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WO2015178560A1 - Résine de polyamide copolymérisée, son procédé de fabrication et produit moulé comprenant la résine - Google Patents

Résine de polyamide copolymérisée, son procédé de fabrication et produit moulé comprenant la résine Download PDF

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Publication number
WO2015178560A1
WO2015178560A1 PCT/KR2014/011779 KR2014011779W WO2015178560A1 WO 2015178560 A1 WO2015178560 A1 WO 2015178560A1 KR 2014011779 W KR2014011779 W KR 2014011779W WO 2015178560 A1 WO2015178560 A1 WO 2015178560A1
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WIPO (PCT)
Prior art keywords
polyamide resin
formula
copolymerized polyamide
dicarboxylic acid
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/011779
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English (en)
Korean (ko)
Inventor
임상균
배신효
권소영
박태준
김준성
김진규
진영섭
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Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020140170879A external-priority patent/KR20150135737A/ko
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Priority to US15/308,159 priority Critical patent/US20170044318A1/en
Priority to CN201480078986.2A priority patent/CN106488945A/zh
Priority to EP14892470.7A priority patent/EP3147305A4/fr
Publication of WO2015178560A1 publication Critical patent/WO2015178560A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment

Definitions

  • the present invention relates to a copolymerized polyamide resin, a method for preparing the same, and a product including the same, and more particularly, to a crystalline high heat-resistant copolymerized polyamide resin, a method for producing the same, and a molded article including the same, having excellent heat resistance and melt processability. will be.
  • High heat resistant nylon can be obtained by condensation polymerization of aromatic dicarboxylic acid or aromatic diamine.
  • the high heat resistant nylon may have a semi-aromatic structure and a semi-crystalline structure, and the heat resistance temperature is significantly higher than that of general nylon products, and thus may be applied to various fields requiring high heat resistance properties.
  • the high heat resistant nylon has a change in physical properties such as heat resistance and fluidity depending on the comonomer and copolymerization ratio.
  • Commonly used high heat resistant nylon is PA4T, PA6T, PA9T, PA10T, PA11T, PA12T and the like.
  • PA4T, PA6T, etc. in which the linear alkylene group has a low carbon number in the main chain, since the melting temperature of the homopolymer is very high, it cannot be processed, a large amount (several%) of comonomer is introduced to improve melt processability.
  • PA6T commonly used comonomers are adipic acid, isophthalic acid, and the like, and short and long chain aliphatic diamines, cyclic aliphatic diamines, and crushed aliphatic diamines and short chains.
  • adipic acid has the same carbon number as terephthalic acid, so that the melting temperature can be lowered without decreasing the crystallinity.
  • An object of the present invention is to provide a crystalline high heat-resistant copolymerized polyamide resin having excellent heat resistance and melt processability and a method for producing the same.
  • Another object of the present invention is to provide a copolymer polyamide resin and a method for producing the same, which can prevent or reduce gas generation at high temperature processing and have improved discoloration.
  • Still another object of the present invention is to provide a molded article formed of the copolymerized polyamide resin.
  • the copolymerized polyamide resin may include repeating units derived from dicarboxylic acid; Repeat units derived from diamines; And a repeating unit represented by the following Chemical Formula 1, wherein the melting temperature (Tm) is about 280 to about 330 ° C.
  • R 1 is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms.
  • the repeating unit represented by Formula 1 may be derived from a cyclic amide compound represented by Formula 2 or an amino acid compound represented by Formula 3 below:
  • R 1 is as defined in Chemical Formula 1.
  • the dicarboxylic acid may include one or more aromatic dicarboxylic acids having 8 to 20 carbon atoms.
  • the dicarboxylic acid may comprise about 60 to about 100 mole percent of the aromatic dicarboxylic acid and about 0 to about 40 mole percent of aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
  • the diamine may include one or more aliphatic diamines having 4 to 20 carbon atoms.
  • the content of the repeating unit represented by Formula 1 is about 5 to about 40 moles, based on about 100 moles of the repeating unit derived from the dicarboxylic acid and the repeating unit derived from the diamine, from the diamine
  • the molar ratio (diamine / dicarboxylic acid) of the repeating unit derived and the repeating unit derived from the dicarboxylic acid may be about 0.95 to about 1.15.
  • the copolymerized polyamide resin may be encapsulated with an end capping agent having one or more terminal groups containing an aliphatic carboxylic acid and an aromatic carboxylic acid.
  • the crystallization temperature (Tc) of the copolymerized polyamide resin may be about 240 to about 300 °C
  • the glass transition temperature (Tg) may be about 70 to about 120 °C.
  • the intrinsic viscosity of the copolymerized polyamide resin may be about 0.5 to about 2.5 dL / g.
  • the copolymerized polyamide resin may have a gas generation amount (weight loss amount) of about 8% by weight or less, and a water absorption rate of about 3% or less according to Equation 1 when heated to about 120 to about 350 ° C. for about 30 minutes. have:
  • W 0 is the initial weight of the specimen
  • W 1 is the weight after the specimen was treated for about 24 hours at about 85 °C
  • relative humidity (RH) about 85% in a thermo-hygrostat.
  • the preparation method is a method for preparing a copolymerized polyamide resin comprising polymerizing a monomer mixture comprising dicarboxylic acid, diamine, and a cyclic amide compound represented by Formula 2 or an amino acid compound represented by Formula 3 above.
  • the copolymerized polyamide resin has a melting temperature (Tm) of about 280 to about 330 ° C.
  • the method of preparing the copolymerized polyamide resin may include preparing a prepolymer by polymerizing the monomer mixture; And solid-phase polymerizing the prepolymer.
  • the prepolymer can have an intrinsic viscosity of about 0.1 to about 0.3 dL / g.
  • the solid phase polymerization may be to heat the prepolymer to a temperature of about 150 to about 280 °C.
  • Another aspect of the present invention relates to a molded article formed from the copolymerized polyamide resin.
  • the present invention is excellent in heat resistance, melt processability and the like, can prevent or reduce the generation of gas during high temperature processing, low hygroscopic crystalline high heat-resistant copolymerized polyamide resin, a method for producing the same and a molded article comprising the same Has
  • the copolymerized polyamide resin according to the present invention comprises (A) a repeating unit derived from dicarboxylic acid, (B) a repeating unit derived from diamine, and (C) a repeating unit represented by the following formula (1), and melting Temperature (Tm) is characterized in that about 280 to about 330 °C.
  • R 1 is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms.
  • dicarboxylic acid or the like refers to dicarboxylic acid, alkyl esters thereof (lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), and acids thereof. Used in the sense including acid anhydride and the like, and reacted with diamines and cyclic amide compounds or amino acid compounds to form repeating units (dicarboxylic acid moiety) derived from dicarboxylic acids. .
  • a dicarboxylic acid moiety, a repeating unit derived from a diamine (diamine moiety), and a repeating unit represented by Formula 1 include dicarboxylic acid, diamine and When the amino acid compound is polymerized, it means a residue and a ring-opened cyclic amide moiety in which a hydrogen atom (removed from an amine group), a hydroxy group or an alkoxy group (removed from a carboxylic acid group) is removed.
  • the repeating unit derived from the dicarboxylic acid according to an embodiment of the present invention is a residue remaining after the hydroxy group or the alkoxy group is removed from the carboxylic acid group of the dicarboxylic acid.
  • the repeating unit may be represented by the following formula (4).
  • R 2 is the remainder except for the carboxylic acid group of the dicarboxylic acid.
  • a hydrocarbon group having 4 to 30 carbon atoms or a hydrocarbon group having 4 to 30 carbon atoms including a hetero atom such as an oxygen atom or a sulfur atom specifically, a linear, branched or cyclic alkylene group having 4 to 18 carbon atoms, and a carbon number It may be an arylene group of 6 to 18, a linear, branched or cyclic alkylene group of 4 to 18 carbon atoms containing a hetero atom or an arylene group of 6 to 18 carbon atoms containing a hetero atom.
  • the dicarboxylic acid may be used without limitation, dicarboxylic acid used in conventional polyamide resin.
  • the dicarboxylic acid may include aromatic dicarboxylic acid.
  • the aromatic dicarboxylic acid may be a compound containing at least one aromatic dicarboxylic acid having 8 to 20 carbon atoms, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicar Acids, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxyphenylene acid, 1,3-phenylenedioxydiacetic acid, defenic acid, 4,4 ' -Oxybis (benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'dicarboxylic acid, 4,4'-diphenylcarboxylic acid, mixtures thereof and the like Can be used, but is not limited thereto. Specifically, it may be terephthalic acid, isophthalic acid or a mixture thereof.
  • the content of the aromatic dicarboxylic acid may be about 60 to about 100 mol%, for example, about 60 to about 90 mol%, specifically about 60 to about 75 mol%, of the total dicarboxylic acids. It may be excellent in the heat resistance, crystallinity and the like of the copolymerized polyamide resin in the above range.
  • the dicarboxylic acid of the present invention may further include an aliphatic dicarboxylic acid in order to further increase the processability of the copolymerized polyamide resin.
  • the aliphatic dicarboxylic acid may be a linear, branched or cyclic aliphatic dicarboxylic acid having 6 to 12 carbon atoms, such as adipic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 -Cyclohexanedicarboxylic acid may be used, but is not limited thereto.
  • the content of the aliphatic dicarboxylic acid may be about 0 to about 40 mol%, for example, about 10 to about 40 mol%, specifically about 25 to about 40 mol%, of the total dicarboxylic acids. In the above range, it is possible to reduce or prevent the gas generation phenomenon during the high-temperature processing of the polyamide resin by aliphatic dicarboxylic acid, it is possible to obtain a copolymerized polyamide resin more excellent in workability.
  • the repeating unit derived from the diamine according to an embodiment of the present invention is a residue remaining after the hydrogen atom is removed from the amine group of the diamine.
  • the repeating unit may be represented by the following formula (5).
  • R 3 is the remainder except for the amine group of the diamine.
  • a C4-C30 hydrocarbon group or a C4-C30 hydrocarbon group containing hetero atoms, such as an oxygen atom and a sulfur atom specifically, a C4-C20 linear, branched or cyclic alkylene group, a carbon number It may be an arylene group having 6 to 30, a linear, branched or cyclic alkylene group having 4 to 20 carbon atoms including a hetero atom, or an arylene group having 6 to 30 carbon atoms including a hetero atom.
  • the diamine may be used without limitation the diamine used in conventional polyamide resin.
  • the diamine may include aliphatic diamine.
  • At least one aliphatic diamine having 4 to 20 carbon atoms may be used as the aliphatic diamine.
  • the aliphatic diamine may be a mixture of aliphatic diamine having 4 to 10 carbon atoms and aliphatic diamine having 11 to 20 carbon atoms, but is not limited thereto.
  • the content of the aliphatic diamine having 4 to 10 carbon atoms in the total aliphatic diamine may be about 1 to about 99 mol%, for example, about 50 to about 95 mol%, specifically about 85 to about 95 mol%.
  • the content of the aliphatic diamine having 11 to 20 carbon atoms may be about 1 to about 99 mol%, for example, about 5 to about 50 mol%, specifically about 5 to about 15 mol%.
  • the copolymer polyamide resin may have excellent heat resistance, moisture absorption rate (water absorption rate), and the like, and a small amount of gas may be generated during high temperature processing.
  • the content of the aliphatic diamine may be about 70 to about 100 mole%, for example about 85 to about 99 mole%, of the total diamine. It is excellent in melt processability, dimensional stability, heat resistance, such as glass transition temperature, etc. of a copolyamide resin in the said range.
  • the diamine (B) of the present invention may further contain an aromatic diamine and / or a cyclic aliphatic diamine in order to increase the heat resistance, crystallinity and the like of the copolymerized polyamide resin.
  • aromatic diamine one or more kinds of aromatic diamines having 6 to 30 carbon atoms can be used.
  • phenylenediamine compounds such as m-phenylenediamine and p-phenylenediamine
  • xylenediamine compounds such as m-xylenediamine and p-xylenediamine
  • naphthalenediamine compound etc.
  • cyclic aliphatic diamine one or more cyclic aliphatic diamines having 6 to 30 carbon atoms can be used.
  • PAM bis (p-aminocyclohexyl) methane
  • MACM bis (p-amino-3-methyl-cyclohexyl) methane
  • the content when the aromatic diamine and / or cyclic aliphatic diamine is used, the content may be about 30 mol% or less, for example, about 1 to about 15 mol% of the total diamine. In the above range, the heat resistance, chemical resistance and the like of the copolymerized polyamide resin may be excellent.
  • the molar ratio (diamine (B) / dicarboxylic acid (A)) of the repeating unit (A) derived from the dicarboxylic acid and the repeating unit (B) derived from the diamine is For example, about 0.95 to about 1.15, for example about 1.00 to about 1.10. It is possible to produce a polymer having a degree of polymerization suitable for molding in the above range, it is possible to prevent the degradation of physical properties by the unreacted monomer.
  • the repeating unit represented by Formula 1 according to the present invention is a residue remaining after the hydrogen atom is removed from the amine group of the ring-opened cyclic amide compound part or the amino acid compound and the hydroxy or alkoxy group is removed from the carboxylic acid group.
  • the cyclic amide (lactam) compound and amino acid compound may be substituted or used together with an aliphatic dicarboxylic acid component used for the purpose of improving melt processability.
  • the melting temperature of the amide resin can be reduced more drastically, which can be used to relatively increase the content of the aromatic dicarboxylic acid moiety in the dicarboxylic acid moiety. Therefore, the copolymerized polyamide of the present invention, in which the cyclic amide compound is ring-opened or the amino acid compound is condensation-polymerized, is superior in heat resistance, crystallinity, and the like to a conventional copolymerized polyamide resin having the same melt processability.
  • the gas generated by the aliphatic dicarboxylic acid moiety may be reduced or prevented during high temperature processing.
  • the cyclic amide compound may be used a cyclic amide compound having 4 to 12 carbon atoms, for example, may include a cyclic amide compound represented by the following formula (2).
  • R 1 is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms, for example, a linear alkylene group having 4 to 12 carbon atoms.
  • cyclic amide compound may include ⁇ -caprolactam, laurolactam, mixtures thereof, and the like, but are not limited thereto.
  • the amino acid compound may be a conventional amino acid having 4 to 12 carbon atoms, for example, may include an amino acid compound represented by the following formula (3).
  • R 1 may be a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms, for example, a linear alkylene group having 4 to 12 carbon atoms.
  • amino acid compound may include 5-aminopentanoic acid, 12-aminododecanoic acid, and mixtures thereof, but are not limited thereto.
  • the content of the repeating unit (cyclic amide compound or amino acid compound) represented by Chemical Formula 1 is about 5 to about 40 moles, eg about 100 moles of the dicarboxylic acid and the diamine. For example from about 10 to about 35 moles. Melt processability, heat resistance, crystallinity, and the balance of physical properties in the above range may be excellent.
  • the copolymerized polyamide resin of the present invention may be one in which the end group is sealed with an end capping agent containing at least one aliphatic carboxylic acid and aromatic carboxylic acid.
  • an end capping agent containing at least one aliphatic carboxylic acid and aromatic carboxylic acid.
  • the end-sealing agent for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauryl acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyl acid , Benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, mixtures thereof and the like may be used, but is not limited thereto.
  • the terminal blocker may be included, for example, about 0.01 to about 3 moles, for example about 0.1 to about 2 moles, based on about 100 moles of the dicarboxylic acid (A) and the diamine (B). This is not restrictive.
  • the copolymerized polyamide resin of the present invention may be prepared according to a conventional polyamide production method, for example, by polymerizing a monomer mixture including the dicarboxylic acid, the diamine, and the cyclic amide compound or amino acid compound. It can manufacture.
  • the polymerization may be carried out according to a conventional polymerization method, for example, may be carried out using a melt polymerization method, etc., and the polymerization temperature may be about 80 to about 300 ° C, for example, about 90 to about 280 ° C.
  • the polymerization pressure may be about 10 to about 40 kgf / cm 2 , but is not limited thereto.
  • the copolymerized polyamide resin may be prepared by polymerizing the monomer mixture to prepare a prepolymer and solidifying the prepolymer.
  • the monomer mixture, catalyst and water are charged to the reactor and stirred at about 80 to about 150 ° C. for about 0.5 to about 2 hours, then at a temperature of about 200 to about 280 ° C.
  • the temperature between the glass transition temperature (Tg) and the melting temperature (Tm) can be obtained through a solid state polymerization (Solid State Polymerization) for about 5 to about 30 hours in a vacuum state.
  • the prepolymer was dissolved in about 98% sulfuric acid solution at a concentration of about 0.5 g / dl, and the intrinsic viscosity [ ⁇ ] measured by an Ubbelodhde viscometer at about 25 ° C. was about 0.1 to about 0.3 dL / g, eg For example, about 0.15 to about 0.25 dL / g. Melt processability may be excellent in the above range.
  • the solid phase polymerization may be to heat the prepolymer to about 150 to about 280 ° C., for example about 180 to about 250 ° C., in a vacuum or in the presence of an inert gas such as nitrogen or argon.
  • an inert gas such as nitrogen or argon.
  • a copolymerized polyamide resin having a weight average molecular weight of about 5,000 to about 50,000 g / mol can be obtained.
  • a catalyst may be used in the copolymerization reaction.
  • a phosphorus-based catalyst may be used.
  • phosphoric acid, phosphorus acid, hypophosphorous acid or salts or derivatives thereof may be used.
  • phosphoric acid, phosphoric acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphinate and the like can be used.
  • the catalyst may be used in an amount of about 3 parts by weight or less, for example, about 0.001 to about 1 part by weight, specifically about 0.01 to about 0.5 part by weight, based on about 100 parts by weight of the total monomer mixture. Do not.
  • the terminal blocker may be used as the content in the method for preparing the polyamide resin, and by adjusting the content of the terminal blocker, the viscosity of the copolymerized polyamide resin may be adjusted.
  • the melting temperature (Tm) of the copolymerized polyamide resin according to the present invention may be about 280 ° C. or more, for example, about 280 ° C. to about 330 ° C. As a high heat resistant resin in the above range, it may be excellent in moldability and heat resistance.
  • the crystallization temperature (Tc) of the copolyamide resin may be about 240 to about 300 °C, for example about 245 to about 280 °C.
  • Copolymer polyamide resin excellent in crystallinity can be obtained in the said range.
  • the glass transition temperature (Tg) of the copolymerized polyamide resin may be about 70 to about 120 °C, for example about 75 to about 115 °C. Within this range, heat resistance and high processability suitable for use of components for electric and electronic materials can be obtained.
  • the copolymerized polyamide resin is heated by using TGA (thermogravimetric analysis) at about 120 to about 350 ° C. for about 30 minutes, and the measured gas generation amount (weight loss) is about 8% by weight or less, for example, about 1 to about 1. About 7.5% by weight.
  • TGA thermogravimetric analysis
  • the copolymerized polyamide resin has a water absorption (moisture absorption) of about 3% or less, for example, about 2% or less, specifically about 0.5 to about 25 hours after the specimen is treated at about 85 ° C. and relative humidity of about 85% for about 24 hours. About 1.5%.
  • the moisture absorption rate is about 90mm ⁇ 50mm ⁇ about 2mm sized specimens vacuum dried at about 120 ° C. for about 4 hours, then the initial weight (W 0 ) of the specimen is measured, and the specimen is measured in a constant temperature and humidity chamber. After the treatment for about 24 hours at °C, relative humidity (RH) of about 85%, the weight (W 1 ) of the specimen may be measured, and then calculated according to Equation 1 below.
  • RH relative humidity
  • W 0 is the initial weight of the specimen
  • W 1 is the weight after the specimen was treated for about 24 hours at about 85 °C
  • relative humidity (RH) about 85% in a thermo-hygrostat.
  • the copolymerized polyamide resin was dissolved in about 98% sulfuric acid solution at a concentration of about 0.5 g / dl, and the intrinsic viscosity [ ⁇ ] measured by an Ubbelodhde viscometer at about 25 ° C. was about 0.5 to about 2.5 dL / g. For example, about 0.5 to about 2.0 dL / g.
  • the copolymerized polyamide resin was measured by heat treatment of a specimen of about 90 mm ⁇ about 50 mm ⁇ about 2 mm in a heat oven at about 250 ° C. for about 10 minutes.
  • YI may be about 5 to about 10, for example about 6 to about 9.5.
  • the copolymerized polyamide resin may have a weight average molecular weight of about 5,000 to about 50,000 g / mol measured by GPC.
  • the molded article according to the present invention may be formed from the copolymerized polyamide resin.
  • the polyamide resin may be made of an electric and electronic material (connector, LED diffusion plate, etc.) requiring high processability and low gas generation amount, but is not limited thereto.
  • the molded article can be easily formed by those skilled in the art to which the present invention pertains.
  • composition of Table 1 as dicarboxylic acid (terephthalic acid (TPA) and adipic acid (AA), diamine (diamine), hexamethylenediamine (HMDA), and cyclic amide, ⁇ -capro
  • TPA terephthalic acid
  • AA adipic acid
  • AA diamine
  • HMDA hexamethylenediamine
  • ⁇ -capro To the monomer mixture comprising lactam and 100 mole parts of the dicarboxylic acid and diamine, 1.49 mole parts of benzoic acid as terminal blocker, 0.1 part by weight of sodium hypophosphinate as catalyst and 74 parts by weight of water based on 100 parts by weight of the monomer mixture.
  • the polyamide resins prepared in Examples and Comparative Examples were evaluated for melting temperature, crystallization temperature, glass transition temperature, intrinsic viscosity, moisture absorption rate, and gas generation amount by the following method, and the results are shown in Table 2 below.
  • Tm Melting temperature
  • Tc crystallization temperature
  • Tg glass transition temperature
  • DSC Differential Scanning Calorimeter
  • the crystallization temperature was measured at an exothermic peak coming out while cooling at 10 ° C./min after 1 minute of holding at 400 ° C., and then raising the temperature to 400 ° C. at a temperature rising rate of 10 ° C./min after 1 minute of holding at 30 ° C. (2nd scan), the glass transition temperature and the melting temperature were measured from the maximum transition point and the maximum end point of the endothermic peak.
  • Intrinsic viscosity (unit: dL / g): The sample was dissolved in 98% sulfuric acid solution at a concentration of 0.5 dL / g and measured at 25 ° C. using an Ubbelodhde viscometer.
  • W 0 is the initial weight of the specimen
  • W 1 is the weight after the specimen was treated for 24 hours at 85 °C
  • Gas generation amount (unit: weight%): The gas generation amount was measured by measuring Isothermal TGA using TGA Q500 by TA Instruments. Specifically, 20 mg of the polyamide resin was quantified in a sample pan, and then heated up to 120 ° C. at a temperature increase rate of 10 ° C. per minute, held for 30 minutes to dry moisture in the resin, and then at a temperature increase rate of 10 ° C. per minute. It heated up to 350 degreeC and maintained for 30 minutes, and measured the generation amount of decomposition gas (weight reduction amount of resin) which arises at this time.
  • the copolymerized polyamide resin (Examples 1 to 5) according to the present invention is a crystalline copolymerized polyamide resin having a melting temperature (Tm) of about 280 to about 330 ° C, and excellent in heat resistance and melt processability. It can be seen. In addition, the moisture absorption rate is lower than 1.4%, the gas generation amount is 7.1 wt% or less can reduce the amount of gas generated during high temperature processing, it can be seen that the yellow index after heat treatment is excellent in discoloration resistance to 9.4 or less.
  • Tm melting temperature
  • the gas generation amount is 7.1 wt% or less can reduce the amount of gas generated during high temperature processing, it can be seen that the yellow index after heat treatment is excellent in discoloration resistance to 9.4 or less.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une résine de polyamide copolymérisée caractérisée en ce qu'elle comprend : un motif de répétition induit à partir d'acide dicarboxylique; un motif de répétition induit à partir d'une diamine; et un motif de répétition représenté par la formule chimique 1, dans laquelle le point de fusion (Tm) de la résine de polyamide copolymérisée s'élève d'environ 280 °C à environ 330°C. Ladite résine de polyamide copolymérisée présente une excellente résistance à la chaleur et une excellente aptitude au traitement à l'état fondu.
PCT/KR2014/011779 2014-05-23 2014-12-03 Résine de polyamide copolymérisée, son procédé de fabrication et produit moulé comprenant la résine Ceased WO2015178560A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/308,159 US20170044318A1 (en) 2014-05-23 2014-12-03 Copolymerized Polyamide Resin, Method for Preparing Same, and Molded Product Comprising Same
CN201480078986.2A CN106488945A (zh) 2014-05-23 2014-12-03 共聚的聚酰胺树脂、用于制备其的方法及包含其的模制品
EP14892470.7A EP3147305A4 (fr) 2014-05-23 2014-12-03 Résine de polyamide copolymérisée, son procédé de fabrication et produit moulé comprenant la résine

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KR970042683A (ko) * 1995-12-27 1997-07-24 백영배 공중합 방향족 폴리아미드 수지 조성물
KR20110032001A (ko) * 2008-07-30 2011-03-29 이 아이 듀폰 디 네모아 앤드 캄파니 폴리하이드록시 중합체를 포함하는 내열성 열가소성 용품
KR20120040069A (ko) * 2010-10-18 2012-04-26 제일모직주식회사 폴리아미드 수지
KR20130073773A (ko) * 2011-12-23 2013-07-03 제일모직주식회사 폴리아미드 수지, 이의 제조 방법 및 이를 포함하는 제품

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KR20120040069A (ko) * 2010-10-18 2012-04-26 제일모직주식회사 폴리아미드 수지
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