyamide may be 70 parts by weight or more to less than 100 parts by weight based on 100 parts by weight of the resin composition.
  • the polyamide resin that can be blended with the polyesteramide resin is not limited as long as it is a polyamide resin, but for example, one selected from the group consisting of nylon-6, nylon-6,6, nylon-6T, and nylon-9T. It could be more than that.
  • Blended products containing the above polyesteramide resin are characterized by improved productivity and improved mechanical properties due to improved crystallization speed and shortened injection time.
  • polyamide resin alloyed with polyesteramide resin has little deterioration in physical properties, and its saturated moisture content can be lowered, thereby greatly improving dimensional stability.
  • the present disclosure can provide a molded article containing the above resin composition.
  • the molded product can be used for electrical or electronic parts such as connectors, automobile parts, mobile phone parts, home appliances such as TVs, refrigerators, or washing machines, or office automation equipment.
  • polyesteramide resin
  • a diacid residue which is a residue of a diacid component containing terephthalic acid
  • a diol residue which is the residue of a diol component including cyclohexanedimethanol
  • a diamine residue which is a residue of a diamine component containing bis(aminomethyl)cyclohexane, wherein the molar ratio of the diacid residue and the diol residue satisfies a specific range.
  • the polyesteramide resin secures mechanical strength, heat resistance, chemical resistance, etc. due to the diacid residue, transparency and impact resistance due to the diol residue, and heat resistance (especially heat resistance) due to the diamine residue. , thermal properties such as Tg) and film physical properties (particularly, physical properties such as tensile strength and storage modulus) are improved.
  • the diamine residue present in the polyesteramide resin has a chemical structure similar to the amide bond of the polyamide resin. Accordingly, compatibility in blended products is improved, enabling stable expression of physical properties of blended products.
  • the blended polyesteramide resin can improve productivity by shortening the injection time. Additionally, a blended polyesteramide resin with improved mechanical properties can be obtained.
  • a polyamide resin was blended with a highly heat-resistant thermoplastic polyesteramide resin that has a low moisture absorption rate under long-term moisture absorption conditions.
  • a polymer compatibilizer it was possible to successfully prepare a new polyesteramide resin composition through improved miscibility of the two resins without the need for a polymer compatibilizer. It was confirmed that the new polyesteramide resin composition produced had excellent compatibility, so there was little deterioration in physical properties, and that the shape stability was greatly improved due to the low saturated moisture content.
  • polyesteramide resin will be described in detail.
  • the 'residue' of the diacid component refers to a portion derived from the diacid component.
  • the diacid component undergoes esterification and amidation reactions with the diol component and the diamine component; And it corresponds to the main monomer that forms polyesteramide resin through polycondensation reaction.
  • the diacid component includes terephthalic acid
  • the polyesteramide resin may have improved physical properties such as mechanical strength, heat resistance, and chemical resistance by the terephthalic acid.
  • the diacid component may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component, or a mixture thereof in addition to terephthalic acid.
  • diacid components other than terephthalic acid may be included in an amount of 1 to 20 mol% based on 100 mol% of the total residues of all diacid components.
  • the aromatic dicarboxylic acid component may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, specifically, an aromatic dicarboxylic acid having 8 to 14 carbon atoms, or a mixture thereof.
  • the aromatic dicarboxylic acids include isophthalic acid, naphthalene dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbendicarboxylic acid, 2, Examples include 5-furandicarboxylic acid and 2,5-thiophenedicarboxylic acid, but specific examples of the aromatic dicarboxylic acid are not limited thereto.
  • the aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms, or a mixture thereof.
  • the aliphatic dicarboxylic acids include cyclohexanedicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecylsuccinic acid,
  • There are linear, branched or cyclic aliphatic dicarboxylic acids such as maleic acid, fumaric acid, adipic acid, glutaric acid and azelaic acid, but specific examples of the aliphatic dicarboxylic acids are not limited thereto.
  • the 'residue' of the diol component refers to a portion derived from the diol component.
  • the diol component corresponds to the main monomer that forms the polyesteramide resin through esterification reaction and polycondensation reaction with the above-mentioned diacid component.
  • the diol component includes cyclohexanedimethanol (CHDM), and cyclohexanedimethanol is a component that contributes to improving the transparency and impact resistance of the polyesteramide.
  • CHDM cyclohexanedimethanol
  • the cyclohexanedimethanol may include at least one selected from the group consisting of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol (1,4-CHDM). You can.
  • 1,4-cyclohexanedimethanol can be used, as described in the examples below.
  • the residue derived from the diol component in the polyesteramide resin is based on 100 mol% of the diacid residue. It may contain 70 to 99 mol%.
  • the effects of the polyesteramide resin on heat resistance and film physical properties may be minimal.
  • the diol residue in the polyesteramide resin is, based on 100 mol% of the diacid residue, 70 mol% or more, 72 mol% or more, 74 mol% or more, 76 mol% or more, 78 mol% or more, or 80 mol%. It may be included in mol% or more, 99 mol% or less, 98.5 mol% or less, 98 mol% or less, 98.5 mol% or less, or 97 mol% or less.
  • the diol component includes ethylene glycol, isosorbide, 1,3-cyclobutanediol, 2,4-dimethylcyclobutane-1,3-diol, 2,4-diethylcyclobutane-1, 3-diol, 2,2-dimethylcyclobutane-1,3-diol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, Decalin dimethanol, tricyclotetradecanedimethanol, norbornene dimethanol, adamantane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetra Oxaspiro[5.5]undecane, bicyclo[2.2.2]octane-2,3-dimethanol, 1,3-cyclohexanedi
  • the ethylene glycol is a component that contributes to improving the transparency and impact resistance of the polyester copolymer produced with cyclohexanedimethanol.
  • the isosorbide is used to improve the processability of the polyester copolymer being produced.
  • the transparency and impact resistance of the polyester copolymer are improved by the diol components of cyclohexanedimethanol and ethylene glycol, but for processability, shear fluidization characteristics must be improved and the crystallization rate must be delayed. It is difficult to achieve this effect with ethylene glycol alone. Accordingly, when isosorbide is included as a diol component, shear fluidization characteristics are improved and the crystallization rate is delayed while transparency and impact resistance are maintained, thereby improving the processability of the polyester copolymer produced.
  • the diamine component is added together with the diacid component and the diol component, and is the main monomer that undergoes amidation reaction and polycondensation reaction with the diacid component to form the polyesteramide resin. do.
  • the diamine component includes bis(aminomethyl)cyclohexane (BAC), and the bis(aminomethyl)cyclohexane has a molecular weight of 140 to 150 g/mol and a boiling point. It is a 235 to 250°C compound that contributes to improving the heat resistance (particularly, thermal properties such as Tg) and film properties (particularly, physical properties such as tensile strength and storage modulus) of the polyesteramide resin.
  • BAC bis(aminomethyl)cyclohexane
  • the bis(aminomethyl)cyclohexane has a molecular weight of 140 to 150 g/mol and a boiling point. It is a 235 to 250°C compound that contributes to improving the heat resistance (particularly, thermal properties such as Tg) and film properties (particularly, physical properties such as tensile strength and storage modulus) of the polyesteramide resin.
  • the bis(aminomethyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), or any of these. May include mixtures.
  • 1,3-bis(aminomethyl)cyclohexane represented by Formula 1 below or 1,4-bis(aminomethyl) represented by Formula 2 below as in the Examples described later.
  • Methyl)cyclohexane can be used as the bis(aminomethyl)cyclohexane represented by Formula 1 below or 1,4-bis(aminomethyl) represented by Formula 2 below.
  • the residue derived from the diamine component in the polyesteramide resin may be included in an amount of 1 to 30 mol% based on 100 mol% of the diacid residue.
  • the content of the diamine residue exceeds the above range, the content of the diol residue is relatively reduced, and the transparency and impact resistance of the polyesteramide resin may be significantly inferior.
  • the effect of the polyesteramide resin may be minimal.
  • the content of the diamine residue satisfies the above range, the heat resistance and film properties of the polyesteramide resin can be improved. Additionally, within the above range, it is possible to appropriately adjust the content of the diamine residue in consideration of the physical properties of the desired polyesteramide resin.
  • the diamine residue in the polyesteramide resin is 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, or 3 mol% or more based on 100 mol% of the diacid residue, It may be included in 30 mol% or less, 28 mol% or less, 26 mol% or less, 24 mol% or less, 22 mol% or less, or 20 mol% or less.
  • the diamine component includes 4,4'-methylenebis(2-methylcyclohexylamine), 4,4'-methylenebis(cyclohexylamine), and 1,4-tetramethylene diamine.
  • the polyester resin is prepared by additionally containing the diamine component. It is confirmed that the glass transition temperature (Tg) and zero shear viscosity (ZSV) of the polyesteramide resin are significantly high.
  • the glass transition temperature and melt viscosity of the polyesteramide resin are increased as a result of the additional introduction of diamine residues into the main chain. ), and it can be seen that the zero shear viscosity increases.
  • the diamine residue present in polyesteramide resin has a chemical structure similar to the amide bond of polyamide resin, improving compatibility in blended products and enabling stable expression of physical properties of blended products. If the content of diamine residues present in the polyesteramide resin is too low, compatibility with polyamide resins such as nylon resins may be poor in the alloy process, making it difficult to develop stable physical properties. On the other hand, if the content of diamine residues in the polyesteramide resin is too high, the product may be discolored or have poor shape stability due to the effects of oxygen or moisture after processing.
  • the diol residue may be included in 70 to 99 mol%, and the diamine residue may be included in 1 to 30 mol%, and this range The content of each residue can be appropriately adjusted.
  • the molar ratio of the diacid residue and the diol residue needs to satisfy a specific range.
  • the diol residue Based on 100 mol% of the diacid residue, the diol residue must satisfy 70 to 99 mol%.
  • the diol residue is included in excess of the above range, the diamine residue content is relatively reduced, and compatibility between the polyesteramide resin and the nylon resin is poor, resulting in surging during the extrusion process. As a result, the extrusion process may become poor or the extruded strand may not be obtained. In addition, the variation in physical properties of the obtained blended product may increase and the physical properties may become unstable.
  • the diol residue is less than the above range, the diamine residue content is relatively excessive, and although compatibility with nylon resin, which is a polyamide resin, is excellent in the extrusion process, color discoloration of existing nylon fibers (e.g. , yellowing) and shape instability problems due to moisture.
  • the diol residue can be adjusted to 70 to 99 mol%, 75 to 98 mol%, or 80 to 97 mol%.
  • the diamine residue may be 1 to 30 mol%.
  • the sum of the diol residues and the diamine residues may be a total of 100 mol%.
  • 70 to 99 mol% of the diol residue and 1 to 30 mol% of the diamine residue may be included.
  • the mole percent of the diamine residue increases, the mole percent of the diol residue decreases, the glass transition temperature and elevated temperature crystallization temperature generally increase, and the melting point, cooled crystallization temperature, intrinsic viscosity, and zero shear viscosity generally tends to decrease.
  • the mole percentage of the diol residue and the diamine residue can be adjusted.
  • the mol% of the diamine residue relative to 100 mol% of the diacid residue can be adjusted to 1 to 30 mol%, 2 to 25 mol%, or 3 to 20 mol%.
  • the mole percentage of the diol residue relative to 100 mole% of the diacid residue may be adjusted to 70 to 99 mol%, 75 to 98 mol%, or 80 to 97 mol%.
  • the polyesteramide resin secures mechanical strength, heat resistance, chemical resistance, etc. due to the diacid residue, transparency and impact resistance due to the diol residue, and is compatible with nylon due to the diamine residue. As the properties become excellent, the crystallization rate increases and the injection time is shortened, thereby improving productivity. Additionally, mechanical strength can be improved to a certain extent through blending with nylon.
  • the polyesteramide resin may have a glass transition temperature (Tg) of 80 to 150 °C. Specifically, it may be 90°C or higher, 95°C or higher, 100°C or higher, 105°C or higher, 110°C or higher, 115°C or higher, or 120°C or higher to 140°C or lower, 135°C or lower, or 130°C or lower.
  • Tg glass transition temperature
  • the polyesteramide resin has a temperature-elevated crystallization temperature (Tcc) of 120 to 200° C., specifically 130 to 190° C.; melting point (Tm) is 240 to 300°C, specifically 250 to 290°C; The crystallization temperature on cooling (Tmc) may be 180 to 250°C, specifically 190 to 240°C.
  • Tcc temperature-elevated crystallization temperature
  • the polyesteramide resin may have an intrinsic viscosity (IV) of 0.45 to 1.20 dl/g. Specifically, 0.45 dl/g or more, 0.45 dl/g or more, 0.50 dl/g or more, 0.55 dl/g or more, 0.60 dl/g or more, 0.65 dl/g or more, 0.70 dl/g or more, or 0.75 dl/g or more. It may be 1.20 dl/g or less, 1.10 dl/g or less, 1.00 dl/g or less, 0.90 dl/g or less, or 0.80 dl/g or less.
  • IV intrinsic viscosity
  • the polyesteramide resin may have a zero shear viscosity of 300 to 600 Pa ⁇ s, specifically 350 to 550 Pa ⁇ s at 290°C.
  • a method for producing a polyesteramide resin is provided by supplying a diacid component and a diol component at a specific mixing ratio together with a diamine component and water to a reactor and copolymerizing them.
  • a monomer mixture containing a diacid component containing terephthalic acid, a diol component containing cyclohexanedimethanol, and a diamine component containing bis(aminomethyl)cyclohexane is esterified.
  • Processing and amidation reactions step 1; and subjecting the esterification and amidation reaction products to a polycondensation reaction (step 2).
  • the molar ratio of the diol component to the diacid component in the monomer mixture satisfies 0.7 to 1.3.
  • polyesteramide resin of the above-described embodiment can be manufactured.
  • the manufacturing method can be performed in a batch, semi-continuous or continuous manner, and includes the esterification and amidation reactions (step 1) and the polycondensation reaction (step 2). ) can be performed under an inert gas atmosphere.
  • a solid phase polymerization reaction can be carried out subsequently. Specifically, after the polycondensation reaction (step 2), crystallizing the prepared polyesteramide resin (step 3); And it may further include solid phase polymerization of the crystallized polyesteramide resin (step 4).
  • the molar ratio of the diol component to the diacid component in the monomer mixture needs to be 0.7 to 1.3.
  • the above range can be appropriately adjusted considering the composition of the desired polyesteramide resin.
  • the diol component to the diacid component can be adjusted to a molar ratio of 0.7 to 1.3, 0.8 to 1.3, 0.9 to 1.3, or 1.0 to 1.3.
  • the monomer mixture may include 1 to 30 moles of the diamine component based on 100 moles of the diacid component.
  • the molar ratio of the diamine component to the diacid component may be 0.01 to 0.30.
  • the above range can be appropriately adjusted considering the composition of the desired polyesteramide resin.
  • the diamine component to the diacid component can be adjusted to a molar ratio of 0.01 to 0.30, 0.02 to 0.25, or 0.03 to 0.20.
  • a slurry can be prepared by adding water to a monomer mixture containing the diacid component, the diol component, and the diamine component.
  • the esterification and amidation reactions can be performed in the slurry.
  • the diacid component and the diamine component undergo an acid-base reaction to form a salt, and then, when the reaction temperature is reached, the salt undergoes an amidation reaction to produce water as a by-product. It includes a series of processes.
  • the diacid component and the diamine component can easily form a salt through an acid-base reaction in a highly fluid slurry with the addition of water, compared to the case where water is not added.
  • both the Tg and IV of the polyesteramide resin copolymerized in the water-added slurry can be increased.
  • the monomer mixture of the diacid component, the diol component, and the diamine component may be included in an amount of 60 to 97% by weight, and water may be included in an amount of 3 to 40% by weight.
  • esterification and amidation reactions can be performed in the presence of a catalyst, and reaction catalysts of various metals and organic compounds can be used.
  • the esterification and amidation reactions can be performed at a pressure of 0 to 10.0 kgf/cm2 and a temperature of 150 to 300°C.
  • the esterification and amidation reaction conditions can be appropriately adjusted depending on the specific characteristics of the polyesteramide resin being produced, the ratio of each component, or process conditions.
  • the esterification and amidation reaction conditions include a pressure of 0 to 5.0 kgf/cm2, more specifically 0.1 to 3.0 kgf/cm2; A temperature of 200 to 290°C, more specifically, 220 to 280°C.
  • the polycondensation reaction can be performed by reacting the esterification and amidation reaction products at a temperature of 150 to 320° C. and reduced pressure of 600 to 0.01 Torr for 1 to 24 hours.
  • This polycondensation reaction has a reaction temperature of 150 to 320°C, specifically 200 to 300°C, more specifically 250 to 290°C; And it may be performed under reduced pressure conditions of 600 to 0.01 Torr, specifically 200 to 0.05 Torr, and more specifically 100 to 0.1 Torr.
  • cyclohexanedimethanol a major by-product of the polycondensation reaction
  • the polycondensation reaction is outside the range of the reduced pressure conditions of 400 to 0.01 Torr, the by-product is removed. may be insufficient.
  • the polycondensation reaction may proceed for an average reaction time of 1 to 24 hours until the intrinsic viscosity of the final reaction product reaches the target level.
  • a polycondensation catalyst Before starting the esterification and amidation reactions, a polycondensation catalyst, stabilizer, coloring agent, crystallizer, antioxidant, branching agent, etc. may be added to the slurry or to the reaction intermediate product.
  • timing of adding the additives is not limited to this and may be added at any time during the manufacturing process of the polyesteramide resin.
  • one or more common titanium, germanium, antimony, aluminum, tin-based compounds, etc. can be appropriately selected and used.
  • the titanium-based catalyst includes 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/silicon dioxide complex, titanium dioxide/zirconium dioxide complex, etc.
  • germanium-based catalyst includes germanium dioxide and complexes using it.
  • phosphorus-based compounds such as phosphoric acid, trimethyl phosphate, and triethyl phosphate can be generally used, and the amount added may be 10 to 500 ppm relative to the weight of the final polyesteramide resin based on the amount of elemental phosphorus.
  • the amount of the stabilizer added is less than 10 ppm, the stabilizing effect is insufficient, and there is a risk that the color of the polymer may turn yellow. If it exceeds 500 ppm, there is a risk that a polyesteramide resin with the desired high degree of polymerization may not be obtained.
  • colorants added to improve the color of the polyesteramide resin include common colorants such as cobalt acetate and cobalt propionate, and the amount added is based on the amount of cobalt element in the final polyester. It may be 10 to 200 ppm based on the weight of the amide resin.
  • anthraquinone-based compounds, perinone-based compounds, azo-based compounds, and methine-based compounds can be used as organic coloring agents.
  • Commercially available products include Clarient Toners such as Polysynthren Blue RLS or Clarient's Solvaperm Red BB can be used.
  • the amount of the organic compound colorant added can be adjusted to 0 to 50 ppm based on the final polymer weight. If the colorant is used in an amount outside the above range, it may not sufficiently cover the yellowing of the polyesteramide resin or may deteriorate its physical properties.
  • crystallizing agent examples include crystal nucleating agents, ultraviolet absorbers, polyolefin resins, and polyamide resins.
  • antioxidants examples include hindered phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants, and mixtures thereof.
  • the branching agent is a typical branching agent having three or more functional groups, for example, trimellitic anhydride, trimethylol propane, trimellitic acid, or mixtures thereof. It can be exemplified.
  • the polycondensation reaction may use a polycondensation reaction catalyst including a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof.
  • titanium-based compounds examples include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, and triethanolamine titanate. nate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, etc.
  • germanium-based compound examples include germanium dioxide, germanium tetrachloride, germanium ethylene glycoxide, germanium acetate, complexes using these, or mixtures thereof.
  • germanium dioxide can be used. This germanium dioxide can be either crystalline or amorphous, and glycol-soluble can also be used.
  • a method for producing a resin composition containing a polyesteramide resin and polyamide is provided.
  • the method for producing the resin composition includes mixing polyesteramide resin and polyamide; blending the mixture and forming it into pellets; and drying the pellets.
  • the polyamide resin may be any polyamide resin and is not limited, but may be, for example, one or more selected from the group consisting of nylon-6, nylon-6,6, nylon-6T, and nylon-9T.
  • the polyesteramide resin includes a diacid residue, which is a residue of a diacid component containing terephthalic acid; A diol residue, which is the residue of a diol component including cyclohexanedimethanol; and a diamine residue, which is a residue of a diamine component containing bis(aminomethyl)cyclohexane, wherein the diol residue is 70 to 99 mol% based on 100 mol% of the diacid residue. It may include
  • the mixture may further include an antioxidant.
  • the antioxidant may be a phenolic antioxidant, that is, a phenolic primary antioxidant.
  • the polyesteramide resin; and mixing polyamide; in the step, the polyamide may be included in an amount of 1 part by weight to 30 parts by weight or 70 parts by weight to less than 100 parts by weight based on 100 parts by weight of the total mixture.
  • the step of blending the mixture and producing pellets may be a step of blending using an extruder.
  • the mixture can be uniformly blended in an extruder to produce pellets.
  • a twin-screw kneading extruder may be used as the extruder, and the extrusion temperature may be 200 to 400°C, or 250 to 300°C.
  • low molecular weight substances or volatile components may be removed during the blending process using an extruder.
  • the step of drying the pellets may be performed at a temperature of 100 to 200°C, specifically 110 to 130°C for 6 hours or more, and may be performed until the moisture content of the pellets is 200 ppm or less.
  • the polyesteramide resin of one embodiment harmonizes the effects of the diacid residue and the diol residue, and at the same time implements the effect of the diamine effect, and has excellent heat resistance compared to generally known polyester resins (especially , Tg, etc.) can be displayed.
  • the polyesteramide resin of the above embodiment when blended with a polyamide resin such as nylon, due to the characteristics of the polyesteramide resin containing a chemical structure similar to the amide bond present in the polyamide resin, it can be used without a compatibilizer. As the extrusion process improves, the extrusion process can be improved. In addition, as a result, the alloyed polyesteramide resin can improve productivity by shortening the injection time, and also obtain a polyesteramide resin with improved mechanical properties.
  • a composition containing a new polyesteramide resin can be provided through stable blending of the two resins without the use of a polymer compatibilizer.
  • the composition containing the new polyesteramide resin produced has excellent compatibility, so there is little deterioration in physical properties, and the shape stability can be greatly improved due to the low saturated moisture content.
  • polyesteramide resin of the embodiment may be produced by copolymerizing the diamine component together with the diacid component and the diol component mixed at a specific molar ratio.
  • esterification and amidation reactions were performed while pressurizing at 1.0 kgf/cm 2 and raising the temperature to 280° C. for 3 hours.
  • the temperature is raised to 290°C, and the polycondensation reaction (step 2) is carried out for 150 minutes at a vacuum degree of 0.5 to 1.0 Torr.
  • the final reactant is discharged as a strand to the outside of the reactor and pelletized through a cooling tank. ) to prepare a polyesteramide resin.
  • Polyester resins of Comparative Examples 2 to 4 were prepared in the same manner as Comparative Example 1 with the respective composition ratios of TPA, IPA, 1,4-CHDM, and EG according to Table 2 below.
  • the residue composition (mol%) contained in each resin sample of Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 4 was determined by dissolving the sample in CDCl 3 solvent at a concentration of 3 mg/mL and then measuring it using a nuclear magnetic resonance device (JEOL, 600 MHz). It was confirmed through a 1H-NMR spectrum obtained at 25°C using FT-NMR).
  • Tg glass transition temperature
  • Tcc crystallization temperature at elevated temperature
  • Tm melting point
  • Tmc crystallization temperature at low temperature
  • a resin sample was filled in an aluminum pan, the temperature was raised from 30°C to 320°C at a rate of 10°C/min, the temperature was maintained at 320°C for 2 minutes, and then the temperature was lowered to 30°C at a rate of -150°C/min. Next, an endothermic curve was obtained when the temperature was raised to 320°C at a rate of 10°C/min.
  • Tg, Tcc, and Tm were obtained.
  • an exothermic curve was obtained when the temperature was lowered to 30°C at a rate of -10°C/min. From this heating curve, Tmc was determined.
  • the resin sample was dissolved in orthochlorophenol (o-chlorophenol) at a concentration of 1.2 g/dl at 150°C, and then the intrinsic viscosity was measured using an Ubbelodhe viscosity tube.
  • orthochlorophenol o-chlorophenol
  • the temperature of the viscosity tube is maintained at 35°C, the time it takes for the solvent to pass through the inner section ab of the viscosity tube (efflux time) is t, and the time it takes for the solution to pass through is T.
  • efflux time the time it takes for the solvent to pass through the inner section ab of the viscosity tube
  • T the time it takes for the solution to pass through
  • the zero shear viscosity value of the complex viscosity obtained by measuring within the range of angular frequency 0.1 to 500 rad/s at 290°C was taken.
  • TPA mole% 100 100 100 1,4-CHDM mole% 97 95 90 80 1,3-BAC mole% 3 5 10 20 Resin physical properties Tg °C 94 97 102 113 Tcc °C 140 147 164 176 Tm °C 282 278 271 257 Tmc °C 223 218 200 216 IV dl/g 0.79 0.76 0.71 0.65 ZSV(290°C) Pa ⁇ s 481 463 466 377
  • the polyesteramide resins of Preparation Examples 1 to 4 are It is at a similar level to the polyester resins of Comparative Preparation Examples 1 to 4. However, in the case of glass transition temperature (Tg) and zero shear viscosity (ZSV), compared to the polyester resins of Comparative Preparation Examples 1 to 4, the The polyesteramide resins of Preparation Examples 1 to 4 are significantly higher.
  • the glass transition temperature, melt viscosity, and zero point of the polyesteramide resin are increased as a result of the additional introduction of diamine residues into the main chain. It can be seen that the shear viscosity increases.
  • Tg and Tcc As the content of diamine residues in the polyesteramide resin of Preparation Examples 1 to 4 increases, Tg and Tcc generally increase, and Tm, Tmc, IV, and ZSV tend to generally decrease. there is.
  • the residue composition in the polyesteramide resin can be adjusted within the scope of the above-described embodiment.
  • the composition of residues in the polyesteramide resin can be controlled by appropriately adjusting the monomer composition, as discussed above.
  • the diacid component and the diamine component can easily form a salt through an acid-base reaction in a highly fluid slurry with the addition of water, compared to the case where water is not added. This indicates that the amidation reaction can proceed easily in the slurry to which water is added, compared to the case where water is not added.
  • a polyesteramide resin with both high Tg and IV could be manufactured in Preparation Example 5.
  • Nylon-6,6 Ultramd C31 01 from BASF
  • PCT polycyclohexylenedimethylene terephthalate
  • Phenol-based primary antioxidant ADEKA’s AO-60
  • Nucleating agent (boron nitride, BN): IND-11 from Spears Advanced Materials, an inorganic nucleating agent
  • Nylon-6,6 Resin 100 parts by weight based on solid content was dried at a temperature of 120°C under a nitrogen atmosphere for more than 6 hours to make the moisture content less than 200 ppm.
  • Nylon-6,6 was mixed with 85 parts by weight based on solid content and 0.1 parts by weight based on solid content of phenol-based primary antioxidant.
  • compositions of Comparative Examples 1 to 8 and Examples 1 to 5 are shown in Tables 4 and 5 below.
  • the specific gravity of each sample was measured according to the ASTM D792 method.
  • the tensile strength of each sample was measured by stress-strain until fracture occurred while stretching at a speed of 50 mm/min with a grip length of 50 mm at room temperature using a universal testing machine UTM 5566A (Instron) in accordance with ASTM D638. Got a curve. The strength at the point where the sample broke was taken as the tensile strength.
  • the flexural strength and flexural modulus of each sample were measured according to ASTM D790. The measurement speed was 2.6 mm/min.
  • the impact strength of each sample was measured according to ASTM D256. A notched sample was used according to the standard, and the impact load was set to 3.2 t.
  • the heat distortion temperature of each sample was measured according to ASTM D648. A high load of 1.8 MPa was applied to the specimen and measurements were made without heat treatment of the specimen.
  • polyesteramide resin with diamine groups introduced, it had excellent compatibility with nylon, allowing normal extrusion without a compatibilizer, and the cooling time was shortened, making it possible to shorten the injection time, which enabled improved productivity. It was confirmed that it was done. In addition, it was confirmed that the mechanical properties, which was one of the problems of PCT, were improved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne une résine de polyesteramide, son procédé de préparation, et un produit mélangé ou composé la comprenant. Spécifiquement, les modes de réalisation de la présente invention concernent une résine de polyesteramide dans laquelle un résidu diaminé est introduit conjointement avec un résidu diacide et un résidu diol, son procédé de préparation, et un produit mélangé ou composé la comprenant.
PCT/KR2023/015197 2022-10-17 2023-10-04 Composition de résine comprenant une résine de polyesteramide et article moulé associé WO2024085502A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4579914A (en) * 1985-03-18 1986-04-01 The Dow Chemical Company Blends of polyesteramides and polyamides
US5321099A (en) * 1992-01-02 1994-06-14 The Dow Chemical Company Blends of semi-crystalline polyamides and polyesteramides
US5672676A (en) * 1995-08-21 1997-09-30 Eastman Chemical Company Polyesteramides with high heat deflection temperatures
KR20120014888A (ko) * 2009-03-13 2012-02-20 바스프 에스이 폴리에스테르 및 폴리아미드의 안정화된 블렌드
KR20150117297A (ko) * 2009-06-19 2015-10-19 로디아 오퍼레이션스 폴리아미드 및 폴리에스테르 수지의 블렌드의 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4579914A (en) * 1985-03-18 1986-04-01 The Dow Chemical Company Blends of polyesteramides and polyamides
US5321099A (en) * 1992-01-02 1994-06-14 The Dow Chemical Company Blends of semi-crystalline polyamides and polyesteramides
US5672676A (en) * 1995-08-21 1997-09-30 Eastman Chemical Company Polyesteramides with high heat deflection temperatures
KR20120014888A (ko) * 2009-03-13 2012-02-20 바스프 에스이 폴리에스테르 및 폴리아미드의 안정화된 블렌드
KR20150117297A (ko) * 2009-06-19 2015-10-19 로디아 오퍼레이션스 폴리아미드 및 폴리에스테르 수지의 블렌드의 조성물

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