WO2014084504A1 - Polyamide resin, and method for preparing same - Google Patents

Polyamide resin, and method for preparing same Download PDF

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Publication number
WO2014084504A1
WO2014084504A1 PCT/KR2013/009383 KR2013009383W WO2014084504A1 WO 2014084504 A1 WO2014084504 A1 WO 2014084504A1 KR 2013009383 W KR2013009383 W KR 2013009383W WO 2014084504 A1 WO2014084504 A1 WO 2014084504A1
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Prior art keywords
polyamide resin
mol
acid
temperature
reaction
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PCT/KR2013/009383
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French (fr)
Korean (ko)
Inventor
조성만
칸다토모미치
시모다토모아키
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제일모직 주식회사
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Priority claimed from JP2012261494A external-priority patent/JP6153717B2/en
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Publication of WO2014084504A1 publication Critical patent/WO2014084504A1/en

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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
    • 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
    • C08G69/28—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
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids

Definitions

  • the present invention relates to a polyamide resin and a method for producing the same. More specifically, it is related with the polyamide resin excellent in mechanical strength, heat resistance, color tone, and the balance of these physical properties, and its manufacturing method.
  • Polyamide resins are widely used in clothing, industrial materials and engineering plastics due to their excellent properties and ease of melt molding.
  • these general-purpose polyamide resins have problems such as lack of heat resistance and poor dimensional stability due to absorption.
  • polyamide resins used in fields such as electric and electronic parts, automobile parts, and the like are required to have more excellent physical properties and functionality than conventional polyamide resins.
  • a method of polycondensing a salt formed by dicarboxylic acid, diamine or the like or a lower order condensate by heating under melting conditions is known.
  • this manufacturing method can be applied also to the manufacturing method of the polyamide resin which used paraxylylenediamine as a diamine component.
  • production of polyamide resins from paraxylylenediamine, metaxylenediamine, and aliphatic dicarboxylic acid Japanese Patent Publication No. 32-6148, Japanese Patent Publication No. 44-20637, Japanese Patent Publication
  • polyamide resins see Japanese Patent Publication No. 47-33277) from paraxylenediamine, hexamethylenediamine, adipic acid and terephthalic acid.
  • Japanese Laid-Open Patent Publication No. 08-3312 discloses a method for producing a polyamide resin containing a structure derived from xylenediamine and benzenedicarboxylic acid by melt multistage polymerization using a plurality of polymerization apparatuses.
  • the production methods are prone to pyrolysis of the product because it requires high temperature to maintain the molten state when applied to high melting point polyamide resin, the polyamide resin produced is mechanical strength, resistance degradation, color tone, etc. There is a fear that the physical properties of the.
  • the polyamide resin prepared from the above production methods may contain a gel, such as a high viscosity and difficult to handle, and may cause a manufacturing problem such as the contents easily remain on the inner wall of the reactor and the yield is low.
  • An object of the present invention is to provide a polyamide resin having excellent mechanical strength, heat resistance, color tone and balance of physical properties thereof.
  • Another object of the present invention is to provide a method for producing a polyamide resin capable of obtaining a polyamide resin having excellent mechanical strength, heat resistance, color tone, and balance of physical properties thereof, which can prevent manufacturing problems such as gelation.
  • the polyamide resin is a dicarboxylic acid component containing 1,4-cyclohexanedicarboxylic acid; And a diamine component containing a xylylenediamine having a content of paraxylenediamine component of about 10 to about 100 mol%, wherein the polymer is a monomer mixture comprising a temperature of about 0.5 g / dL in concentrated sulfuric acid.
  • the logarithmic viscosity (IV) measured at 25 ° C. and the number average molecular weight (Mn) determined by the titration method satisfy the following Equations 1 and 2:
  • the dicarboxylic acid component contains 5 to about 50 mole percent of the 1,4-cyclohexanedicarboxylic acid, and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid, wherein
  • the diamine component may contain about 50 to about 100 mole percent of the xyleneylene diamine and about 0 to about 50 mole percent of diamines other than xyleneylene diamine.
  • the polyamide resin may have a melting point of about 270 ° C. or more, a glass transition temperature of about 100 ° C. or more, and a flexural modulus of about 4 GPa or more.
  • the xylylenediamine may comprise from about 10 to about 90 mole percent of the metaxylenediamine component.
  • the preparation method comprises a diamine component containing 1,4-cyclohexanedicarboxylic acid and a diamine component containing xyleneylene diamine having a content of about 10 to about 100 mol% of the paracarboxylic acid dicarboxylic acid component at least about 200 ° C.
  • the reaction is performed for about 0.5 to about 4 hours at a reaction temperature of less than about 230 ° C. and a reaction pressure of about 0.5 to about 3 MPa.
  • the polycondensation reaction is carried out under the condition that the water content in the reaction system is about 15 to about 35 wt%.
  • the dicarboxylic acid component contains about 5 to about 50 mole percent of the 1,4-cyclohexanedicarboxylic acid, and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid
  • the diamine component may contain about 50 to about 100 mole percent of the xylylenediamine and about 0 to about 50 mole percent of diamines other than xylylenediamine.
  • the maximum reaction temperature of the solid phase polymerization may be less than or equal to the lower of about 230 ° C. and about 20 ° C. lower than the melting point of the lower condensate.
  • This invention has the effect of providing the polyamide resin which is excellent in mechanical strength, heat resistance, color tone, and the balance of these physical properties, and the manufacturing method of the said polyamide resin which can prevent manufacturing problems, such as gelation.
  • the polyamide resin according to the present invention comprises a dicarboxylic acid component containing 1,4-cyclohexanedicarboxylic acid; And a diamine component containing a xylylenediamine having a content of paraxylenediamine component of about 10 to about 100 mol%, wherein the polymer is a monomer mixture comprising a temperature of about 0.5 g / dL in concentrated sulfuric acid.
  • the logarithmic viscosity (IV) measured at 25 ° C. and the number average molecular weight (Mn) determined by the titration method satisfy the following formulas (1) and (2).
  • the dicarboxylic acid component contains about 5 to about 50 mole percent of 1,4-cyclohexanedicarboxylic acid and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid. In the above range, a polyamide resin having excellent mechanical strength, heat resistance, color tone, and balance of physical properties thereof can be obtained. The total amount of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid is 100 mol%.
  • the content of 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid component is about 5 to about 50 mol%, for example about 10 to about 50 mol%, specifically about 15 to about 45 mol%. Within this range, a polyamide resin having good heat resistance and crystallinity and easy molding processing can be obtained. If the content of the 1,4-cyclohexanedicarboxylic acid is less than about 5 mol%, sufficient heat resistance may not be obtained. If the content of the 1,4-cyclohexanedicarboxylic acid is less than about 50 mol%, the melting point may be excessively increased and melt molding may be difficult.
  • dicarboxylic acids other than the 1,4-cyclohexanedicarboxylic acid include maronic acid, dimethylmaronic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimeric acid, Aliphatic dicarboxylic acids such as 2,2-dimethylglutal acid, 3,3-diethyl succinic acid, subric acid, azelaic acid, sebacic acid, undecane diacid, and dodecane diacid; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid; Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphene Aromatic dicarboxy
  • the content of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid component is about 50 to about 95 mole%, for example about 50 to about 90 mole%, specifically about 55 to about 85 mole%. Within this range, a polyamide resin having good heat resistance and crystallinity and easy molding processing can be obtained. If the content of dicarboxylic acids other than the 1,4-cyclohexanedicarboxylic acid is more than about 95 mol%, there is a fear that sufficient heat resistance may not be obtained. If the content is less than about 50 mol%, the melting point rises excessively, and melt molding is difficult. Can be done.
  • polyhydric carboxylic acid components such as trimellitic acid, trimesic acid, a pyromellitic acid, can also be used together.
  • the diamine component contains about 50 to about 100 mol% of xylylenediamine having a content of paraxylenediamine component of about 10 to about 100 mol%, and about 0 to about 50 mol% of diamines other than xylylenediamine. do. In the above range, a polyamide resin having excellent mechanical strength, heat resistance, color tone, and balance of physical properties thereof can be obtained.
  • the total amount of diamines other than the xylene diamine and xylene diamine is 100 mol%.
  • xylylene diamine includes three kinds of isomers, ortho-xylylene diamine (o-xylylene diamine) and methaxylene diamine (m-xylylene diamine, MXDA). ) And para-xylylene diamine (PXDA).
  • the content of paraxylenediamine component in the xyleneylene diamine is about 10 to about 100 mol%, for example about 10 to about 90 mol%, specifically about 20 to about 80 mol%. If the content of the paraxylylenediamine component is less than about 10 mol% in 100 mol% of the total xylene diamine, there is a possibility that the mechanical strength is lowered.
  • metha xylylenediamine for example, of about 10 to about 90 mol%, specifically about 20 to about It may contain 80 mol%.
  • the content of xylylenediamine in the diamine component is about 50 to about 100 mol%, for example about 60 to about 100 mol%, specifically about 70 to about 100 mol%.
  • content of the said xylene diamine is less than about 50 mol% in a diamine component, there exists a possibility that the mechanical strength, heat resistance, color tone, and balance of these physical properties of a polyamide resin may fall.
  • diamines other than the xyleneylene diamine include ethylenediamine, propanediamine, 1,4-butanediamine, 1,6-hexanediamine (hexamethylenediamine), 1,7-heptanediamine, 1,8- Octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl- Aliphatic alkylenediamines such as 1,9-nonanediamine; Cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, 1,3-bisaminomethylcyclohexane
  • the content of other diamines other than xylylenediamine in the diamine component is about 0 to about 50 mol%, for example about 0 to about 40 mol%, specifically about 0 to about 30 mol%.
  • content of diamine other than the said xylene diamine exceeds about 50 mol% in a diamine component, there exists a possibility that the mechanical strength, heat resistance, color tone, and balance of these physical properties of a polyamide resin may fall.
  • the logarithmic viscosity (IV) measured at a temperature of about 25 ° C. at a concentration of about 0.5 g / dL in concentrated sulfuric acid has a value satisfying the following formula (1).
  • the logarithmic viscosity (IV) of the polyamide is for example about 0.5 to about 1.4, specifically about 0.6 to about 1.3. The said IV can be measured by the method as described in the Example mentioned later more specifically.
  • Equation 2 indicates that the logarithmic viscosity (IV) is sufficiently low with respect to the number average molecular weight (Mn), and the component that is abnormally high molecular weight due to the uneven reaction progress or the crosslinking reaction of the copolymerization component is sufficiently low. Or not. Therefore, the polyamide resin of the present invention that satisfies Equation 2 may have good moldability and excellent balance of physical properties such as mechanical strength, heat resistance and color tone.
  • the Mn / IV of the polyamide resin When the Mn / IV of the polyamide resin is less than about 12,000, the logarithmic viscosity (IV) is high with respect to the number average molecular weight (Mn), and the component is abnormally high molecular weight due to uneven reaction progress or crosslinking reaction of the copolymerization component. This shows a lot. Therefore, such a polyamide resin may lower productivity, workability, and physical property balance such as mechanical strength, heat resistance and color tone.
  • the Mn / IV of the polyamide resin is, for example, about 12,500 or more.
  • the upper limit of Mn / IV is not specifically limited, For example, it is about 18,000 or less from a viewpoint which does not change the fluidity
  • the number average molecular weight (Mn) of the said polyamide resin is the value measured by the titration method, More specifically, it can measure by the method as described in the Example mentioned later.
  • IV and Mn / IV are adjusted to about 0.95 to about 1.05, for example, about 0.97 to about 1.03, using the specific raw material composition of the present invention and adjusting the charged molar ratio (diamine / dicarboxylic acid) of diamine and dicarboxylic acid. It can control by manufacturing in the manufacturing conditions range of the low order condensate and solid-phase polymerization which are shown by this invention.
  • the melting point of the polyamide resin of the present invention may be, for example, about 270 ° C. or more, specifically about 275 to about 320 ° C.
  • the glass transition temperature of the polyamide resin of the present invention may be, for example, about 100 ° C or more, specifically about 101 to about 120 ° C.
  • the flexural modulus of the polyamide resin of the present invention may be, for example, about 4 GPa or more, specifically about 4.2 to about 4.5 GPa.
  • the melting point, glass transition temperature and flexural modulus can be specifically measured by the method described in Examples.
  • the polyamide resin according to the present invention includes, for example, a process for preparing a lower condensate formed of the dicarboxylic acid component and the diamine component, a step of discharging and cooling the lower condensate, and cooling the lower condensate. It can obtain by the manufacturing method including the process of solid-phase polymerization.
  • the process for preparing the polyamide resin according to the present invention comprises about 5 to about 50 mol% of 1,4-cyclohexanedicarboxylic acid as the dicarboxylic acid component, and about 50 dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid. From about 50 to about 100 mol% of xylylenediamine having from about 10 to about 100 mol% of a paraxylenediamine component as a diamine component, and from about 0 to about 95 mol% of diamine other than xylylenediamine.
  • a method for producing a polyamide resin containing from about 50 mol% wherein the polycondensation reaction of the dicarboxylic acid component and the diamine component is carried out at a reaction temperature of about 200 ° C. to about 230 ° C., and a reaction pressure of about 0.5 to about 3 MPa, the reaction time is about 0.5 to about 4 hours, and after completion of the reaction, the water content in the reaction system is carried out under the condition of about 15 to about 35% by weight to prepare a lower condensate, under an inert gas atmosphere, Discharging and cooling the lower order condensate at a pressure below the pressure, and solidifying the cooled lower order condensate, wherein the cooled lower condensate is at a concentration of about 0.5 g / dL in concentrated sulfuric acid.
  • the algebraic viscosity measured at a temperature of about 25 ° C. is about 0.07 to about 0.40 dL / g.
  • a production problem hardly occurs such as a gel is generated during production, and a polyamide resin having excellent physical balance such as mechanical strength, heat resistance and color tone can be obtained.
  • the polycondensation reaction of the dicarboxylic acid component and the diamine component is carried out to produce a lower order condensate of the polyamide resin.
  • the said lower order condensate is synthesize
  • the said aqueous solvent is a solvent which has water as a main component.
  • the solvent used in addition to water is not particularly limited as long as it does not affect polycondensation reactivity or solubility.
  • alcohols such as methanol, ethanol, propanol, butanol and ethylene glycol can be used.
  • the amount of water in the reaction system at the start of the polycondensation reaction is preferably such that the amount of water in the reaction system is about 15 to about 35% by weight. Specifically, the amount of water in the reaction system at the start of the polycondensation reaction is, for example, about 17 to about 60% by weight.
  • it becomes a nearly uniform solution phase and may not use much time and energy to distill and remove water in the polycondensation process, and thermal degradation of the lower condensate by extension of the reaction time Can be reduced.
  • a phosphorus catalyst can be used for the purpose of improving the polycondensation rate and preventing deterioration during the polycondensation reaction.
  • the phosphorus-based catalyst may include hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, phosphate ester, polymetaphosphates, polyphosphates, phosphine oxides, phosphonium halide compounds, mixtures thereof, and the like. It is not limited. For example, hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, mixtures thereof and the like can be used.
  • hypophosphite examples include sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, vanadium hypophosphite, manganese hypophosphite, zinc hypophosphite, lead hypophosphite, nickel hypophosphite, hypophosphite Cobalt, ammonium hypophosphite, etc. are preferable, and sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are more preferable.
  • the phosphate salt examples include sodium phosphate, potassium phosphate, potassium dihydrogen phosphate, calcium phosphate, vanadium phosphate, magnesium phosphate, manganese phosphate, lead phosphate, nickel phosphate, cobalt phosphate, ammonium phosphate, and diammonium phosphate.
  • ethyl octadecyl phosphate etc. can be used, for example.
  • the polymetaphosphates examples include sodium trimethaphosphate, sodium pentametaphosphate, sodium hexametaphosphate, polymetaphosphate, and the like.
  • sodium tetrapolyphosphate etc. can be used, for example.
  • hexamethyl phosphoamide etc. can be used as said phosphine oxides, for example.
  • the phosphorus catalysts may be in the form of hydrates.
  • the addition amount of the phosphorus catalyst may be about 0.0001 to about 5 parts by weight, for example, about 0.001 to about 1 part by weight based on about 100 parts by weight of the monomer.
  • the addition time may be added at any time until the solid phase polymerization is completed, but it is preferred to be between the time of starting the raw material and the completion of the polycondensation of the lower condensate. Moreover, you may add in several times and may add in combination of 2 or more types of other phosphorus catalysts.
  • this process can perform the said polycondensation reaction in presence of terminal blocker.
  • the use of the terminal sealing agent makes it easier to control the molecular weight of the lower condensate and the finally produced polyamide resin, and improve the melt stability of the lower condensate and the finally produced polyamide resin.
  • the terminal blocker is not particularly limited as long as it is a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group in the lower condensate.
  • acid anhydrides such as monocarboxylic acid, monoamine, phthalic anhydride, monoisocyanate, monoacid halides, monoesters, monoalcohols, and the like can be exemplified, but are not limited thereto.
  • the terminal blocker may be used alone or in combination of two or more thereof.
  • monocarboxylic acid or monoamine may be used in consideration of reactivity and the end stability of the encapsulation, and specifically, monocarboxylic acid having excellent handleability may be used.
  • the monocarboxylic acid is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid and myristic acid.
  • Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, pivalic acid and isobutyl acid; Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalene carboxylic acid, ⁇ -naphthalene carboxylic acid, methylnaphthalene carboxylic acid, and phenylacetic acid; Mixtures thereof and the like can be used.
  • acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, benzoic acid, etc. Etc. can be used.
  • the monoamine is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group.
  • Aliphatic monoamines such as diethylamine, dipropylamine and dibutylamine
  • Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine
  • Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; Mixtures thereof and the like can be used.
  • butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, aniline, etc. may be used in view of reactivity, boiling point, bag end stability and price.
  • the amount of the terminal encapsulating agent may vary depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the terminal encapsulating agent, but, for example, about 0.1 to about 100 moles of dicarboxylic acid or diamine About 15 mole parts.
  • Synthesis of the lower condensate of the present invention can be done by raising and raising the temperature under stirring of the reactants.
  • the polymerization temperature (reaction temperature) can be adjusted after the addition of the raw material, the polymerization pressure (reaction pressure) can be adjusted in accordance with the progress of the polymerization.
  • the reaction temperature in this process is about 200 ° C. or more and less than about 230 ° C., for example, about 200 ° C. to about 225 ° C. In the above range, side reactions such as gelation do not occur well, so that the target lower-order condensate can be efficiently obtained.
  • the reaction pressure in this process is, for example, about 0.5 to about 3.0 MPa, specifically about 1.0 to about 2.5 MPa. Within this range, it is easy to control the temperature in the reaction system or the amount of water in the reaction system, and the discharge of the lower condensate may be easy. In addition, since a reactor having a low pressure resistance can be used, it is economically advantageous, and the degree of polymerization of the lower condensate can be increased by lowering the amount of water in the reaction system.
  • reaction time in the present process may be, for example, about 0.5 to about 4 hours, specifically about 1 to about 3 hours.
  • the reaction time represents the time required until the discharge operation starts after reaching the reaction temperature of the present invention. Sufficient reaction rate can be reached within this range, so that unreacted material hardly remains, whereby a lower condensate of uniform properties can be obtained. In addition, high-quality low-order condensates can be obtained without giving excessive heat history.
  • the amount of water in the reaction system at the end of the reaction of the lower condensate may be about 15 to about 35 weight percent, for example about 20 to about 35 weight percent.
  • finish of reaction it means the time of starting discharge operation of the low order condensate which reached
  • the amount of condensed water may be adjusted in consideration of the amount of condensed water to be generated, or a device having a condenser and a pressure control valve may be adjusted by distilling and removing a predetermined amount of water when adjusting the reaction pressure.
  • the process may optionally add a salt bath process and / or a concentration process before the lower condensate polymerization.
  • the salting step is a step of generating a salt with a dicarboxylic acid component and a diamine component, and may be adjusted to a pH of about ⁇ 0.5 at the neutralization point of the salt, for example, to a pH of about ⁇ 0.3 at the neutralization point of the salt.
  • the concentration of the raw material input concentration is preferably about +2 to about + 90% by weight, more preferably to a concentration of about +5 to about + 80% by weight.
  • the temperature of the concentration process is preferably in the range of about 90 to about 220 ° C, more preferably about 100 to about 210 ° C, particularly preferably about 130 to about 200 ° C.
  • the pressure of the concentration process is, for example, about 0.1 to about 2.0 MPa. Typically, the pressure at concentration is controlled below the pressure at the time of polymerization. In addition, forcibly discharging operation may be performed by nitrogen stream or the like to promote concentration.
  • the concentration process may be effective for shortening the polymerization time.
  • the logarithmic viscosity (IV) measured at a temperature of about 25 ° C. at a concentration of about 0.5 g / dL in concentrated sulfuric acid after removal from the reaction vessel (after cooling) is about 0.07 to about 0.40 dL / g,
  • the reaction is carried out to be about 0.10 to about 0.25 dL / g.
  • fusion between resin powders and adhesion in the apparatus during solid phase polymerization due to the presence of low melting point substances can be suppressed, and precipitation, solidification, etc. in the reaction system can be suppressed during the production of the lower condensate.
  • the polycondensation reaction for obtaining the lower condensate can be carried out batchwise or continuously.
  • the prepared lower polymer is discharged and cooled in the reaction vessel.
  • the evacuation and cooling process is to remove the lower condensate produced in the process from the reaction vessel.
  • the evacuation and cooling process is a lower order condensate when the temperature of the reaction system is in the range of about 200 ° C. or more and less than about 230 ° C., and the amount of water in the reaction system at the end of the reaction is in the range of about 15 to about 35% by weight. It is preferable to carry out from the reaction vessel under inert gas atmosphere under pressure conditions of atmospheric pressure or less.
  • the inert gas atmosphere may have an oxygen concentration of about 1% by volume or less in order to prevent oxidative degradation of the lower condensate.
  • the discharge rate of the lower condensate from the reaction vessel can be appropriately adjusted depending on the size of the reaction vessel, the amount of the contents in the reaction vessel, the temperature, the size of the acquisition port, the length of the acquisition nozzle, and the like.
  • the discharge may be performed such that the discharge rate per outlet cross-sectional area is about 2,000 to about 20,000 kg / s / m 2.
  • the apparatus used in the solid phase polymerization process Can improve the volumetric efficiency.
  • the lower order condensate discharged from the reaction vessel for example, hardly deteriorates due to thermal degradation and oxygen because its temperature is momentarily lowered to about 100 ° C. or lower due to latent heat of evaporation of water at the time of acquisition.
  • the lower condensate discharged evaporates most of the moisture accompanied by the sensible heat of the lower condensate
  • cooling and drying treatment of the lower condensate can be performed simultaneously.
  • the discharge treatment under an inert gas atmosphere such as nitrogen and / or a pressure lower than atmospheric pressure, the drying and cooling efficiency can be improved, which is preferable.
  • a cyclone-type solid-gas separator as the discharge vessel, it is possible to suppress out-of-system scattering of the powder during discharge and to increase the drying and cooling efficiency since the discharge treatment can be performed under a high gas flux.
  • the low-order condensate thus obtained has a sufficiently high algebraic viscosity and a low residual amount of unreacted material, so that solid phase polymerization can be carried out at a high temperature without fusion or agglomeration between the low-order condensate particles and less deterioration due to side reactions. .
  • the compacting process and the granulation process for making a particle size uniform can be further performed as needed.
  • the discharged and cooled low-order condensate is subjected to solid phase polymerization to produce a polyamide resin.
  • the solid phase polymerization reaction can be carried out continuously using the low order condensate obtained from the reaction vessel, and can be carried out after drying the low order condensate taken out of the reaction vessel. It is also possible to carry out after storing the lower condensate taken out of the reaction vessel once, or may be carried out after the compaction or granulation treatment is performed on the lower condensate taken out of the reaction vessel.
  • the polymerization method and conditions in the solid phase polymerization of the lower order condensate are not particularly limited, and any method and conditions capable of performing high polymerization while maintaining the solid state without causing fusion, agglomeration, or deterioration of the lower order condensate may be used. .
  • solid phase polymerization may be performed in an inert gas atmosphere such as helium gas, argon gas, nitrogen gas, carbon dioxide gas or under reduced pressure.
  • the reaction temperature is not particularly limited, but it is preferable that the highest reaction temperature is lower than or equal to the lower of the temperature of about 230 ° C and about 20 ° C lower than the melting point of the lower condensate. That is, when the melting point of the lower condensate is about 250 ° C. or less, the highest reaction temperature of the solid phase polymerization is preferably about 20 ° C. or less lower than the melting point of the lower condensate. When the melting point of the lower condensate exceeds about 250 ° C., the maximum reaction temperature of the solid phase polymerization is preferably about 230 ° C. or less.
  • the solid phase polymerization is possible at a lower temperature than that of the prior art, that is, a milder condition than the conventional art. Accordingly, a polyamide resin that satisfies the relationship of Formulas 1 and 2 can be obtained more efficiently.
  • the time point at which the highest reaction temperature is reached may be any time from the start of solid phase polymerization to the end.
  • the highest reaction temperature is below the lower temperature of about 225 ° C and about 30 ° C lower than the melting point of the lower condensate.
  • the apparatus for solid state polymerization used in this process is not particularly limited, and any known apparatus can be used.
  • Specific examples of the solid phase polymerization apparatus may include a uniaxial disk type, a kneader, a biaxial paddle type, a vertical column type device, a vertical column type device, a rotary drum type or a double cone type solid phase polymerization device, a dryer, and the like.
  • the reaction time of the solid phase polymerization is not particularly limited, but may be, for example, about 1 to about 20 hours.
  • the lower condensate may be mechanically stirred or stirred by gas flow.
  • various fiber materials such as glass fibers and carbon fibers, inorganic powder fillers, organic powder fillers, colorants, ultraviolet rays and, if necessary, at any stage after the step of preparing the lower condensate, the solid phase polymerization process or the solid phase polymerization.
  • Additives such as absorbents, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, plasticizers, lubricants, and other polymers may be added.
  • the production method of the present invention does not cause production problems such as gelation, and a polyamide resin having excellent physical balance such as mechanical strength, heat resistance and color tone can be obtained.
  • the polyamide resin obtained by the production method of the present invention is excellent in the balance of physical properties such as low water absorption, chemical resistance in addition to mechanical strength, heat resistance and color tone. Accordingly, the polyamide resin of the present invention can exhibit such properties by various conventional molding or spinning methods such as injection molding, blow molding, It can be molded into various molded articles, fibers, etc. through molding methods such as extrusion molding, compression molding, stretching, vacuum molding, and melt spinning.
  • the molded article and the fiber obtained in this way can be effectively used for various uses such as industrial materials such as electronic / electrical device parts, automobile parts, office equipment parts, industrial materials, household goods, etc. as well as the use as engineering plastics.
  • a sample solution was prepared by dissolving the sample at a concentration of 0.5 g / dL in 96% concentrated sulfuric acid.
  • the 96% concentrated sulfuric acid and the sample solution were measured using the Uberode viscometer at a temperature of 25 ° C., and the number of seconds dropped was calculated by the following Equation 3.
  • Equation 3 ⁇ rel is t1 / t0 (where t1 is the number of falling seconds of the sample and t0 is the number of falling seconds of the blank), and c is the solution velocity (g / dL).
  • amino terminal terminal concentration [NH 2 ] and carboxyl terminal terminal concentration [COOH] of the obtained polyamide resin were measured by the method shown below, and it calculated by the following formula
  • Each end group concentration was determined by titration of a polyamide resin sample solution adjusted to the following conditions using an automatic titrator COM-1700 manufactured by Hiranuma Sangyo Co., Ltd.
  • the sample in an amorphous state was heated at a temperature of 10 ° C./min to 30 ° C. higher than the polymer melting peak at 10 ° C./min under a nitrogen atmosphere at a flow rate of 10 ml / min, Hold for 5 minutes, and measure the glass transition temperature by measuring the glass transition temperature at the temperature reduction rate of 10 °C / min, and again the endothermic peak temperature due to melting at elevated temperature melting point, the exothermic peak temperature due to crystallization at lower temperature as crystallization temperature Each was measured.
  • the YI value was measured using the small colorimeter NW-11 manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • a rectangular test piece (size 80 mm x 10 mm x 4.0 mm) was manufactured under the conditions shown in Table 2 below, using SE18DUZ, an injection molding machine manufactured by Sumitomo Jukikai Co., Ltd.
  • Molding temperature 260-310 degreeC (The temperature 10 degreeC higher than melting
  • the universal testing machine 2001-5 manufactured by Intesco Co., Ltd. was used, and in accordance with JIS K7171: 2008 (ISO178: 2001), the test speed was 2 mm / min and the point-to-point distance 64 mm at 23 ° C and 50% RH. Flexural strength and flexural modulus were determined by bending test.
  • JIS K7191-1: 2007 JIS K7191-2: 2007 (ISO75-2: 2004) using the automatic HDT tester 6A-2 type manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the test piece was installed in a flatwise size and measured under the condition of a test stress of 1.80 MPa.
  • the discharge valve nozzle diameter was 1 mm, and the discharge time was 50 seconds.
  • the oxygen concentration of the discharged vessel was 0.1% by volume, to obtain a white, powdery low order condensate.
  • the low order condensate immediately after the discharge was a temperature of 81 ° C. and a water content of 2.2% by weight.
  • the obtained lower order condensate had an IV of 0.15 dL / g and a melting point of 267 ° C.
  • 300 g of the obtained lower condensate was placed in a 1,000 mL round bottom flask, installed in an oil bath rotary evaporator, and replaced with nitrogen, and then immersed in an oil bath at 210 ° C. while rotating the flask under a 1 L / min nitrogen flow to The temperature was raised to 203 ° C. for 1 hour, and then a solid phase polymerization reaction was performed at the same temperature for 4 hours. After predetermined reaction time passed, it cooled to room temperature (25 degreeC), and obtained the high polymerization polyamide resin.
  • the obtained polyamide resin had an IV of 0.85 dL / g and Mn of 11,640 g / mol, exhibiting properties satisfying Equations 1 and 2 above.
  • the melting point by DSC measurement was 283 ° C, the glass transition temperature was 105 ° C, the crystallization temperature was 229 ° C, and the high heat-resistant polyamide resin having high polymerization degree and good color was obtained with YI of 4.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the flexural strength was 181 MPa
  • the flexural modulus was 4.4 GPa
  • the load deformation temperature was 110 °C, indicating high strength, high rigidity, and high heat resistance.
  • IV of the obtained polyamide resin was 0.93 dL / g
  • Mn showed 12,063 g / mol and the said Formulas 1 and 2 were satisfied.
  • the melting point by DSC measurement was 288 degreeC
  • the glass transition temperature was 103 degreeC
  • the crystallization temperature was 231 degreeC
  • YI was highly polymerized to 5
  • the high heat resistant polyamide resin with favorable color was obtained.
  • the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the flexural strength was 176 MPa
  • the flexural modulus was 4.4 GPa
  • the load deformation temperature was 110 °C, indicating high strength, high rigidity, and high heat resistance.
  • IV of the obtained polyamide resin was 0.78 dL / g
  • Mn showed 9,751 g / mol and the said Formulas 1 and 2 were satisfied.
  • fusing point by DSC measurement was 286 degreeC
  • glass transition temperature was 101 degreeC
  • crystallization temperature was 238 degreeC
  • YI was highly polymerized to 5, and the high heat resistant polyamide resin with favorable color was obtained.
  • the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the flexural strength was 182 MPa
  • the flexural modulus was 4.3 GPa
  • the load deformation temperature was 105 °C, indicating high strength, high rigidity, and high heat resistance.
  • IV of the obtained polyamide resin was 0.72 dL / g
  • Mn showed the property which satisfy
  • the melting point by DSC measurement was 314 ° C
  • the glass transition temperature was 101 ° C
  • the crystallization temperature was 242 ° C
  • YI was highly polymerized to 5 to obtain a high heat-resistant polyamide resin having good color.
  • the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the flexural strength was 185 MPa
  • the flexural modulus was 4.3 GPa
  • the load deflection temperature was 106 ° C, indicating high strength, high rigidity, and high heat resistance.
  • Example 2 Except that the lower condensate was discharged under the condition of distilling / removing 41 g of water by controlling the polymerization temperature of the lower condensate to 225 ° C and controlling the reaction pressure to 2.5 MPa, and the maximum temperature of the solid phase polymerization was 224 ° C.
  • a lower-order condensate and a polyamide resin were prepared.
  • the obtained lower order condensate had an IV of 0.21 dL / g and a melting point of 269 ° C.
  • IV of the obtained polyamide resin was 1.21 dL / g
  • Mn showed 17,316 g / mol and the said Formulas 1 and 2 were satisfied.
  • the melting point by DSC measurement was 282 ° C, the glass transition temperature was 106 ° C, the crystallization temperature was 231 ° C, YI was highly polymerized to 5, and a high heat-resistant polyamide resin having good color was obtained. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the flexural strength was 195 MPa
  • the flexural modulus was 4.4 GPa
  • the load deformation temperature was 112 ° C, indicating high strength, high rigidity, and high heat resistance.
  • IV of the obtained polyamide resin was 0.81 dL / g, Mn was 10,753 g / mol, and showed the property which satisfy
  • a high heat-resistant polyamide resin having a high polymerization degree with a melting point of 295 ° C., a glass transition temperature of 112 ° C., a crystallization temperature of 246 ° C., and a YI of 4 was obtained by DSC measurement. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the flexural strength was 190 MPa
  • the flexural modulus was 4.4 GPa
  • the load deflection temperature was 120 ° C, indicating high strength, high rigidity, and high heat resistance.
  • IV of the obtained polyamide resin was 0.69 dL / g, Mn showed 9,799 g / mol and the said Formulas 1 and 2 were satisfied.
  • the glass transition temperature by DSC measurement was 110 degreeC, and melting
  • YI was highly polymerized to 5 and a polyamide resin having good color was obtained.
  • the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
  • a lower order condensate and a polyamide resin were prepared in the same manner as in Example 2 except that the polymerization temperature of the lower order condensate was 250 ° C. and the reaction pressure was controlled to 3.2 MPa.
  • the obtained lower order condensate had an IV of 0.18 dL / g and a melting point of 264 ° C.
  • IV of the obtained polyamide resin was 0.95 dL / g and Mn did not satisfy Formula 2 at 7,435 g / mol.
  • fusing point by DSC measurement was 267 degreeC, glass transition temperature was 104 degreeC, crystallization temperature was 218 degreeC, YI was 9, and it was a polyamide resin inferior to heat resistance and crystallinity.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the foreign material was present in the test piece, the flexural strength was 106 MPa, the flexural modulus was 4.2 GPa, and the load deflection temperature was 110 ° C.
  • the lower condensate was made in the same manner as in Example 2 except that the amount of the raw material was adjusted in the same manner as in Example 1, the polymerization temperature of the lower condensate was controlled to 240 ° C., the reaction pressure was controlled to 2.9 MPa, and the solid phase polymerization temperature was 212 ° C. And polyamide resins.
  • the obtained lower order condensate had an IV of 0.18 dL / g and a melting point of 262 ° C.
  • IV of the obtained polyamide resin was 1.15 dL / g and Mn was 12,821 g / mol and did not satisfy Formula 2. Melting
  • fusing point by DSC measurement was 269 degreeC, glass transition temperature was 103 degreeC, crystallization temperature was 220 degreeC, and YI was 8, and polyamide resin was inferior to heat resistance and crystallinity slightly.
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated.
  • the foreign material was present in the test piece, the flexural strength was 142 MPa, the flexural modulus was 4.2 GPa, and the load deflection temperature was 110 ° C.
  • the lower condensate and the polyamide were prepared in the same manner as in Example 2, except that the amount of starting materials was the same as in Example 1, and the polymerization temperature of the lower condensate was 230 ° C., the reaction pressure was 2.7 MPa, and the reaction time was 5 hours. Resin was prepared. IV of the obtained lower condensate was 0.18 dL / g, and melting
  • the obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. Foreign matter was present in the specimen, flexural strength was 138 MPa, flexural modulus was 4.2 GPa, and the load deformation temperature was 110 ° C.
  • the lower condensate and the polyamide resin were prepared in the same manner as in Example 1 except that the polymerization temperature of the lower condensate was 230 ° C. and the maximum temperature of the solid phase polymerization was 234 ° C.
  • the obtained lower order condensate had an IV of 0.18 dL / g and a melting point of 262 ° C.
  • the obtained polyamide resin could not be analyzed due to the presence of many gel-like compounds which were insoluble in an analytical solvent such as concentrated sulfuric acid.
  • the melting point was 250 ° C, the glass transition temperature was 101 ° C, and the crystallization temperature was 168 by DSC measurement. °C, YI was 16, poor heat resistance and color.
  • the obtained polyamide resin contained many gel-like compounds, and the test piece was not obtained.
  • IV of the obtained polyamide resin was 0.84 dL / g
  • Mn showed 12,143 g / mol and the said Formulas 1 and 2 were satisfied.
  • fusing point by DSC measurement was 238 degreeC
  • glass transition temperature was 86 degreeC
  • crystallization temperature was 181 degreeC
  • YI was 5.
  • the obtained polyamide resin was produced into test pieces by injection molding, and mechanical properties were evaluated.
  • the flexural strength was 151 MPa
  • the flexural modulus was 4.6 GPa
  • the load deflection temperature was 95 ° C.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
  • Raw material dicarboxylic acid CHDA 30mol% 30mol% 20mol% 20mol% 30mol% 40mol% AdA 70 mol% 70 mol% 80 mol% 80 mol% 70 mol% 60mol%
  • Raw material diamine PXDA 30mol% 40mol% 50 mol% 70 mol% 30mol% 30mol% 30mol% MXDA 70 mol% 60mol% 50 mol% 30mol% 70 mol% 70 mol% catalyst
  • SHM 0.1 parts by weight ⁇ ⁇ ⁇ ⁇ ⁇ Input 18wt% 40wt% 18wt% ⁇ ⁇ ⁇ Reaction temperature (°C) 220 220 220 220 225 220 Reaction pressure (MPa) 1.9 1.9 1.9 1.9 1.9 2.5 1.9 Reaction time (hr) 2 2 2 2 2 2 2 2 2 2 Reaction system moisture at discharge (wt%) 28 28 28 28 21 28 Discharge vessel pressure Atmospheric pressure ⁇ ⁇ ⁇ ⁇
  • the polyamide resin of the present invention obtained in Examples 1 to 6 has excellent physical balance (balance) such as mechanical strength, heat resistance and color tone.
  • the polyamide resin produced by the production method of the present invention does not cause manufacturing problems such as gelation.

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Abstract

A polyamide resin of the present invention is a polymer of a monomer mixture including: a dicarboxylic acid ingredient containing 1 and 4-cyclohexanedicarboxylic acid; and a diamine ingredient containing xylylenediamine having a para-xylylenediamine ingredient at a content of about 10 to 100 mole%, and said resin is characterized in that the number average molecular weight (Mn) satisfies equations 1 and 2 set forth in the claims, wherein the Mn is obtained using the titration method and inherent viscosity (IV) measured at the temperature of about 25°C and at a concentration of about 0.5 g/dL in concentrated sulfuric acid. The polyamide resin has excellent mechanical strength, heat resistance, color tone, and a balance of physical properties thereof.

Description

폴리아미드 수지 및 그 제조방법Polyamide Resin and Manufacturing Method Thereof
본 발명은 폴리아미드 수지 및 그 제조방법에 관한 것이다. 보다 구체적으로는, 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 우수한 폴리아미드 수지 및 그 제조방법에 관한 것이다.The present invention relates to a polyamide resin and a method for producing the same. More specifically, it is related with the polyamide resin excellent in mechanical strength, heat resistance, color tone, and the balance of these physical properties, and its manufacturing method.
폴리아미드 수지는 그 우수한 특성과 용융성형의 용이성으로 인해 의류용, 산업자재용 섬유, 엔지니어링 플라스틱 등으로 널리 이용되고 있다. 그러나, 이들 범용 폴리아미드 수지는 내열성 부족, 흡수에 의한 치수안정성 불량 등의 문제점이 있다. 더욱이, 전기·전자부품, 자동차부품 등의 분야에서 이용되는 폴리아미드 수지는 기존의 폴리아미드 수지에 비해 더욱 우수한 물성 및 기능성이 요구되고 있다. 예를 들면, 고내열성과 함께 치수안정성, 역학적 특성, 내약품성, 중합 시 또는 성형가공 시의 취급성 등이 더욱 우수한 폴리아미드 수지의 개발이 요구되고 있다.Polyamide resins are widely used in clothing, industrial materials and engineering plastics due to their excellent properties and ease of melt molding. However, these general-purpose polyamide resins have problems such as lack of heat resistance and poor dimensional stability due to absorption. Moreover, polyamide resins used in fields such as electric and electronic parts, automobile parts, and the like are required to have more excellent physical properties and functionality than conventional polyamide resins. For example, there is a demand for the development of a polyamide resin that is more excellent in dimensional stability, mechanical properties, chemical resistance, handling property during polymerization or molding processing, together with high heat resistance.
통상의 폴리아미드 수지의 제조방법으로는 디카르복시산과 디아민 등으로 형성된 염이나 저차 축합물을 용융조건 하에서 가열하여 중축합시키는 방법이 알려져 있다. 또한, 이러한 제조방법을 파라크실리렌디아민을 디아민 성분으로 이용한 폴리아미드 수지의 제조방법에도 적용할 수 있다는 것이 알려져 있다. 예를 들어, 파라크실리렌디아민, 메타크실리렌디아민, 및 지방족 디카르복시산으로부터 폴리아미드 수지의 제조(일본 특허공고공보 소32-6148호, 일본 특허공고공보 소44-20637호, 일본 특허공고공보 소47-15106호 참조), 파라크실리렌디아민, 헥사메틸렌디아민, 아디프산 및 테레프탈산으로부터 폴리아미드 수지의 제조(일본 특허공고공보 소47-33277호 참조) 등을 들 수 있다.As a conventional method for producing a polyamide resin, a method of polycondensing a salt formed by dicarboxylic acid, diamine or the like or a lower order condensate by heating under melting conditions is known. Moreover, it is known that this manufacturing method can be applied also to the manufacturing method of the polyamide resin which used paraxylylenediamine as a diamine component. For example, production of polyamide resins from paraxylylenediamine, metaxylenediamine, and aliphatic dicarboxylic acid (Japanese Patent Publication No. 32-6148, Japanese Patent Publication No. 44-20637, Japanese Patent Publication) And the production of polyamide resins (see Japanese Patent Publication No. 47-33277) from paraxylenediamine, hexamethylenediamine, adipic acid and terephthalic acid.
또한, 일본 공개특허공보 평08-3312호에는 크실리렌디아민 및 벤젠디카르복시산에서 유래되는 구조를 함유하는 폴리아미드 수지를 복수의 중합장치를 이용하는 용융다단중합으로 제조하는 방법이 개시되어 있다.Further, Japanese Laid-Open Patent Publication No. 08-3312 discloses a method for producing a polyamide resin containing a structure derived from xylenediamine and benzenedicarboxylic acid by melt multistage polymerization using a plurality of polymerization apparatuses.
그러나, 상기 제조방법들은 고융점 폴리아미드 수지에 적용할 경우, 용융상태를 유지하기 위해 고온을 필요로 하기 때문에 생성물이 열분해를 일으키기 쉽고, 제조된 폴리아미드 수지는 기계적 강도, 내성 열화성, 색조 등의 물성이 저하될 우려가 있다. 또한, 상기 제조방법들로부터 제조된 폴리아미드 수지는 겔을 포함하는 등 점도가 높고 취급이 곤란하며, 반응기 내벽에 내용물이 잔존하기 쉬워 수율이 낮아지는 등 제조상의 문제가 발생할 수 있다.However, the production methods are prone to pyrolysis of the product because it requires high temperature to maintain the molten state when applied to high melting point polyamide resin, the polyamide resin produced is mechanical strength, resistance degradation, color tone, etc. There is a fear that the physical properties of the. In addition, the polyamide resin prepared from the above production methods may contain a gel, such as a high viscosity and difficult to handle, and may cause a manufacturing problem such as the contents easily remain on the inner wall of the reactor and the yield is low.
본 발명의 목적은 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 우수한 폴리아미드 수지를 제공하기 위한 것이다.An object of the present invention is to provide a polyamide resin having excellent mechanical strength, heat resistance, color tone and balance of physical properties thereof.
본 발명의 다른 목적은 겔화 등 제조상의 문제를 방지할 수 있는, 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 우수한 폴리아미드 수지를 얻을 수 있는 폴리아미드 수지의 제조방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing a polyamide resin capable of obtaining a polyamide resin having excellent mechanical strength, heat resistance, color tone, and balance of physical properties thereof, which can prevent manufacturing problems such as gelation.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 하나의 관점은 폴리아미드 수지에 관한 것이다. 상기 폴리아미드 수지는 1,4-시클로헥산디카르복시산을 함유하는 디카르복시산 성분; 및 파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민을 함유하는 디아민 성분;을 포함하는 단량체 혼합물의 중합체이며, 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도(IV)및 적정법으로 구한 수평균분자량(Mn)이 하기 식 1 및 식 2를 만족하는 것을 특징으로 한다:One aspect of the invention relates to polyamide resins. The polyamide resin is a dicarboxylic acid component containing 1,4-cyclohexanedicarboxylic acid; And a diamine component containing a xylylenediamine having a content of paraxylenediamine component of about 10 to about 100 mol%, wherein the polymer is a monomer mixture comprising a temperature of about 0.5 g / dL in concentrated sulfuric acid. The logarithmic viscosity (IV) measured at 25 ° C. and the number average molecular weight (Mn) determined by the titration method satisfy the following Equations 1 and 2:
[식 1][Equation 1]
약 0.4 ≤ IV ≤ 약 1.5About 0.4 ≤ IV ≤ about 1.5
[식 2][Equation 2]
약 12,000 ≤ Mn/IVAbout 12,000 ≤ Mn / IV
구체예에서, 상기 디카르복시산 성분은 상기 1,4-시클로헥산디카르복시산 5 내지 약 50 몰%, 및 1,4-시클로헥산디카르복시산 이외의 디카르복시산 약 50 내지 약 95 몰%를 함유하며, 상기 디아민 성분은 상기 크실리렌디아민 약 50 내지 약 100 몰%와 크실리렌디아민 이외의 디아민 약 0 내지 약 50 몰%를 함유할 수 있다.In embodiments, the dicarboxylic acid component contains 5 to about 50 mole percent of the 1,4-cyclohexanedicarboxylic acid, and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid, wherein The diamine component may contain about 50 to about 100 mole percent of the xyleneylene diamine and about 0 to about 50 mole percent of diamines other than xyleneylene diamine.
구체예에서, 상기 폴리아미드 수지는 융점이 약 270℃ 이상이고 유리전이온도가 약 100℃ 이상이며, 또 굴곡탄성률이 약 4 GPa 이상일 수 있다.In embodiments, the polyamide resin may have a melting point of about 270 ° C. or more, a glass transition temperature of about 100 ° C. or more, and a flexural modulus of about 4 GPa or more.
구체예에서, 상기 크실리렌디아민은 메타크실리렌디아민 성분을 약 10 내지 약 90 몰% 포함할 수 있다.In embodiments, the xylylenediamine may comprise from about 10 to about 90 mole percent of the metaxylenediamine component.
본 발명의 다른 관점은 상기 폴리아미드 수지의 제조방법에 관한 것이다. 상기 제조방법은 1,4-시클로헥산디카르복시산을 함유하는 디카르복시산 성분과 파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민을 함유하는 디아민 성분을 약 200℃ 이상 약 230℃ 미만의 반응온도 및 약 0.5 내지 약 3 MPa의 반응압력 하에서 약 0.5 내지 약 4시간 동안 반응시키고, 반응 종료 후, 반응계 내의 수분량이 약 15 내지 약 35 중량%인 조건으로 중축합 반응을 실시하여, 저차 축합물을 제조하는 공정; 불활성가스 분위기 하, 대기압 이하의 압력으로 상기 저차 축합물을 배출 및 냉각하는 공정; 및 상기 배출 및 냉각한 저차 축합물을 고상중합하는 공정;을 포함하며, 상기 배출 및 냉각한 저차 축합물은 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도가 약 0.07 내지 약 0.40 dL/g인 것을 특징으로 한다.Another aspect of the present invention relates to a method for producing the polyamide resin. The preparation method comprises a diamine component containing 1,4-cyclohexanedicarboxylic acid and a diamine component containing xyleneylene diamine having a content of about 10 to about 100 mol% of the paracarboxylic acid dicarboxylic acid component at least about 200 ° C. The reaction is performed for about 0.5 to about 4 hours at a reaction temperature of less than about 230 ° C. and a reaction pressure of about 0.5 to about 3 MPa. After completion of the reaction, the polycondensation reaction is carried out under the condition that the water content in the reaction system is about 15 to about 35 wt%. Performing a lower order condensate; Discharging and cooling the lower order condensate under an inert gas atmosphere at a pressure below atmospheric pressure; And solid-phase polymerization of the discharged and cooled lower condensates, wherein the discharged and cooled lower condensates have a logarithmic viscosity measured at a temperature of about 25 ° C. at a concentration of about 0.5 g / dL in concentrated sulfuric acid. 0.07 to about 0.40 dL / g.
구체예에서, 상기 디카르복시산 성분은 상기 1,4-시클로헥산디카르복시산 약 5 내지 약 50 몰%, 및 1,4-시클로헥산디카르복시산 이외의 디카르복시산 약 50 내지 약 95 몰%를 함유하며, 상기 디아민 성분은 상기 크실리렌디아민 약 50 내지 약 100 몰%와 크실리렌디아민 이외의 디아민 약 0 내지 약 50 몰%를 함유할 수 있다.In an embodiment, the dicarboxylic acid component contains about 5 to about 50 mole percent of the 1,4-cyclohexanedicarboxylic acid, and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid, The diamine component may contain about 50 to about 100 mole percent of the xylylenediamine and about 0 to about 50 mole percent of diamines other than xylylenediamine.
구체예에서, 상기 고상중합의 최고 반응온도는, 약 230℃ 및 상기 저차 축합물의 융점보다 약 20℃ 낮은 온도 중 낮은 쪽 온도 이하일 수 있다.In an embodiment, the maximum reaction temperature of the solid phase polymerization may be less than or equal to the lower of about 230 ° C. and about 20 ° C. lower than the melting point of the lower condensate.
본 발명은 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 우수한 폴리아미드 수지, 및 겔화 등 제조상의 문제를 방지할 수 있는 상기폴리아미드 수지의 제조방법을 제공하는 발명의 효과를 갖는다.This invention has the effect of providing the polyamide resin which is excellent in mechanical strength, heat resistance, color tone, and the balance of these physical properties, and the manufacturing method of the said polyamide resin which can prevent manufacturing problems, such as gelation.
이하, 본 발명을 상세히 설명하면, 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 폴리아미드 수지는 1,4-시클로헥산디카르복시산을 함유하는 디카르복시산 성분; 및 파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민을 함유하는 디아민 성분;을 포함하는 단량체 혼합물의 중합체이며, 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도(IV)및 적정법으로 구한 수평균분자량(Mn)이 하기 식 1 및 식 2를 만족하는 것을 특징으로 한다.The polyamide resin according to the present invention comprises a dicarboxylic acid component containing 1,4-cyclohexanedicarboxylic acid; And a diamine component containing a xylylenediamine having a content of paraxylenediamine component of about 10 to about 100 mol%, wherein the polymer is a monomer mixture comprising a temperature of about 0.5 g / dL in concentrated sulfuric acid. The logarithmic viscosity (IV) measured at 25 ° C. and the number average molecular weight (Mn) determined by the titration method satisfy the following formulas (1) and (2).
[식 1][Equation 1]
약 0.4 ≤ IV ≤ 약 1.5About 0.4 ≤ IV ≤ about 1.5
[식 2][Equation 2]
약 12,000 ≤ Mn/IVAbout 12,000 ≤ Mn / IV
[디카르복시산 성분][Dicarboxylic Acid Component]
상기 디카르복시산 성분은 1,4-시클로헥산디카르복시산 약 5 내지 약 50 몰% 및 1,4-시클로헥산디카르복시산 이외의 디카르복시산 약 50 내지 약 95 몰%를 함유한다. 상기 범위에서 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 우수한 폴리아미드 수지를 얻을 수 있다. 상기 1,4-시클로헥산디카르복시산과 1,4-시클로헥산디카르복시산 이외의 디카르복시산의 합계량은 100 몰%이다.The dicarboxylic acid component contains about 5 to about 50 mole percent of 1,4-cyclohexanedicarboxylic acid and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid. In the above range, a polyamide resin having excellent mechanical strength, heat resistance, color tone, and balance of physical properties thereof can be obtained. The total amount of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid is 100 mol%.
상기 디카르복시산 성분 중, 1,4-시클로헥산디카르복시산의 함유량은 약 5 내지 약 50 몰%, 예를 들면 약 10 내지 약 50 몰%, 구체적으로 약 15 내지 약 45 몰%이다. 상기 범위에서 내열성, 결정성이 양호하고, 성형가공이 용이한 폴리아미드 수지를 얻을 수 있다. 상기 1,4-시클로헥산디카르복시산의 함유량이 약 5 몰% 미만이면, 충분한 내열성을 얻지 못할 우려가 있고, 약 50 몰%를 초과하면, 과도하게 융점이 상승하여 용융성형이 곤란해질 수 있다.The content of 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid component is about 5 to about 50 mol%, for example about 10 to about 50 mol%, specifically about 15 to about 45 mol%. Within this range, a polyamide resin having good heat resistance and crystallinity and easy molding processing can be obtained. If the content of the 1,4-cyclohexanedicarboxylic acid is less than about 5 mol%, sufficient heat resistance may not be obtained. If the content of the 1,4-cyclohexanedicarboxylic acid is less than about 50 mol%, the melting point may be excessively increased and melt molding may be difficult.
상기 1,4-시클로헥산디카르복시산 이외의 디카르복시산의 구체예로는 마론산, 디메틸마론산, 숙신산, 글루탈산, 아디프산, 2-메틸아디프산, 트리메틸아디프산, 피메린산, 2,2-디메틸글루탈산, 3,3-디에틸숙신산, 스베르산, 아젤라인산, 세바스산, 운데칸이산, 도데칸이산 등의 지방족 디카르복시산; 1,3-시클로펜탄디카르복시산 등의 지환식 디카르복시산; 테레프탈산, 이소프탈산, 2,6-나프탈렌디카르복시산, 2,7-나프탈렌디카르복시산, 1,4-나프탈렌디카르복시산, 1,4-페닐렌디옥시디아세트산, 1,3-페닐렌디옥시디아세트산, 디펜산, 4,4'-옥시디벤조산, 디페닐메탄-4,4'-디카르복시산, 디페닐술폰-4,4'-디카르복시산, 4,4'-비페닐디카르복시산 등의 방향족 디카르복시산을 예시할 수 있으나, 이에 제한되지 않는다. 이러한 디카르복시산들은 단독 또는 2종 이상 혼합하여 사용할 수도 있다. 예를 들면 아디프산, 세바스산 등의 직쇄 지방족 디카르복시산을 사용할 수 있다.Specific examples of dicarboxylic acids other than the 1,4-cyclohexanedicarboxylic acid include maronic acid, dimethylmaronic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimeric acid, Aliphatic dicarboxylic acids such as 2,2-dimethylglutal acid, 3,3-diethyl succinic acid, subric acid, azelaic acid, sebacic acid, undecane diacid, and dodecane diacid; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid; Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphene Aromatic dicarboxylic acids such as acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid It can be illustrated, but is not limited thereto. These dicarboxylic acids may be used alone or in combination of two or more thereof. For example, linear aliphatic dicarboxylic acids such as adipic acid and sebacic acid can be used.
상기 디카르복시산 성분 중 1,4-시클로헥산디카르복시산 이외의 디카르복시산의 함유량은 약 50 내지 약 95 몰%, 예를 들면 약 50 내지 약 90 몰%, 구체적으로 약 55 내지 약 85 몰%이다. 상기 범위에서 내열성, 결정성이 양호하고, 성형가공이 용이한 폴리아미드 수지를 얻을 수 있다. 상기 1,4-시클로헥산디카르복시산 이외의 디카르복시산의 함유량이 약 95 몰%를 초과하면, 충분한 내열성을 얻지 못할 우려가 있고, 약 50 몰% 미만이면, 과도하게 융점이 상승하여 용융성형이 곤란해질 수 있다.The content of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid component is about 50 to about 95 mole%, for example about 50 to about 90 mole%, specifically about 55 to about 85 mole%. Within this range, a polyamide resin having good heat resistance and crystallinity and easy molding processing can be obtained. If the content of dicarboxylic acids other than the 1,4-cyclohexanedicarboxylic acid is more than about 95 mol%, there is a fear that sufficient heat resistance may not be obtained. If the content is less than about 50 mol%, the melting point rises excessively, and melt molding is difficult. Can be done.
필요에 따라, 트리멜리트산, 트리메신산, 피로멜리트산 등의 다가 카르복시산 성분을 소량 병용할 수도 있다.As needed, a small amount of polyhydric carboxylic acid components, such as trimellitic acid, trimesic acid, a pyromellitic acid, can also be used together.
[디아민 성분][Diamine component]
상기 디아민 성분은 파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민 약 50 내지 약 100 몰%, 및 크실리렌디아민 이외의 디아민 약 0 내지 약 50 몰%를 함유한다. 상기 범위에서 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 우수한 폴리아미드 수지를 얻을 수 있다. 상기 크실리렌디아민과 크실리렌디아민 이외의 디아민의 합계량은 100 몰%이다.The diamine component contains about 50 to about 100 mol% of xylylenediamine having a content of paraxylenediamine component of about 10 to about 100 mol%, and about 0 to about 50 mol% of diamines other than xylylenediamine. do. In the above range, a polyamide resin having excellent mechanical strength, heat resistance, color tone, and balance of physical properties thereof can be obtained. The total amount of diamines other than the xylene diamine and xylene diamine is 100 mol%.
본 발명의 명세서에서, 상기 "크실리렌디아민(xylylene diamine)"이라고 하는 용어에는 3종의 이성체인 오르토크실리렌디아민(o-xylylene diamine), 메타크실리렌디아민(m-xylylene diamine, MXDA) 및 파라크실리렌디아민(p-xylylene diamine, PXDA)이 포함된다.In the specification of the present invention, the term "xylylene diamine" includes three kinds of isomers, ortho-xylylene diamine (o-xylylene diamine) and methaxylene diamine (m-xylylene diamine, MXDA). ) And para-xylylene diamine (PXDA).
상기 크실리렌디아민 중 파라크실리렌디아민 성분의 함유량은 약 10 내지 약 100 몰%, 예를 들면 약 10 내지 약 90 몰%, 구체적으로 약 20 내지 약 80 몰%이다. 상기 파라크실리렌디아민 성분의 함량이 전체 크실리렌디아민 100 몰% 중, 약 10 몰% 미만이면, 기계적 강도가 저하될 우려가 있다.The content of paraxylenediamine component in the xyleneylene diamine is about 10 to about 100 mol%, for example about 10 to about 90 mol%, specifically about 20 to about 80 mol%. If the content of the paraxylylenediamine component is less than about 10 mol% in 100 mol% of the total xylene diamine, there is a possibility that the mechanical strength is lowered.
상기 폴리아미드 수지의 기계적 강도를 유지하면서 성형가공성을 제어하기 위하여, 크실리렌디아민 전체 100 몰% 중, 메타크실리렌디아민을 예를 들면 약 10 내지 약 90 몰%, 구체적으로 약 20 내지 약 80 몰% 포함할 수 있다.In order to control the molding processability while maintaining the mechanical strength of the polyamide resin, metha xylylenediamine, for example, of about 10 to about 90 mol%, specifically about 20 to about It may contain 80 mol%.
상기 디아민 성분 중 크실리렌디아민의 함유량은 약 50 내지 약 100 몰%, 예를 들면 약 60 내지 약 100 몰%, 구체적으로 약 70 내지 약 100 몰%이다. 상기 크실리렌디아민의 함유량이 디아민 성분 중 약 50 몰% 미만이면, 폴리아미드 수지의 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 저하될 우려가 있다.The content of xylylenediamine in the diamine component is about 50 to about 100 mol%, for example about 60 to about 100 mol%, specifically about 70 to about 100 mol%. When content of the said xylene diamine is less than about 50 mol% in a diamine component, there exists a possibility that the mechanical strength, heat resistance, color tone, and balance of these physical properties of a polyamide resin may fall.
상기 크실리렌디아민 이외의 다른 디아민의 구체예로는 에틸렌디아민, 프로판디아민, 1,4-부탄디아민, 1,6-헥산디아민(헥사메틸렌디아민), 1,7-헵탄디아민, 1,8-옥탄디아민, 1,9-노난디아민, 1,10-데칸디아민, 1,11-운데칸디아민, 1,12-도데칸디아민, 2-메틸-1,5-펜탄디아민, 3-메틸-1,5-펜탄디아민, 2,2,4-트리메틸-1,6-헥산디아민, 2,4,4-트리메틸-1,6-헥산디아민, 2-메틸-1,8-옥탄디아민, 5-메틸-1,9-노난디아민 등의 지방족 알킬렌디아민; 시클로헥산디아민, 메틸시클로헥산디아민, 이소포론디아민, 비스(4-아미노시클로헥실)메탄, 1,3-비스아미노메틸시클로헥산, 1,4-비스아미노메틸시클로헥산, 노르보르난디메탄아민, 트리시클로데칸디메탄아민 등의 지환식 디아민; 파라페닐렌디아민, 메타페닐렌디아민, 4,4'-디아미노디페닐술폰, 4,4'-디아미노디페닐에테르 등의 방향족 디아민 등을 예시할 수 있으나, 이에 제한되지 않는다. 상기 다른 디아민들은 단독 또는 2종 이상 혼합하여 사용할 수도 있다. 예를 들면 헥사메틸렌디아민 등의 직쇄 지방족 디아민을 사용할 수 있다.Specific examples of diamines other than the xyleneylene diamine include ethylenediamine, propanediamine, 1,4-butanediamine, 1,6-hexanediamine (hexamethylenediamine), 1,7-heptanediamine, 1,8- Octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl- Aliphatic alkylenediamines such as 1,9-nonanediamine; Cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, norbornanedimethanamine, tri Alicyclic diamines such as cyclodecane dimethanamine; Aromatic diamines, such as paraphenylenediamine, metaphenylenediamine, 4,4'- diamino diphenyl sulfone, and 4,4'- diamino diphenyl ether, etc. can be illustrated, but it is not limited to these. The other diamines may be used alone or in combination of two or more thereof. For example, linear aliphatic diamines, such as hexamethylenediamine, can be used.
상기 디아민 성분 중 크실리렌디아민 이외의 다른 디아민의 함유량은 약 0 내지 약 50 몰%, 예를 들면 약 0 내지 약 40 몰%, 구체적으로 약 0 내지 약 30 몰%이다. 상기 크실리렌디아민 이외의 다른 디아민의 함유량이 디아민 성분 중 약 50 몰%를 초과하면, 폴리아미드 수지의 기계적 강도, 내열성, 색조 및 이들의 물성 발란스가 저하될 우려가 있다.The content of other diamines other than xylylenediamine in the diamine component is about 0 to about 50 mol%, for example about 0 to about 40 mol%, specifically about 0 to about 30 mol%. When content of diamine other than the said xylene diamine exceeds about 50 mol% in a diamine component, there exists a possibility that the mechanical strength, heat resistance, color tone, and balance of these physical properties of a polyamide resin may fall.
상기 디카르복시산 성분과 디아민 성분을 가지는 본 발명의 폴리아미드 수지는 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도(IV)가 하기 식 1을 만족하는 값을 가진다.In the polyamide resin of the present invention having the dicarboxylic acid component and the diamine component, the logarithmic viscosity (IV) measured at a temperature of about 25 ° C. at a concentration of about 0.5 g / dL in concentrated sulfuric acid has a value satisfying the following formula (1).
[식 1][Equation 1]
약 0.4 ≤ IV ≤ 약 1.5About 0.4 ≤ IV ≤ about 1.5
상기 폴리아미드 수지의 IV가 약 0.4 미만인 경우, 용융점도가 과도하게 낮아지기 때문에 성형가공 시, 버(burr) 등의 성형불량이 발생할 뿐만 아니라, 기계적 강도도 불충분해질 우려가 있다. 또한, IV가 약 1.5를 초과하는 경우, 성형가공 시 유동성이 저하될 수 있으며, 이에 따라, 가공온도를 분해온도 근방까지 높여야 하거나, 양호한 가공조건을 쉽게 찾을 수 없어, 고상중합 시, 열이력이 지나치게 커지기 때문에 양호한 성상의 폴리아미드 수지를 얻기 어려울 수 있다. 상기 폴리아미드의 대수점도(IV)는 예를 들면 약 0.5 내지 약 1.4, 구체적으로 약 0.6 내지 약 1.3이다. 상기 IV는 보다 구체적으로는 후술하는 실시예에 기재된 방법에 의해 측정할 수 있다.When the IV of the polyamide resin is less than about 0.4, since the melt viscosity is excessively low, there is a possibility that not only molding defects such as burrs occur during molding processing but also insufficient mechanical strength. In addition, if IV exceeds about 1.5, fluidity may decrease during molding, and thus, the processing temperature must be increased to near the decomposition temperature, or good processing conditions cannot be easily found. Since it becomes too large, it may be difficult to obtain a polyamide resin of good properties. The logarithmic viscosity (IV) of the polyamide is for example about 0.5 to about 1.4, specifically about 0.6 to about 1.3. The said IV can be measured by the method as described in the Example mentioned later more specifically.
또한, 본 발명의 폴리아미드 수지의 적정법으로 측정한 수평균분자량(Mn) 및 대수점도(IV)는 하기 식 2로 나타내는 관계를 만족한다.In addition, the number average molecular weight (Mn) and logarithmic viscosity (IV) measured by the titration method of the polyamide resin of this invention satisfy | fill the relationship shown by following formula (2).
[식 2][Equation 2]
약 12,000 ≤ Mn/IVAbout 12,000 ≤ Mn / IV
상기 식 2의 관계는 수평균분자량(Mn)에 대해 대수점도(IV)가 충분히 낮다는 것을 나타내고 있으며, 공중합 성분의 불균일한 반응 진행이나 가교화 반응 등에 의해 비정상적으로 고분자량화된 성분이 충분히 적거나 없다는 것을 나타낸다. 따라서, 상기 식 2를 만족하는 본 발명의 폴리아미드 수지는 성형가공성이 양호하고, 기계적 강도, 내열성, 색조 등의 물성 발란스가 우수할 수 있다.The relationship of Equation 2 indicates that the logarithmic viscosity (IV) is sufficiently low with respect to the number average molecular weight (Mn), and the component that is abnormally high molecular weight due to the uneven reaction progress or the crosslinking reaction of the copolymerization component is sufficiently low. Or not. Therefore, the polyamide resin of the present invention that satisfies Equation 2 may have good moldability and excellent balance of physical properties such as mechanical strength, heat resistance and color tone.
상기 폴리아미드 수지의 Mn/IV가 약 12,000 미만인 경우, 수평균분자량(Mn)에 대해 대수점도(IV)가 높고, 공중합 성분의 불균일한 반응 진행이나 가교화 반응 등에 의해 비정상적으로 고분자량화한 성분이 많은 것을 나타낸다. 따라서, 이러한 폴리아미드 수지는 생산성, 가공성이 저하되고 기계적 강도, 내열성, 색조 등의 물성 발란스가 저하될 우려가 있다.When the Mn / IV of the polyamide resin is less than about 12,000, the logarithmic viscosity (IV) is high with respect to the number average molecular weight (Mn), and the component is abnormally high molecular weight due to uneven reaction progress or crosslinking reaction of the copolymerization component. This shows a lot. Therefore, such a polyamide resin may lower productivity, workability, and physical property balance such as mechanical strength, heat resistance and color tone.
상기 폴리아미드 수지의 Mn/IV는 예를 들면 약 12,500 이상이다. Mn/IV의 상한치는 특별히 제한되지 않지만, 성형가공 시의 유동성을 크게 변동시키지 않는 관점에서 예를 들면 약 18,000 이하이다.The Mn / IV of the polyamide resin is, for example, about 12,500 or more. Although the upper limit of Mn / IV is not specifically limited, For example, it is about 18,000 or less from a viewpoint which does not change the fluidity | liquidity at the time of shaping | molding process significantly.
여기서, 상기 폴리아미드 수지의 수평균분자량(Mn)은 적정법에 의해 측정한 값이며, 보다 구체적으로는 후술하는 실시예에 기재된 방법에 의해 측정할 수 있다.Here, the number average molecular weight (Mn) of the said polyamide resin is the value measured by the titration method, More specifically, it can measure by the method as described in the Example mentioned later.
상기 IV 및 Mn/IV의 값은 본 발명의 특정 원료 조성 성분을 이용하고, 디아민과 디카르복시산의 투입 몰비(디아민/디카르복시산)를 약 0.95 내지 약 1.05, 예를 들면 약 0.97 내지 약 1.03로 조정하여, 본 발명에서 나타내는 저차 축합물 및 고상중합의 제조 조건 범위에서 제조하는 것에 의해 제어할 수 있다.The values of IV and Mn / IV are adjusted to about 0.95 to about 1.05, for example, about 0.97 to about 1.03, using the specific raw material composition of the present invention and adjusting the charged molar ratio (diamine / dicarboxylic acid) of diamine and dicarboxylic acid. It can control by manufacturing in the manufacturing conditions range of the low order condensate and solid-phase polymerization which are shown by this invention.
본 발명의 폴리아미드 수지의 융점은 예를 들면 약 270℃ 이상, 구체적으로 약 275 내지 약 320℃일 수 있다. 본 발명의 폴리아미드 수지의 유리전이온도는 예를 들면 약 100℃ 이상, 구체적으로 약 101 내지 약 120℃일 수 있다. 또한, 본 발명의 폴리아미드 수지의 굴곡탄성률은 예를 들면 약 4 GPa 이상, 구체적으로 약 4.2 내지 약 4.5 GPa일 수 있다. 상기 융점, 유리전이온도 및 굴곡탄성률은 구체적으로는 실시예에 기재된 방법에 의해 측정할 수 있다.The melting point of the polyamide resin of the present invention may be, for example, about 270 ° C. or more, specifically about 275 to about 320 ° C. The glass transition temperature of the polyamide resin of the present invention may be, for example, about 100 ° C or more, specifically about 101 to about 120 ° C. In addition, the flexural modulus of the polyamide resin of the present invention may be, for example, about 4 GPa or more, specifically about 4.2 to about 4.5 GPa. The melting point, glass transition temperature and flexural modulus can be specifically measured by the method described in Examples.
본 발명에 따른 폴리아미드 수지는 예를 들어, 상기 디카르복시산 성분과 상기 디아민 성분으로 형성되는 저차 축합물을 제조하는 공정, 상기 저차 축합물을 배출 및 냉각하는 공정, 및 냉각한 상기 저차 축합물을 고상중합하는 공정을 포함하는 제조방법에 의해 얻을 수 있다.The polyamide resin according to the present invention includes, for example, a process for preparing a lower condensate formed of the dicarboxylic acid component and the diamine component, a step of discharging and cooling the lower condensate, and cooling the lower condensate. It can obtain by the manufacturing method including the process of solid-phase polymerization.
구체예에서, 본 발명에 따른 폴리아미드 수지의 제조방법은 디카르복시산 성분으로 1,4-시클로헥산디카르복시산 약 5 내지 약 50 몰%, 및 1,4-시클로헥산디카르복시산 이외의 디카르복시산 약 50 내지 약 95 몰%를 함유하고, 디아민 성분으로 파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민 약 50 내지 약 100 몰%과 크실리렌디아민 이외의 디아민 약 0 내지 약 50 몰%를 함유하는 폴리아미드 수지의 제조방법으로서, 상기 디카르복시산 성분과 상기 디아민 성분의 중축합 반응을 반응온도가 약 200℃ 이상 약 230℃ 미만이고, 반응압력이 약 0.5 내지 약 3 MPa이며, 반응시간이 약 0.5 내지 약 4시간이며, 반응 종료 후 반응계 내의 수분량이 약 15 내지 약 35 중량%인 조건으로 실시하여 저차 축합물을 제조하는 공정, 불활성가스 분위기 하, 대기압 이하의 압력으로 상기 저차 축합물을 배출 및 냉각하는 공정, 및 냉각한 상기 저차 축합물을 고상중합하는 공정을 포함하고, 상기 냉각한 저차 축합물은 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도가 약 0.07 내지 약 0.40 dL/g인 것을 특징으로 한다.In an embodiment, the process for preparing the polyamide resin according to the present invention comprises about 5 to about 50 mol% of 1,4-cyclohexanedicarboxylic acid as the dicarboxylic acid component, and about 50 dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid. From about 50 to about 100 mol% of xylylenediamine having from about 10 to about 100 mol% of a paraxylenediamine component as a diamine component, and from about 0 to about 95 mol% of diamine other than xylylenediamine. A method for producing a polyamide resin containing from about 50 mol%, wherein the polycondensation reaction of the dicarboxylic acid component and the diamine component is carried out at a reaction temperature of about 200 ° C. to about 230 ° C., and a reaction pressure of about 0.5 to about 3 MPa, the reaction time is about 0.5 to about 4 hours, and after completion of the reaction, the water content in the reaction system is carried out under the condition of about 15 to about 35% by weight to prepare a lower condensate, under an inert gas atmosphere, Discharging and cooling the lower order condensate at a pressure below the pressure, and solidifying the cooled lower order condensate, wherein the cooled lower condensate is at a concentration of about 0.5 g / dL in concentrated sulfuric acid. The algebraic viscosity measured at a temperature of about 25 ° C. is about 0.07 to about 0.40 dL / g.
본 발명에 따른 제조방법은 제조 중에 겔이 발생하는 등 제조상의 문제가 거의 발생하지 않으며, 기계적 강도, 내열성, 색조 등의 물성 발란스가 우수한 폴리아미드 수지를 얻을 수 있다.In the production method according to the present invention, a production problem hardly occurs such as a gel is generated during production, and a polyamide resin having excellent physical balance such as mechanical strength, heat resistance and color tone can be obtained.
이하, 본 발명의 제조방법에 대해 공정별로 상세하게 설명하면, 다음과 같다.Hereinafter, the manufacturing method of the present invention will be described in detail for each step.
<저차 축합물을 제조하는 공정><Step of Preparing Lower Condensate>
본 공정에서는 디카르복시산 성분과 디아민 성분의 중축합 반응을 실시하여 폴리아미드 수지의 저차 축합물을 제조한다.In this step, the polycondensation reaction of the dicarboxylic acid component and the diamine component is carried out to produce a lower order condensate of the polyamide resin.
상기 저차 축합물은 상기 단량체 또는 염의 수용액 등을 예를 들어, 통상 이용되는 가압 중합조에 넣고, 수성용매 중에서 교반하며 중축합 반응하는 것에 의해 합성된다.The said lower order condensate is synthesize | combined by putting the aqueous solution of the said monomer or a salt, etc. into a pressurized polymerization tank normally used, for example, stirring in an aqueous solvent, and carrying out polycondensation reaction.
상기 수성용매는 물을 주성분으로 하는 용매이다. 물 이외에 이용되는 용매로는 중축합 반응성이나 용해도에 영향을 주지 않는 것이라면 특별히 제한되지 않으나, 예를 들면, 메탄올, 에탄올, 프로판올, 부탄올, 에틸렌글리콜 등의 알코올류를 사용할 수 있다.The said aqueous solvent is a solvent which has water as a main component. The solvent used in addition to water is not particularly limited as long as it does not affect polycondensation reactivity or solubility. For example, alcohols such as methanol, ethanol, propanol, butanol and ethylene glycol can be used.
중축합 반응을 개시할 때의 반응계 내 수분량은 반응 종료 시 반응계 내 수분량이 약 15 내지 약 35 중량%가 되는 양인 것이 바람직하다. 구체적으로는 중축합 반응을 개시할 때의 반응계 내 수분량은 예를 들면 약 17 내지 약 60 중량%이다. 상기 범위에서 중축합 반응을 개시할 때 거의 균일한 용액상이 되어 중축합 공정에서의 수분을 증류 및 제거하는데 많은 시간 및 에너지를 사용하지 않을 수 있고, 반응 시간의 연장에 의한 저차 축합물의 열열화를 저감시킬 수 있다.The amount of water in the reaction system at the start of the polycondensation reaction is preferably such that the amount of water in the reaction system is about 15 to about 35% by weight. Specifically, the amount of water in the reaction system at the start of the polycondensation reaction is, for example, about 17 to about 60% by weight. When starting the polycondensation reaction in the above range, it becomes a nearly uniform solution phase and may not use much time and energy to distill and remove water in the polycondensation process, and thermal degradation of the lower condensate by extension of the reaction time Can be reduced.
본 공정에서는 중축합 속도의 향상 및 중축합 반응 시의 열화 방지 등의 목적으로 인계 촉매를 이용할 수 있다. 상기 인계 촉매의 구체예로는 차아인산염, 인산염, 차아인산, 인산, 인산에스테르, 폴리메타인류, 폴리인산류, 포스핀옥사이드류, 포스포늄할로겐 화합물, 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다. 예를 들면 차아인산염, 인산염, 차아인산, 인산, 이들의 혼합물 등을 사용할 수 있다. 상기 차아인산염으로는 예를 들어 차아인산나트륨, 차아인산칼륨, 차아인산칼슘, 차아인산마그네슘, 차아인산알루미늄, 차아인산바나듐, 차아인산망간, 차아인산아연, 차아인산납, 차아인산니켈, 차아인산코발트, 차아인산암모늄 등이 바람직하고, 차아인산나트륨, 차아인산칼륨, 차아인산칼슘, 차아인산마그네슘이 보다 바람직하다. 상기 인산염으로는 예를 들어 인산나트륨, 인산칼륨, 인산이수소칼륨, 인산칼슘, 인산바나듐, 인산마그네슘, 인산망간, 인산납, 인산니켈, 인산코발트, 인산암모늄, 인산수소이암모늄 등이 바람직하다. 상기 인산에스테르로는 예를 들어 인산에틸옥타데실 등을 사용할 수 있다. 상기 폴리메타인산류로는 예를 들어 트리메타인산나트륨, 펜타메타인산나트륨, 헥사메타인산나트륨, 폴리메타인산 등을 사용할 수 있다. 상기 폴리인산류로는 예를 들어 테트라폴리인산나트륨 등을 사용할 수 있다. 또한, 상기 포스핀옥사이드류로는 예를 들어 헥사메틸포스포아미드 등을 사용할 수 있다. 상기 인계 촉매들은 수화물의 형태일 수도 있다.In this step, a phosphorus catalyst can be used for the purpose of improving the polycondensation rate and preventing deterioration during the polycondensation reaction. Specific examples of the phosphorus-based catalyst may include hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, phosphate ester, polymetaphosphates, polyphosphates, phosphine oxides, phosphonium halide compounds, mixtures thereof, and the like. It is not limited. For example, hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, mixtures thereof and the like can be used. Examples of the hypophosphite include sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, vanadium hypophosphite, manganese hypophosphite, zinc hypophosphite, lead hypophosphite, nickel hypophosphite, hypophosphite Cobalt, ammonium hypophosphite, etc. are preferable, and sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are more preferable. Examples of the phosphate salt include sodium phosphate, potassium phosphate, potassium dihydrogen phosphate, calcium phosphate, vanadium phosphate, magnesium phosphate, manganese phosphate, lead phosphate, nickel phosphate, cobalt phosphate, ammonium phosphate, and diammonium phosphate. As said phosphate ester, ethyl octadecyl phosphate etc. can be used, for example. Examples of the polymetaphosphates include sodium trimethaphosphate, sodium pentametaphosphate, sodium hexametaphosphate, polymetaphosphate, and the like. As said polyphosphate, sodium tetrapolyphosphate etc. can be used, for example. Moreover, hexamethyl phosphoamide etc. can be used as said phosphine oxides, for example. The phosphorus catalysts may be in the form of hydrates.
상기 인계 촉매의 첨가량은 단량체 약 100 중량부에 대하여, 약 0.0001 내지 약 5 중량부, 예를 들면 약 0.001 내지 약 1 중량부일 수 있다. 또한, 첨가 시기는 고상중합 완료까지라면 언제든 첨가시켜도 되지만, 원료 투입 시부터 저차 축합물의 중축합 완료까지의 사이인 것이 바람직하다. 또한, 여러 번으로 나누어 첨가해도 되며, 2종 이상의 다른 인계 촉매를 조합하여 첨가할 수도 있다.The addition amount of the phosphorus catalyst may be about 0.0001 to about 5 parts by weight, for example, about 0.001 to about 1 part by weight based on about 100 parts by weight of the monomer. In addition, the addition time may be added at any time until the solid phase polymerization is completed, but it is preferred to be between the time of starting the raw material and the completion of the polycondensation of the lower condensate. Moreover, you may add in several times and may add in combination of 2 or more types of other phosphorus catalysts.
또한, 본 공정은 상기 중축합 반응을 말단봉지제의 존재 하에 실시할 수 있다. 말단봉지제를 사용하면 저차 축합물 및 최종적으로 제조하는 폴리아미드 수지의 분자량 조절이 보다 용이해지며, 저차 축합물 및 최종적으로 제조하는 폴리아미드 수지의 용융안정성이 향상될 수 있다. 상기 말단봉지제로는 저차 축합물에서의 말단아미노기 또는 말단카르복실기와 반응성을 가지는 단관능성의 화합물이면 특별히 제한은 없다. 예를 들면, 모노카르복시산, 모노아민, 무수프탈산 등의 산무수물, 모노이소시아네이트, 모노산할로겐화물, 모노에스테르류, 모노알코올류 등을 예시할 수 있으나, 이에 제한되지 않는다. 상기 말단봉지제는 단독 또는 2종 이상 혼합하여 사용할 수도 있다. 예를 들면 반응성 및 봉지말단 안정성 등을 고려하여, 모노카르복시산 또는 모노아민을 사용할 수 있으며, 구체적으로 취급 용이성이 우수한 모노카르복시산을 사용할 수 있다.In addition, this process can perform the said polycondensation reaction in presence of terminal blocker. The use of the terminal sealing agent makes it easier to control the molecular weight of the lower condensate and the finally produced polyamide resin, and improve the melt stability of the lower condensate and the finally produced polyamide resin. The terminal blocker is not particularly limited as long as it is a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group in the lower condensate. For example, acid anhydrides such as monocarboxylic acid, monoamine, phthalic anhydride, monoisocyanate, monoacid halides, monoesters, monoalcohols, and the like can be exemplified, but are not limited thereto. The terminal blocker may be used alone or in combination of two or more thereof. For example, monocarboxylic acid or monoamine may be used in consideration of reactivity and the end stability of the encapsulation, and specifically, monocarboxylic acid having excellent handleability may be used.
상기 모노카르복시산으로는 아미노기와의 반응성을 가지는 모노카르복시산이면 특별히 제한은 없고, 예를 들어, 아세트산, 프로피온산, 부티르산, 발레르산, 카프로산, 카프릴산, 라우르산, 트리데실산, 미리스트산, 팔미트산, 스테아르산, 피바린산, 이소부틸산 등의 지방족 모노카르복시산; 시클로헥산카르복시산 등의 지환식 모노카르복시산; 벤조산, 톨루인산, α-나프탈렌카르복시산, β-나프탈렌카르복시산, 메틸나프탈렌카르복시산, 페닐아세트산 등의 방향족 모노카르복시산; 이들의 혼합물 등을 사용할 수 있다. 예를 들면 반응성, 봉지말단 안정성, 가격 등의 점에서 아세트산, 프로피온산, 부티르산, 발레르산, 카프로산, 카프릴산, 라우르산, 트리데실산, 미리스트산, 팔미트산, 스테아르산, 벤조산 등을 사용할 수 있다.The monocarboxylic acid is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid and myristic acid. Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, pivalic acid and isobutyl acid; Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalene carboxylic acid, β-naphthalene carboxylic acid, methylnaphthalene carboxylic acid, and phenylacetic acid; Mixtures thereof and the like can be used. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, benzoic acid, etc. Etc. can be used.
상기 모노아민으로는 카르복실기와의 반응성을 가지는 모노아민이면 특별히 제한은 없고, 예를 들어, 메틸아민, 에틸아민, 프로필아민, 부틸아민, 헥실아민, 옥틸아민, 데실아민, 스테아릴아민, 디메틸아민, 디에틸아민, 디프로필아민, 디부틸아민 등의 지방족 모노아민; 시클로헥실아민, 디시클로헥실아민 등의 지환식 모노아민; 아닐린, 톨루이딘, 디페닐아민, 나프틸아민 등의 방향족 모노아민; 이들의 혼합물 등을 사용할 수 있다. 예를 들면 반응성, 비점, 봉지말단 안정성 및 가격 등의 점에서 부틸아민, 헥실아민, 옥틸아민, 데실아민, 스테아릴아민, 시클로헥실아민, 아닐린 등을 사용할 수 있다.The monoamine is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine Aliphatic monoamines such as diethylamine, dipropylamine and dibutylamine; Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; Mixtures thereof and the like can be used. For example, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, aniline, etc. may be used in view of reactivity, boiling point, bag end stability and price.
저차 축합물 제조 시, 말단봉지제의 사용량은 사용하는 말단봉지제의 반응성, 비점, 반응장치, 반응조건 등에 따라 다를 수 있지만, 예를 들면, 디카르복시산 또는 디아민 약 100 몰부에 대하여, 약 0.1 내지 약 15 몰부일 수 있다.In the preparation of the lower condensate, the amount of the terminal encapsulating agent may vary depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the terminal encapsulating agent, but, for example, about 0.1 to about 100 moles of dicarboxylic acid or diamine About 15 mole parts.
본 발명의 저차 축합물의 합성은 반응물의 교반 하에, 승온 및 승압하는 것에 의해 행해질 수 있다. 중합온도(반응온도)는 원료 투입 후 조절할 수 있고, 중합압력(반응압력)은 중합의 진행에 맞춰 조절될 수 있다.Synthesis of the lower condensate of the present invention can be done by raising and raising the temperature under stirring of the reactants. The polymerization temperature (reaction temperature) can be adjusted after the addition of the raw material, the polymerization pressure (reaction pressure) can be adjusted in accordance with the progress of the polymerization.
본 공정에서의 반응온도는 약 200℃ 이상 약 230℃ 미만, 예를 들면 약 200 내지 약 225℃이다. 상기 범위에서 겔화 등의 부반응이 잘 일어나지 않아 목적으로 하는 저차 축합물을 효율적으로 얻을 수 있다.The reaction temperature in this process is about 200 ° C. or more and less than about 230 ° C., for example, about 200 ° C. to about 225 ° C. In the above range, side reactions such as gelation do not occur well, so that the target lower-order condensate can be efficiently obtained.
본 공정에서 반응압력은 예를 들면 약 0.5 내지 약 3.0 MPa, 구체적으로 약 1.0 내지 약 2.5 MPa이다. 상기 범위에서 반응계 내의 온도나 반응계 내의 수분량의 제어가 용이하고, 저차 축합물의 배출이 용이할 수 있다. 또한, 내압성이 낮은 반응장치를 사용할 수 있기 때문에 경제적으로 유리하고, 반응계 내의 수분량을 낮춤으로써 저차 축합물의 중합도를 높일 수 있다.The reaction pressure in this process is, for example, about 0.5 to about 3.0 MPa, specifically about 1.0 to about 2.5 MPa. Within this range, it is easy to control the temperature in the reaction system or the amount of water in the reaction system, and the discharge of the lower condensate may be easy. In addition, since a reactor having a low pressure resistance can be used, it is economically advantageous, and the degree of polymerization of the lower condensate can be increased by lowering the amount of water in the reaction system.
또한, 본 공정에서 반응시간은 예를 들면, 약 0.5 내지 약 4시간, 구체적으로 약 1 내지 약 3시간일 수 있다. 본 명세서에서, 상기 반응시간은 본 발명의 반응온도에 도달한 후, 배출 조작 개시까지의 소요시간을 나타낸다. 상기 범위에서 충분한 반응률에 도달하여 미반응물이 거의 잔존하지 않아 균일한 성상의 저차 축합물을 얻을 수 있다. 또한, 과도한 열이력을 주는 일없이 고품질의 저차 축합물을 얻을 수 있다.In addition, the reaction time in the present process may be, for example, about 0.5 to about 4 hours, specifically about 1 to about 3 hours. In the present specification, the reaction time represents the time required until the discharge operation starts after reaching the reaction temperature of the present invention. Sufficient reaction rate can be reached within this range, so that unreacted material hardly remains, whereby a lower condensate of uniform properties can be obtained. In addition, high-quality low-order condensates can be obtained without giving excessive heat history.
본 공정에서, 저차 축합물의 반응 종료 시 반응계 내의 수분량은 약 15 내지 약 35 중량%, 예를 들면 약 20 내지 약 35 중량%일 수 있다. 본 명세서에서, 반응 종료 시는 소정의 중합도에 도달한 저차 축합물을 배출 조작 개시하는 시점을 의미하며, 수분량은 반응 중에 발생하는 축합수도 포함시킨 것이다. 상기 범위로 수분량을 조절하기 위해서는 발생할 축합수량을 고려하여 투입 수분량을 조절하거나, 콘덴서, 압력 조정 밸브를 구비한 장치로 반응압력 조정 시에 소정량의 물을 증류 및 제거하여 조절할 수 있다. 상기 범위에서 반응계 내에서 저차 축합물의 석출이나 고화가 거의 일어나지 않고, 저차 축합물의 배출이 용이할 수 있다. 또한, 충분한 중합도의 저차 축합물을 얻기 쉽고, 배출 시에 증발 분리시키는 수분량이 적기 때문에 배출속도를 높일 수 있어 제조 효율을 향상시킬 수 있다.In this process, the amount of water in the reaction system at the end of the reaction of the lower condensate may be about 15 to about 35 weight percent, for example about 20 to about 35 weight percent. In this specification, at the time of completion | finish of reaction, it means the time of starting discharge operation of the low order condensate which reached | attained the predetermined | prescribed degree of polymerization, and the moisture content also includes the condensation water which arises during reaction. In order to control the amount of water in the above range, the amount of condensed water may be adjusted in consideration of the amount of condensed water to be generated, or a device having a condenser and a pressure control valve may be adjusted by distilling and removing a predetermined amount of water when adjusting the reaction pressure. In the above range, precipitation or solidification of the lower condensate may hardly occur in the reaction system, and the lower condensate may be easily discharged. In addition, it is easy to obtain a low degree of condensate having a sufficient degree of polymerization, and the amount of water to be evaporated and separated at the time of discharging is small, so that the discharging rate can be increased and the production efficiency can be improved.
상기 공정은 필요에 따라, 저차 축합물 중합 전에 염조 공정 및/또는 농축 공정을 추가할 수도 있다. 상기 염조 공정은 디카르복시산 성분과 디아민 성분으로 염을 생성하는 공정이며, 염의 중화점의 pH±약 0.5의 범위로, 예를 들면 염의 중화점의 pH±약 0.3의 범위로 조절할 수 있다. 상기 농축 공정은 원료투입 농도의 값을 약 ＋2 내지 약 ＋90 중량%로 하는 것이 바람직하고, 약 ＋5 내지 약 ＋80 중량%의 농도까지 농축하는 것이 더욱 바람직하다. 상기 농축 공정의 온도는 약 90 내지 약 220℃의 범위가 바람직하고, 약 100 내지 약 210℃가 더욱 바람직하며, 약 130 내지 약 200℃가 특히 바람직하다. 상기 농축 공정의 압력은 예를 들면 약 0.1 내지 약 2.0 MPa이다.통상적으로, 농축 시 압력은 중합 시 압력 이하로 컨트롤된다. 또한, 농축 촉진을 위해 질소기류 등에 의해 강제 배출조작을 할 수도 있다. 상기 농축공정은 중합시간의 단축에 효과적일 수 있다.The process may optionally add a salt bath process and / or a concentration process before the lower condensate polymerization. The salting step is a step of generating a salt with a dicarboxylic acid component and a diamine component, and may be adjusted to a pH of about ± 0.5 at the neutralization point of the salt, for example, to a pH of about ± 0.3 at the neutralization point of the salt. In the concentration step, the concentration of the raw material input concentration is preferably about +2 to about + 90% by weight, more preferably to a concentration of about +5 to about + 80% by weight. The temperature of the concentration process is preferably in the range of about 90 to about 220 ° C, more preferably about 100 to about 210 ° C, particularly preferably about 130 to about 200 ° C. The pressure of the concentration process is, for example, about 0.1 to about 2.0 MPa. Typically, the pressure at concentration is controlled below the pressure at the time of polymerization. In addition, forcibly discharging operation may be performed by nitrogen stream or the like to promote concentration. The concentration process may be effective for shortening the polymerization time.
본 공정에서는 반응용기에서 꺼낸 후(냉각 후)의 저차 축합물을 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도(IV)가 약 0.07 내지 약 0.40 dL/g, 예를 들면 약 0.10 내지 약 0.25 dL/g가 되도록 반응을 실시한다. 상기 범위에서 저융점물의 존재로 인한 고상중합 시의 수지 분체간 융착이나 장치 내 부착을 억제할 수 있으며, 저차 축합물 제조 시 반응계 내에서의 석출, 고화 등을 억제할 수 있다.In this process, the logarithmic viscosity (IV) measured at a temperature of about 25 ° C. at a concentration of about 0.5 g / dL in concentrated sulfuric acid after removal from the reaction vessel (after cooling) is about 0.07 to about 0.40 dL / g, For example, the reaction is carried out to be about 0.10 to about 0.25 dL / g. In the above range, fusion between resin powders and adhesion in the apparatus during solid phase polymerization due to the presence of low melting point substances can be suppressed, and precipitation, solidification, etc. in the reaction system can be suppressed during the production of the lower condensate.
본 공정에서 저차 축합물을 얻기 위한 중축합 반응은 배치식 또는 연속식으로 실시할 수 있다. 또한, 반응 용기에 대한 저차 축합물의 부착 방지나 중축합 반응의 균일한 진행 등을 위하여, 저차 축합물을 생성시키기 위한 중축합 반응을 교반 하에 실시하는 것이 바람직하다.In this step, the polycondensation reaction for obtaining the lower condensate can be carried out batchwise or continuously. In addition, in order to prevent adhesion of the lower condensate to the reaction vessel, to uniformly proceed the polycondensation reaction, etc., it is preferable to carry out the polycondensation reaction for producing the lower condensate under stirring.
<저차 축합물을 배출 및 냉각하는 공정><Process to discharge and cool lower condensate>
본 공정에서는 제조된 저차 중합물을 반응 용기에서 배출 및 냉각한다. 상기 배출 및 냉각 공정은 상기 공정에서 제조된 저차 축합물을 반응 용기에서 꺼내는 것이다. 상기 배출 및 냉각 공정은 반응계의 온도가 상기한 약 200℃ 이상 약 230℃ 미만의 범위 내에 있고, 반응 종료 시 반응계에의 수분량이 상기 약 15 내지 약 35 중량%의 범위 내에 있을 때, 저차 축합물을 반응 용기로부터 불활성 가스 분위기 하, 대기압 이하의 압력 조건에서 실시하는 것이 바람직하다. 본 발명의 배출 및 냉각 공정은 소정 압력으로 조절한 취득용 압력용기를 사용할 필요가 없고, 반응 용기 내에 수증기를 별도로 공급하면서 저차 축합물을 반응 용기로부터 꺼내는 작업도 불필요하다. 또한, 열열화가 적고 대수점도가 충분히 높으며, 부피비중이 높은 비발포 분립체형상(분말형 또는 과립형)인 저차 축합물을 간단하고 효율적으로 얻을 수 있다.In this process, the prepared lower polymer is discharged and cooled in the reaction vessel. The evacuation and cooling process is to remove the lower condensate produced in the process from the reaction vessel. The evacuation and cooling process is a lower order condensate when the temperature of the reaction system is in the range of about 200 ° C. or more and less than about 230 ° C., and the amount of water in the reaction system at the end of the reaction is in the range of about 15 to about 35% by weight. It is preferable to carry out from the reaction vessel under inert gas atmosphere under pressure conditions of atmospheric pressure or less. In the discharge and cooling process of the present invention, there is no need to use an acquisition pressure vessel adjusted to a predetermined pressure, and it is also unnecessary to take out the lower condensate from the reaction vessel while supplying steam separately into the reaction vessel. In addition, it is possible to obtain a low-order condensate that is low in thermal degradation, sufficiently high in logarithmic viscosity, and has a high volume specific gravity.
여기서, 상기 불활성가스 분위기는 저차 축합물의 산화 열화를 방지하기 위하여, 산소 농도가 약 1 체적% 이하일 수 있다.Here, the inert gas atmosphere may have an oxygen concentration of about 1% by volume or less in order to prevent oxidative degradation of the lower condensate.
반응 용기로부터 상기 저차 축합물의 배출 속도는 반응 용기의 크기, 반응용기 내 내용물의 양, 온도, 취득구의 크기, 취득 노즐부의 길이 등에 따라 적절히 조절할 수 있다. 예를 들면, 배출구 단면적당 배출 속도가 약 2,000 내지 약 20,000 kg/s/㎡가 되도록 하여 배출할 수 있다. 상기 범위에서 후술하는 고상중합 공정 시, 붕괴, 응집, 반응기벽에 대한 융착 등을 줄이거나 방지할 수 있고, 취급성이 우수하며, 중합장치 등에 많이 충전하는 것이 가능하여 고상중합 공정에서 이용되는 장치의 용적효율을 향상시킬 수 있다.The discharge rate of the lower condensate from the reaction vessel can be appropriately adjusted depending on the size of the reaction vessel, the amount of the contents in the reaction vessel, the temperature, the size of the acquisition port, the length of the acquisition nozzle, and the like. For example, the discharge may be performed such that the discharge rate per outlet cross-sectional area is about 2,000 to about 20,000 kg / s / m 2. In the solid phase polymerization process to be described later in the above range, it is possible to reduce or prevent collapse, agglomeration, fusion to the reactor wall, etc., excellent handling properties, and can be filled in a polymerization apparatus, etc., the apparatus used in the solid phase polymerization process Can improve the volumetric efficiency.
상기 반응 용기에서 배출되는 저차 축합물은 예를 들면, 취득 시 물의 증발 잠열에 의해 그 온도가 순간적으로 약 100℃ 이하로 저하되기 때문에 열열화 및 산소에 의한 열화는 거의 발생하지 않는다.The lower order condensate discharged from the reaction vessel, for example, hardly deteriorates due to thermal degradation and oxygen because its temperature is momentarily lowered to about 100 ° C. or lower due to latent heat of evaporation of water at the time of acquisition.
또한, 배출되는 저차 축합물은 저차 축합물이 가지는 현열에 의해 동반되는 수분의 대부분을 증발시키기 때문에, 본 공정에서 저차 축합물의 냉각과 건조처리는 동시에 이루어질 수 있다. 질소 등의 불활성 가스 분위기 및/또는 대기압보다 낮은 압력 하에서 배출 처리 시, 건조 및 냉각의 효율을 높일 수 있어 바람직하다. 또한, 배출 용기로서 사이클론형 고체-기체 분리장치를 설치함으로써 배출 시 가루의 계외 비산을 억제할 수 있고, 높은 가스선속 하에서 배출처리가 가능하기 때문에 건조 및 냉각 효율을 높이는 것이 가능하다.In addition, since the lower condensate discharged evaporates most of the moisture accompanied by the sensible heat of the lower condensate, cooling and drying treatment of the lower condensate can be performed simultaneously. In the discharge treatment under an inert gas atmosphere such as nitrogen and / or a pressure lower than atmospheric pressure, the drying and cooling efficiency can be improved, which is preferable. In addition, by installing a cyclone-type solid-gas separator as the discharge vessel, it is possible to suppress out-of-system scattering of the powder during discharge and to increase the drying and cooling efficiency since the discharge treatment can be performed under a high gas flux.
이와 같이 얻어지는 저차 축합물은 상기와 같이 대수점도가 충분히 높고 미반응물의 잔존량도 낮기 때문에 저차 축합물 입자간의 융착이나 응집 현상 없이 높은 온도에서 고상중합을 실시할 수 있으며, 부반응에 의한 열화가 적다.The low-order condensate thus obtained has a sufficiently high algebraic viscosity and a low residual amount of unreacted material, so that solid phase polymerization can be carried out at a high temperature without fusion or agglomeration between the low-order condensate particles and less deterioration due to side reactions. .
또한, 본 공정에서는 필요에 따라 입경을 균일하게 하기 위한 컴팩팅 처리나 조립 처리를 추가로 실시할 수 있다.Moreover, in this process, the compacting process and the granulation process for making a particle size uniform can be further performed as needed.
<고상중합><Solid state polymerization>
본 공정에서는 상기 배출 및 냉각된 저차 축합물을 고상중합하여, 폴리아미드 수지를 제조한다. 상기 고상중합 반응은 반응 용기로부터 취득한 그대로의 저차 축합물을 사용하여 연속으로 실시할 수 있고, 반응 용기에서 꺼낸 저차 축합물을 건조시킨 뒤에 실시할 수 있다. 또한, 반응 용기에서 꺼낸 저차 축합물을 일단 저장한 뒤에 실시할 수 있으며, 반응 용기에서 꺼낸 저차 축합물에 상기 컴팩팅 처리나 조립 처리를 한 뒤에 실시할 수도 있다. 본 발명의 제조방법에 따라 제조된 저차 축합물을 사용하여, 본 발명에 따른 고상중합(고중합도화)을 실시하면 열열화가 보다 적은 폴리아미드 수지를 얻을 수 있다.In this step, the discharged and cooled low-order condensate is subjected to solid phase polymerization to produce a polyamide resin. The solid phase polymerization reaction can be carried out continuously using the low order condensate obtained from the reaction vessel, and can be carried out after drying the low order condensate taken out of the reaction vessel. It is also possible to carry out after storing the lower condensate taken out of the reaction vessel once, or may be carried out after the compaction or granulation treatment is performed on the lower condensate taken out of the reaction vessel. By carrying out the solid phase polymerization (high polymerization degree) according to the present invention using the lower order condensate produced according to the production method of the present invention, a polyamide resin having less thermal degradation can be obtained.
저차 축합물을 고상중합할 때의 중합 방법 및 조건은 특별히 제한되지 않으며, 저차 축합물의 융착, 응집, 열화 등을 일으키는 일 없이 고체상태를 유지하면서 고중합도화를 실시할 수 있는 방법 및 조건이면 된다.The polymerization method and conditions in the solid phase polymerization of the lower order condensate are not particularly limited, and any method and conditions capable of performing high polymerization while maintaining the solid state without causing fusion, agglomeration, or deterioration of the lower order condensate may be used. .
예를 들면, 저차 축합물 및 생성되는 폴리아미드 수지의 산화 열화를 방지하기 위해 헬륨가스, 아르곤가스, 질소가스, 탄산가스 등의 불활성 가스 분위기 중 또는 감압 하에서 고상중합할 수 있다.For example, in order to prevent oxidative deterioration of the lower order condensate and the resulting polyamide resin, solid phase polymerization may be performed in an inert gas atmosphere such as helium gas, argon gas, nitrogen gas, carbon dioxide gas or under reduced pressure.
고상중합에서 반응 온도는 특별히 제한되지 않지만, 최고 반응 온도가 약 230℃ 및 상기 저차 축합물의 융점보다 약 20℃ 낮은 온도 중, 낮은 쪽 온도 이하인 것이 바람직하다. 즉, 저차 축합물의 융점이 약 250℃ 이하인 경우, 고상중합의 최고 반응온도는 상기 저차 축합물의 융점보다 약 20℃ 낮은 온도 이하인 것이 바람직하다. 저차 축합물의 융점이 약 250℃를 넘는 경우, 고상중합의 최고 반응온도는 약 230℃ 이하인 것이 바람직하다. 본 발명은 이와 같이 종래에 비해 낮은 온도, 즉, 종래에 비해 온화한 조건으로 고상중합이 가능하다. 이에 따라, 상기 식 1 및 식 2의 관계를 만족하는 폴리아미드 수지가 보다 효율적으로 얻어질 수 있다.In solid phase polymerization, the reaction temperature is not particularly limited, but it is preferable that the highest reaction temperature is lower than or equal to the lower of the temperature of about 230 ° C and about 20 ° C lower than the melting point of the lower condensate. That is, when the melting point of the lower condensate is about 250 ° C. or less, the highest reaction temperature of the solid phase polymerization is preferably about 20 ° C. or less lower than the melting point of the lower condensate. When the melting point of the lower condensate exceeds about 250 ° C., the maximum reaction temperature of the solid phase polymerization is preferably about 230 ° C. or less. In the present invention, the solid phase polymerization is possible at a lower temperature than that of the prior art, that is, a milder condition than the conventional art. Accordingly, a polyamide resin that satisfies the relationship of Formulas 1 and 2 can be obtained more efficiently.
또한, 상기 최고 반응온도에 도달하는 시점은 고상중합 개시부터 종료까지 어떤 시점이든 가능하다. 구체적으로 상기 최고 반응온도는 약 225℃ 및 상기 저차 축합물의 융점보다 약 30℃ 낮은 온도 중, 낮은 쪽 온도 이하이다.In addition, the time point at which the highest reaction temperature is reached may be any time from the start of solid phase polymerization to the end. Specifically, the highest reaction temperature is below the lower temperature of about 225 ° C and about 30 ° C lower than the melting point of the lower condensate.
본 공정에서 이용되는 고상중합의 장치는 특별한 제한이 없으며, 공지된 모든 장치를 사용할 수 있다. 고상중합 장치의 구체예로는 1축 디스크식, 니더, 2축 패들식, 종형 탑식 장치, 종형 탑식 기기, 회전드럼식 또는 더블콘형 고상중합 장치, 건조기기 등을 예시할 수 있다.The apparatus for solid state polymerization used in this process is not particularly limited, and any known apparatus can be used. Specific examples of the solid phase polymerization apparatus may include a uniaxial disk type, a kneader, a biaxial paddle type, a vertical column type device, a vertical column type device, a rotary drum type or a double cone type solid phase polymerization device, a dryer, and the like.
상기 고상중합의 반응시간은 특별히 제한되지 않지만, 예를 들면, 약 1 내지 약 20시간일 수 있다. 상기 고상중합 반응 중에 저차 축합물을 기계적으로 교반하거나 기체류에 의해 교반할 수도 있다.The reaction time of the solid phase polymerization is not particularly limited, but may be, for example, about 1 to about 20 hours. During the solid phase polymerization reaction, the lower condensate may be mechanically stirred or stirred by gas flow.
본 발명에서는 저차 축합물을 제조하는 공정, 고상중합하는 공정 또는 고상중합 후의 임의의 단계에서, 필요에 따라, 유리섬유, 탄소섬유 등의 각종 섬유재료, 무기분말상 필러, 유기분말상 필러, 착색제, 자외선흡수제, 광안정제, 산화방지제, 대전방지제, 난연제, 결정화촉진제, 가소제, 윤활제 등의 첨가제, 다른 폴리머 등을 첨가할 수도 있다.In the present invention, various fiber materials such as glass fibers and carbon fibers, inorganic powder fillers, organic powder fillers, colorants, ultraviolet rays and, if necessary, at any stage after the step of preparing the lower condensate, the solid phase polymerization process or the solid phase polymerization. Additives such as absorbents, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, plasticizers, lubricants, and other polymers may be added.
상기한 바와 같이, 본 발명의 제조방법은 겔화 등 제조상의 문제가 발생되지 않으며, 기계적 강도, 내열성, 색조 등의 물성 발란스가 우수한 폴리아미드 수지를 얻을 수 있다.As described above, the production method of the present invention does not cause production problems such as gelation, and a polyamide resin having excellent physical balance such as mechanical strength, heat resistance and color tone can be obtained.
또한, 본 발명의 제조방법에 의해 얻어지는 폴리아미드 수지는 기계적 강도, 내열성 및 색조 외에도 저흡수성, 내약품성 등의 물성 발란스가 우수하다. 따라서, 본 발명의 폴리아미드 수지는 이러한 특성들을 나타낼 수 있도록 수지 단독, 또는 필요에 따라 상기 각종 첨가제나 다른 폴리머와의 조성물의 형태로 통상적인 각종 성형법이나 방사법, 예를 들어 사출성형, 블로우성형, 압출성형, 압축성형, 연신, 진공성형 등의 성형법이나 용융방사법 등을 통해 각종 성형품이나 섬유 등으로 성형할 수 있다. 이와 같이 얻어지는 성형품이나 섬유 등은 엔지니어링 플라스틱으로서의 용도를 비롯하여 전자·전기기기 부품, 자동차 부품, 사무기기 부품 등의 산업자재나 공업재료, 가정용품 등의 각종 용도에 효과적으로 사용할 수 있다.In addition, the polyamide resin obtained by the production method of the present invention is excellent in the balance of physical properties such as low water absorption, chemical resistance in addition to mechanical strength, heat resistance and color tone. Accordingly, the polyamide resin of the present invention can exhibit such properties by various conventional molding or spinning methods such as injection molding, blow molding, It can be molded into various molded articles, fibers, etc. through molding methods such as extrusion molding, compression molding, stretching, vacuum molding, and melt spinning. The molded article and the fiber obtained in this way can be effectively used for various uses such as industrial materials such as electronic / electrical device parts, automobile parts, office equipment parts, industrial materials, household goods, etc. as well as the use as engineering plastics.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로, 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
물성 평가 방법Property evaluation method
대수점도(IV), 융점, 유리전이온도, 결정화 온도 및 색상의 평가, 시험편의 제작 및 물성평가는 하기 방법에 의해 실시하였다.Logarithmic viscosity (IV), melting point, glass transition temperature, crystallization temperature and color evaluation, test piece preparation and physical property evaluation were performed by the following method.
(1) 대수점도(IV)(1) Algebraic viscosity (IV)
96% 진한 황산 중에 시료를 0.5 g/dL의 농도로 용해시켜 시료용액을 조제하였다. 96% 진한 황산 및 시료용액을 25℃의 온도에서 우베로데 점도계를 이용하여 낙하 초 수를 측정하고 이하의 식 3에 의해 산출하였다.A sample solution was prepared by dissolving the sample at a concentration of 0.5 g / dL in 96% concentrated sulfuric acid. The 96% concentrated sulfuric acid and the sample solution were measured using the Uberode viscometer at a temperature of 25 ° C., and the number of seconds dropped was calculated by the following Equation 3.
[식 3][Equation 3]
ηinh(대수점도) = In(ηrel)/cη inh (algebra viscosity) = In (η rel ) / c
상기 식 3에서, ηrel는 t1/t0(여기서, t1: 시료의 낙하 초 수, t0: Blank의 낙하 초 수)이고, c은 용액속도(g/dL)이다.In Equation 3, η rel is t1 / t0 (where t1 is the number of falling seconds of the sample and t0 is the number of falling seconds of the blank), and c is the solution velocity (g / dL).
(2) 수평균분자량(Mn)(2) Number average molecular weight (Mn)
얻어진 폴리아미드 수지의 아미노기말단 농도[NH2] 및 카르복실기말단 농도[COOH]를 아래에 나타내는 방법으로 측정하고 이하의 식 4에 의해 산출하였다.The amino terminal terminal concentration [NH 2 ] and carboxyl terminal terminal concentration [COOH] of the obtained polyamide resin were measured by the method shown below, and it calculated by the following formula | equation 4.
[식 4][Equation 4]
Mn=2/([NH2]+[COOH])Mn = 2 / ([NH 2 ] + [COOH])
각 말단기 농도는 히라누마산교 주식회사에서 제조한 자동적정장치 COM-1700을 이용하여 하기 조건으로 조정한 폴리아미드 수지 샘플용액의 적정에 의해 구하였다.Each end group concentration was determined by titration of a polyamide resin sample solution adjusted to the following conditions using an automatic titrator COM-1700 manufactured by Hiranuma Sangyo Co., Ltd.
카르복실기말단 농도[COOH] 분석:Carboxyl Terminal Concentration [COOH] Analysis:
시료 0.5 g과 오르토크레졸 20 mL를 질소 분위기 하에서 교반하면서 170℃에서, 30분 동안 가열하여 시료를 용해시켰다. 용해 후, 냉각하고 15 mL의 벤질알코올과 75 ㎕의 포름알데히드를 첨가하여 5분간 교반하였다. 교반 후 0.1N KOH 메탄올 용액으로 중화 적정하여 농도를 구하였다.0.5 g of the sample and 20 mL of orthocresol were heated at 170 ° C. for 30 minutes with stirring under a nitrogen atmosphere to dissolve the sample. After dissolution, the mixture was cooled, and 15 mL of benzyl alcohol and 75 μl of formaldehyde were added and stirred for 5 minutes. After stirring, neutralization titration was performed with 0.1 N KOH methanol solution to determine the concentration.
아미노기말단 농도[NH2] 분석: Amino terminal concentration [NH 2 ] analysis:
시료 0.5 g과 헥사플루오로이소프로판올 8 mL를 실온(25℃)에서 교반하면서 용해시켰다. 완전하게 용해되면 페놀/에탄올(80 체적%/20 체적%) 30 mL를 첨가하여 다시 5분간 교반하였다. 교반 후 1N HCl 수용액으로 중화 적정하여 농도를 구하였다.0.5 g of the sample and 8 mL of hexafluoroisopropanol were dissolved while stirring at room temperature (25 ° C). Upon complete dissolution, 30 mL of phenol / ethanol (80% by volume / 20% by volume) was added and stirred for another 5 minutes. After stirring, the mixture was neutralized and titrated with 1N HCl aqueous solution to determine the concentration.
(3) 폴리아미드 수지의 조성 분석(3) Analysis of composition of polyamide resin
닛폰덴시 주식회사에서 제조한 ECX400P형 핵자기공명장치(측정핵: 1H, 400MHz, 측정모드: 싱글펄스, 펄스폭: 45°, 적산횟수: 512회, 측정온도: 50℃, 화학시프트기준: HFIP 4.4 ppm)를 이용하고, 폴리아미드 수지 시료 약 20 mg을 중수소헥사플루오로이소프로판올(HFIP)에 용해하여 1H-NMR을 측정하였다.Reference 50 ℃, chemical shifts: Nippon a ECX400P type nuclear magnetic resonance apparatus manufactured by Den when Ltd. (Measurement nucleus: 1 H, 400MHz, Measurement mode: single pulse, pulse width: 45 °, the accumulated number of times: 512 times Measuring temperature: HFIP 4.4 ppm) was used, and about 20 mg of polyamide resin sample was dissolved in deuterium hexafluoroisopropanol (HFIP) to measure 1 H-NMR.
본 실시예에서는 하기 표 1에 나타내는 각 성분에 귀속되는 시그널 피크의 적분값을 각 조성유닛 내의 수소원자의 수로 환산하여 폴리아미드 중의 각 조성비를 구하였다.In this example, the integral value of the signal peaks attributed to the components shown in Table 1 below was converted into the number of hydrogen atoms in each composition unit to determine the respective composition ratios in the polyamide.
표 1
* 크실리렌디아민 성분: 화학시프트치 7.1∼7.5 ppm(벤젠고리 상의 수소수 4), 파라체, 메타체 비율은 화학시프트치 7.2 ppm의 메타체 유래 피크를 기준으로 하여 산출
* 1,4-시클로헥산디카르복시산: 시스체 화학시프트치 1.8∼1.9 ppm(시클로헥산환 2급탄소 상의 수소수 8), 트랜스체 화학시프트치 1.5, 2.0 ppm(시클로헥산환 2급탄소 상의 수소수 8)
* 아디프산: 화학시프트치 1.7 ppm(카르보닐탄산과 결합되지 않은 메틸렌기 상의 수소수 4)
Table 1
* Xylylenediamine component: Chemical shift value of 7.1-7.5 ppm (4 hydrogens in a benzene ring), para-body, and meta-body ratio are computed based on meta-body peak of 7.2 ppm of chemical shift value.
* 1,4-cyclohexanedicarboxylic acid: cis-chemistry shift value 1.8-1.9 ppm (number of hydrogen on cyclohexane ring secondary carbon 8), trans-chemistry shift value 1.5, 2.0 ppm (number of cyclohexane ring secondary carbon phase Prime 8)
Adipic acid: 1.7 ppm of chemical shift (4 hydrogens on methylene group not bonded to carbonylcarbonate)
(4) 융점, 유리전이온도, 결정화 온도(4) melting point, glass transition temperature, crystallization temperature
세이코인스트루먼츠 주식회사에서 제조한 DSC를 이용하여 비결정화 상태의 샘플을 10 ml/min의 유속으로 질소 분위기 하, 승온속도 10 ℃/min로 30℃에서 폴리머 융해 피크보다 20℃ 높은 온도까지 승온시킨 후, 5분간 유지하고, 강온속도 10 ℃/min로 100℃까지 측정하여 유리전이온도를 측정, 다시 승온 시의 융해에 의한 흡열피크 온도를 융점, 강온 시의 결정화에 의한 발열피크 온도를 결정화 온도로 하여 각각 계측하였다.Using a DSC manufactured by Seiko Instruments Co., Ltd., the sample in an amorphous state was heated at a temperature of 10 ° C./min to 30 ° C. higher than the polymer melting peak at 10 ° C./min under a nitrogen atmosphere at a flow rate of 10 ml / min, Hold for 5 minutes, and measure the glass transition temperature by measuring the glass transition temperature at the temperature reduction rate of 10 ℃ / min, and again the endothermic peak temperature due to melting at elevated temperature melting point, the exothermic peak temperature due to crystallization at lower temperature as crystallization temperature Each was measured.
(5) 색상(YI)(5) Color (YI)
닛폰덴쇼쿠고교 주식회사에서 제조한 소형 색채백도계 NW-11을 이용하여 YI치를 측정하였다.The YI value was measured using the small colorimeter NW-11 manufactured by Nippon Denshoku Kogyo Co., Ltd.
(6) 시험편의 제작(6) Preparation of test piece
스미토모주키카이고교 주식회사에서 제조한 사출성형기인 SE18DUZ를 이용하여 하기 표 2의 조건으로 직사각형 시험편(크기 80mm×10mm×4.0mm)을 제작하였다.A rectangular test piece (size 80 mm x 10 mm x 4.0 mm) was manufactured under the conditions shown in Table 2 below, using SE18DUZ, an injection molding machine manufactured by Sumitomo Jukikai Co., Ltd.
표 2
* 성형온도: 260∼310℃ (각 실시예에서 얻어지는 폴리아미드 수지의 융점보다 10℃ 높은 온도를 설정하였다.)
* 금형온도: 150℃
* 사출압력: 120∼140 MPa
* 사출속도: 30 mm/초
* 스크루회전수: 150 rpm
* 냉각시험: 45초
TABLE 2
Molding temperature: 260-310 degreeC (The temperature 10 degreeC higher than melting | fusing point of the polyamide resin obtained by each Example was set.)
* Mold temperature: 150 ℃
* Injection pressure: 120 ~ 140 MPa
* Injection speed: 30 mm / s
* Screw speed: 150 rpm
* Cooling test: 45 seconds
(7) 시험편의 물성 평가(7) Evaluation of physical properties of the test piece
a) 굽힘시험a) bending test
주식회사 인테스코에서 제조한 만능재료시험기 2001-5형을 이용하고, JIS K7171: 2008(ISO178: 2001)에 준거하여, 23℃, 50%RH 환경에서 시험속도 2 mm/min, 지점간 거리 64mm로 굽힘시험을 하여 굴곡강도 및 굴곡탄성률을 구하였다.The universal testing machine 2001-5 manufactured by Intesco Co., Ltd. was used, and in accordance with JIS K7171: 2008 (ISO178: 2001), the test speed was 2 mm / min and the point-to-point distance 64 mm at 23 ° C and 50% RH. Flexural strength and flexural modulus were determined by bending test.
b) 하중변형온도b) load deflection temperature
주식회사 도요세이키세이사쿠쇼에서 제조한 자동 HDT 시험기 6A-2형을 이용하고, JIS K7191-1: 2007(ISO75-1: 2004), JIS K7191-2: 2007(ISO75-2: 2004)에 준거하여, 시험편을 플랫와이즈로 설치하고 시험응력 1.80 MPa의 조건으로 측정하였다.It conforms to JIS K7191-1: 2007 (ISO75-1: 2004), JIS K7191-2: 2007 (ISO75-2: 2004) using the automatic HDT tester 6A-2 type manufactured by Toyo Seiki Seisakusho Co., Ltd. The test piece was installed in a flatwise size and measured under the condition of a test stress of 1.80 MPa.
실시예Example
실시예 1Example 1
원료로서, 1,4-시클로헥산디카르복시산(CHDA, 제조사: 도쿄카세이고교 주식회사, 시스체, 트랜스체 혼합물, 시스/트랜스비(몰비)=80/20) 66.35 g(0.385 몰=30 몰%), 아디프산(AdA) 131.40 g(0.899 몰=70 몰%), 파라크실리렌디아민(PXDA) 52.27 g(0.384 몰=30 몰%), 메타크실리렌디아민(MXDA) 121.97 g(0.896 몰=70 몰%), 차아인산나트륨1수화물 0.372 g(투입 원료 100 중량부에 대하여, 0.1 중량부) 및 물 82 g(투입 원료 100 중량부에 대하여, 18 중량부)을 분축기, 압력조정밸브, 내시용 창 및 저부 배출밸브를 구비한 내용적 1리터의 오토클레이브 반응조에 넣고 질소치환을 실시하였다. 이를 교반하면서 1시간 동안 180℃까지 승온시키고 0.5시간 유지하여 내용물이 균일 용액이 되는 것을 확인하였다. 다음으로, 1시간 동안 내부온도를 220℃까지 승온시키고 밀폐 상태에서 2시간 동안 유지하였다. 이 때 반응조의 내압은 1.9 MPa이었다. 소정 반응시간이 경과한 후, 반응조의 온도 및 반응계 내의 수분량(28 중량%)을 유지한 채로 생성된 저차 축합물을 저부 배출밸브로부터 질소 분위기 하, 상온(25℃) 및 대기압 조건으로 용기에 배출하였다. 이 때, 배출밸브 노즐 지름은 1 mm이며, 배출 시간은 50초였다. 배출되는 용기의 산소농도는 0.1 체적%이며, 백색, 분말상의 저차 축합물을 얻었다. 배출 직후의 저차 축합물은 온도 81℃, 수분량 2.2 중량%였다. 얻어진 저차 축합물의 IV는 0.15 dL/g이며 융점은 267℃였다.As a raw material, 66.35 g (0.385 mol = 30 mol%) of 1,4-cyclohexanedicarboxylic acid (CHDA, Tokyo Kasei Kogyo Co., Ltd., cis body, trans body mixture, cis / trans ratio (molar ratio) = 80/20) , 131.40 g (0.8A mol = 70 mol%) of adipic acid (AdA), 52.27 g (0.384 mol = 30 mol%) of paraxylylenediamine (PXDA), 121.97 g (0.896 mol) of methaxylylenediamine (MXDA) = 70 mol%), 0.372 g of sodium hypophosphite monohydrate (0.1 parts by weight based on 100 parts by weight of the feedstock) and 82 g (18 parts by weight of 100 parts by weight of the feedstock) are divided into pressure reducer valves. Into a 1 liter autoclave reactor equipped with an end window and a bottom discharge valve, nitrogen replacement was performed. While stirring this, the temperature was raised to 180 ° C. for 1 hour and maintained for 0.5 hour to confirm that the contents became a homogeneous solution. Next, the internal temperature was raised to 220 ° C. for 1 hour and kept in a closed state for 2 hours. At this time, the internal pressure of the reactor was 1.9 MPa. After the prescribed reaction time has elapsed, the resulting lower condensate is discharged from the bottom discharge valve to the vessel at room temperature (25 ° C.) and atmospheric pressure from the bottom discharge valve while maintaining the temperature of the reactor and the water content (28 wt%) in the reaction system. It was. At this time, the discharge valve nozzle diameter was 1 mm, and the discharge time was 50 seconds. The oxygen concentration of the discharged vessel was 0.1% by volume, to obtain a white, powdery low order condensate. The low order condensate immediately after the discharge was a temperature of 81 ° C. and a water content of 2.2% by weight. The obtained lower order condensate had an IV of 0.15 dL / g and a melting point of 267 ° C.
얻어진 저차 축합물 300 g을 1,000 mL 둥근바닥 플라스크에 넣고 오일배스 로터리 증발기(evaporator)에 설치하여 질소 치환한 후에, 1 L/min의 질소 유통 하에서 플라스크를 회전시키면서 210℃의 오일배스에 침지하여 내부온도를 203℃까지 1시간 동안 승온시킨 후, 같은 온도에서 4시간 동안 고상중합 반응을 수행하였다. 소정 반응시간이 경과한 후에 실온(25℃)까지 냉각하여 고중합도화한 폴리아미드 수지를 얻었다. 얻어진 폴리아미드 수지의 IV는 0.85 dL/g이었고, Mn은 11,640 g/mol로 상기 식 1 및 2를 만족하는 성상을 나타내었다. DSC 측정에 의한 융점은 283℃이고, 유리전이온도는 105℃이고, 결정화 온도는 229℃이며, YI는 4로 고중합도화되고 색상이 양호한 고내열 폴리아미드 수지가 얻어졌다. NMR 분석을 통해 얻어진 폴리아미드 수지의 조성을 분석하였다. 그 결과, (CHDA/AdA):(MXDA/PXDA)=(30/70):(30/70)(몰비)인 것을 확인하였으며, 이를 통하여 원료 조성비와 동일한 조성비인 것을 확인하였다.300 g of the obtained lower condensate was placed in a 1,000 mL round bottom flask, installed in an oil bath rotary evaporator, and replaced with nitrogen, and then immersed in an oil bath at 210 ° C. while rotating the flask under a 1 L / min nitrogen flow to The temperature was raised to 203 ° C. for 1 hour, and then a solid phase polymerization reaction was performed at the same temperature for 4 hours. After predetermined reaction time passed, it cooled to room temperature (25 degreeC), and obtained the high polymerization polyamide resin. The obtained polyamide resin had an IV of 0.85 dL / g and Mn of 11,640 g / mol, exhibiting properties satisfying Equations 1 and 2 above. The melting point by DSC measurement was 283 ° C, the glass transition temperature was 105 ° C, the crystallization temperature was 229 ° C, and the high heat-resistant polyamide resin having high polymerization degree and good color was obtained with YI of 4. The composition of the polyamide resin obtained through NMR analysis was analyzed. As a result, it was confirmed that (CHDA / AdA) :( MXDA / PXDA) = (30/70) :( 30/70) (molar ratio), and through this, it was confirmed that it was the same composition ratio as the raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하여 시험편을 제작하고, 기계적 물성을 평가하였다. 굴곡강도는 181 MPa이고, 굴곡탄성률은 4.4 GPa이며, 하중변형온도는 110℃로 고강도, 고강성, 고내열의 성상을 나타냈다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The flexural strength was 181 MPa, the flexural modulus was 4.4 GPa, and the load deformation temperature was 110 ℃, indicating high strength, high rigidity, and high heat resistance.
실시예 2Example 2
원료로서, 1,4-시클로헥산디카르복시산 66.35 g(0.385 몰=30 몰%), 아디프산 131.40 g(0.899 몰=70 몰%), 파라크실리렌디아민 69.70 g(0.512 몰=40 몰%), 메타크실리렌디아민 104.55 g(0.768 몰=60 몰%), 차아인산나트륨1수화물 0.372 g(투입 원료 100 중량부에 대하여, 0.1 중량부) 및 물 248 g(투입 원료 100 중량부에 대하여, 40 중량부)을 분축기, 압력조정밸브, 내시용창 및 저부 배출밸브를 구비한 내용적 1리터의 오토클레이브 반응조에 넣고 질소치환을 실시하였다. 교반하면서 1시간 동안 180℃까지 승온시키고, 0.5시간 동안 유지하여 내용물이 균일 용액이 되는 것을 확인하였다. 다음으로, 1시간 동안 내부 온도를 220℃까지 승온시키고 유지하였다. 내압이 1.9 MPa에 도달한 후, 같은 압력으로 유지되도록 물을 166 g 증류/제거한 후에 밀폐하는 조건으로 같은 온도에서 2시간 동안 반응을 수행하였다. 다음으로, 실시예 1과 동일한 방법으로 저차 축합물의 배출 및 고상중합을 실시하였다. 얻어진 저차 축합물의 IV는 0.15 dL/g이며, 융점은 278℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.93 dL/g이고, Mn은 12,063 g/mol으로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 융점은 288℃이고, 유리전이온도는 103℃이고, 결정화 온도는 231℃이며, YI는 5로 고중합도화되고 색상이 양호한 고내열 폴리아미드 수지가 얻어졌다. 또한, 얻어진 폴리아미드 수지의 조성비를 실시예 1과 동일한 방법으로 분석하였으며, 원료 조성비와 동일한 것을 확인하였다.As raw materials, 66.35 g (0.385 mol = 30 mol%) of 1,4-cyclohexanedicarboxylic acid, 131.40 g (0.899 mol = 70 mol%) of adipic acid, 69.70 g (0.512 mol = 40 mol%) of paraxylylenediamine ), 104.55 g of metaxylylenediamine (0.768 mol = 60 mol%), 0.372 g of sodium hypophosphite monohydrate (0.1 parts by weight based on 100 parts by weight of the feedstock) and 248 g of water (100 parts by weight of the feedstock) , 40 parts by weight) was placed in a one-liter autoclave reactor equipped with a splitter, a pressure regulating valve, an endoscope window and a bottom discharge valve, and subjected to nitrogen replacement. It heated up to 180 degreeC for 1 hour, stirring, and maintained for 0.5 hours, and confirmed that the content became a uniform solution. Next, the internal temperature was raised to 220 ° C. for 1 hour and maintained. After the internal pressure reached 1.9 MPa, the reaction was carried out for 2 hours at the same temperature under the condition of 166 g distillation / removal of water so as to maintain the same pressure and then sealed. Next, the low-order condensate was discharged and solid-phase polymerization was carried out in the same manner as in Example 1. The obtained lower order condensate had an IV of 0.15 dL / g and a melting point of 278 ° C. In addition, IV of the obtained polyamide resin was 0.93 dL / g, Mn showed 12,063 g / mol and the said Formulas 1 and 2 were satisfied. The melting point by DSC measurement was 288 degreeC, the glass transition temperature was 103 degreeC, the crystallization temperature was 231 degreeC, YI was highly polymerized to 5, and the high heat resistant polyamide resin with favorable color was obtained. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하여 시험편을 제작하고, 기계적 물성을 평가하였다. 굴곡강도는 176 MPa이고, 굴곡탄성률은 4.4 GPa이며, 하중변형온도는 110℃로 고강도, 고강성, 고내열의 성상을 나타냈다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The flexural strength was 176 MPa, the flexural modulus was 4.4 GPa, and the load deformation temperature was 110 ℃, indicating high strength, high rigidity, and high heat resistance.
실시예 3Example 3
원료로서, 1,4-시클로헥산디카르복시산 44.63 g(0.259 몰=20 몰%), 아디프산 151.54 g(1.037 몰=80 몰%), 파라크실리렌디아민 87.91 g(0.646 몰=50 몰%) 및 메타크실리렌디아민 87.91 g(0.646 몰=50 몰%)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.16 dL/g이며 융점은 278℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.78 dL/g이고, Mn은 9,751 g/mol로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 융점은 286℃이고, 유리전이온도는 101℃이고, 결정화 온도는 238℃이며, YI는 5로 고중합도화되고 색상이 양호한 고내열 폴리아미드 수지가 얻어졌다. 또한, 얻어진 폴리아미드 수지의 조성비를 실시예 1과 동일한 방법으로 분석하였으며, 원료 조성비와 동일한 것을 확인하였다.As raw materials, 44.63 g (0.259 mol = 20 mol%) of 1,4-cyclohexanedicarboxylic acid, 151.54 g (1.037 mol = 80 mol%) of adipic acid, 87.91 g (0.646 mol = 50 mol%) of paraxylylenediamine ) And a lower order condensate and a polyamide resin were prepared in the same manner as in Example 1 except that 87.91 g (0.646 mol = 50 mol%) of methacrylicindiamine were used. The obtained lower order condensate had an IV of 0.16 dL / g and a melting point of 278 ° C. In addition, IV of the obtained polyamide resin was 0.78 dL / g, Mn showed 9,751 g / mol and the said Formulas 1 and 2 were satisfied. Melting | fusing point by DSC measurement was 286 degreeC, glass transition temperature was 101 degreeC, crystallization temperature was 238 degreeC, YI was highly polymerized to 5, and the high heat resistant polyamide resin with favorable color was obtained. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하여 시험편을 제작하고, 기계적 물성을 평가하였다. 굴곡강도는 182 MPa이고, 굴곡탄성률은 4.3 GPa이며, 하중변형온도는 105℃로 고강도, 고강성, 고내열의 성상을 나타냈다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The flexural strength was 182 MPa, the flexural modulus was 4.3 GPa, and the load deformation temperature was 105 ℃, indicating high strength, high rigidity, and high heat resistance.
실시예 4Example 4
원료로서, 1,4-시클로헥산디카르복시산 44.63 g(0.259 몰=20 몰%), 아디프산 151.54 g(1.037 몰=80 몰%), 파라크실리렌디아민 123.08 g(0.904 몰=70 몰%) 및 메타크실리렌디아민 52.75 g(0.387 몰=30 몰%)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.19 dL/g이며, 융점은 310℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.72 dL/g이고, Mn은 10,251 g/mol로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 융점은 314℃이고, 유리전이온도는 101℃이고, 결정화 온도는 242℃이며, YI는 5로 고중합도화되고 색상이 양호한 고내열 폴리아미드 수지가 얻어졌다. 또한, 얻어진 폴리아미드 수지의 조성비를 실시예 1과 동일한 방법으로 분석하였으며, 원료 조성비와 동일한 것을 확인하였다.As raw materials, 44.63 g (0.259 mol = 20 mol%) of 1,4-cyclohexanedicarboxylic acid, 151.54 g (1.037 mol = 80 mol%) of adipic acid, 123.08 g (0.904 mol = 70 mol% of paraxylylenediamine) ) And a lower order condensate and a polyamide resin were prepared in the same manner as in Example 1, except that 52.75 g (0.387 mol = 30 mol%) of metha xyylenediamine was used. IV of the obtained lower condensate was 0.19 dL / g, and melting | fusing point was 310 degreeC. In addition, IV of the obtained polyamide resin was 0.72 dL / g, Mn showed the property which satisfy | fills said Formula 1 and 2 at 10,251 g / mol. The melting point by DSC measurement was 314 ° C, the glass transition temperature was 101 ° C, the crystallization temperature was 242 ° C, and YI was highly polymerized to 5 to obtain a high heat-resistant polyamide resin having good color. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하여 시험편을 제작하고, 기계적 물성을 평가하였다. 굴곡강도는 185 MPa이고, 굴곡탄성률은 4.3 GPa이며, 하중변형온도는 106℃로 고강도, 고강성, 고내열의 성상을 나타냈다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The flexural strength was 185 MPa, the flexural modulus was 4.3 GPa, and the load deflection temperature was 106 ° C, indicating high strength, high rigidity, and high heat resistance.
실시예 5Example 5
저차 축합물의 중합온도를 225℃로 하고 반응압력을 2.5 MPa로 제어하여 41 g의 물을 증류/제거하는 조건으로 저차 축합물을 배출하고, 고상중합의 최고 온도를 224℃로 한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물, 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.21 dL/g이며 융점은 269℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 1.21 dL/g이고, Mn은 17,316 g/mol으로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 융점은 282℃이고, 유리전이온도는 106℃이고, 결정화 온도는 231℃이며, YI는 5로 고중합도화되고 색상이 양호한 고내열 폴리아미드 수지가 얻어졌다. 또한, 얻어진 폴리아미드 수지의 조성비를 실시예 1과 동일한 방법으로 분석하였으며, 원료 조성비와 동일한 것을 확인하였다.Except that the lower condensate was discharged under the condition of distilling / removing 41 g of water by controlling the polymerization temperature of the lower condensate to 225 ° C and controlling the reaction pressure to 2.5 MPa, and the maximum temperature of the solid phase polymerization was 224 ° C. In the same manner as in Example 1, a lower-order condensate and a polyamide resin were prepared. The obtained lower order condensate had an IV of 0.21 dL / g and a melting point of 269 ° C. In addition, IV of the obtained polyamide resin was 1.21 dL / g, Mn showed 17,316 g / mol and the said Formulas 1 and 2 were satisfied. The melting point by DSC measurement was 282 ° C, the glass transition temperature was 106 ° C, the crystallization temperature was 231 ° C, YI was highly polymerized to 5, and a high heat-resistant polyamide resin having good color was obtained. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하여 시험편을 제작하고, 기계적 물성을 평가하였다. 굴곡강도는 195 MPa이고, 굴곡탄성률은 4.4 GPa이며, 하중변형온도는 112℃로 고강도, 고강성, 고내열의 성상을 나타냈다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The flexural strength was 195 MPa, the flexural modulus was 4.4 GPa, and the load deformation temperature was 112 ° C, indicating high strength, high rigidity, and high heat resistance.
실시예 6Example 6
원료로서, 1,4-시클로헥산디카르복시산 87.68 g(0.509 몰=40 몰%), 아디프산 111.63 g(0.764 몰=60 몰%), 파라크실리렌디아민 51.81 g(0.380 몰=30 몰%) 및 메타크실리렌디아민 120.89 g(0.888 몰=70 몰%)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.17 dL/g이며, 융점은 277℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.81 dL/g이고, Mn은 10,753 g/mol으로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 융점은 295℃, 유리전이온도는 112℃, 결정화 온도는 246℃, YI는 4로 고중합도화되고 색상이 양호한 고내열 폴리아미드 수지가 얻어졌다. 또한, 얻어진 폴리아미드 수지의 조성비를 실시예 1과 동일한 방법으로 분석하였으며, 원료 조성비와 동일한 것을 확인하였다.As raw materials, 87.68 g (0.509 mol = 40 mol%) of 1,4-cyclohexanedicarboxylic acid, 111.63 g (0.764 mol = 60 mol%) of adipic acid, 51.81 g (0.380 mol = 30 mol%) of paraxylylenediamine ) And lower condensates and polyamide resins were prepared in the same manner as in Example 1, except that 120.89 g (0.888 mol = 70 mol%) of methacrylicindiamine were used. The obtained lower order condensate had an IV of 0.17 dL / g and a melting point of 277 ° C. In addition, IV of the obtained polyamide resin was 0.81 dL / g, Mn was 10,753 g / mol, and showed the property which satisfy | fills said Formula 1 and 2. A high heat-resistant polyamide resin having a high polymerization degree with a melting point of 295 ° C., a glass transition temperature of 112 ° C., a crystallization temperature of 246 ° C., and a YI of 4 was obtained by DSC measurement. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하여 시험편을 제작하고, 기계적 물성을 평가하였다. 굴곡강도는 190 MPa이고, 굴곡탄성률은 4.4 GPa이며, 하중변형온도는 120℃로 고강도, 고강성, 고내열의 성상을 나타냈다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The flexural strength was 190 MPa, the flexural modulus was 4.4 GPa, and the load deflection temperature was 120 ° C, indicating high strength, high rigidity, and high heat resistance.
비교예 1Comparative Example 1
원료로서, 1,4-시클로헥산디카르복시산 108.63 g(0.631 몰=50 몰%), 아디프산 92.20 g(0.631 몰=50 몰%) 및 메타크실리렌디아민 171.17 g(1.257 몰=100 몰%)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.16 dL/g이며, 융점은 340℃로 명료한 융해 피크를 나타내지 않았다. 또한, 얻어진 폴리아미드 수지의 IV는 0.69 dL/g이고, Mn은 9,799 g/mol로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 유리전이온도는 110℃이고, 융점은 351℃로 명료한 융해 피크를 나타내지 않았다. YI는 5로 고중합도화되고 색상이 양호한 폴리아미드 수지가 얻어졌다. 또한, 얻어진 폴리아미드 수지의 조성비를 실시예 1과 동일한 방법으로 분석하였으며, 원료 조성비와 동일한 것을 확인하였다.As raw materials, 108.63 g (0.631 mol = 50 mol%) of 1,4-cyclohexanedicarboxylic acid, 92.20 g (0.631 mol = 50 mol%) of adipic acid and 171.17 g (1.257 mol = 100 mol%) of methacrylicindiamine A lower order condensate and a polyamide resin were prepared in the same manner as in Example 1, except that () was used. The obtained lower order condensate had an IV of 0.16 dL / g and did not exhibit a clear melting peak at 340 ° C. In addition, IV of the obtained polyamide resin was 0.69 dL / g, Mn showed 9,799 g / mol and the said Formulas 1 and 2 were satisfied. The glass transition temperature by DSC measurement was 110 degreeC, and melting | fusing point did not show a clear melting peak at 351 degreeC. YI was highly polymerized to 5 and a polyamide resin having good color was obtained. Furthermore, the composition ratio of the obtained polyamide resin was analyzed by the same method as Example 1, and it confirmed that it was the same as a raw material composition ratio.
얻어진 폴리아미드 수지를 사출성형하려고 했으나, 용융되는 370℃의 조건에서는 분해가스가 다량으로 발생하여 시험편을 얻을 수 없었다.An injection molding of the obtained polyamide resin was attempted, but a large amount of cracked gas was generated under conditions of melting at 370 ° C., so that a test piece could not be obtained.
비교예 2Comparative Example 2
저차 축합물의 중합온도를 250℃로 하고 반응압력을 3.2 MPa로 제어한 것을 제외하고는 실시예 2와 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.18 dL/g이며, 융점은 264℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.95 dL/g이며, Mn은 7,435 g/mol로 식 2를 만족하지 않았다. DSC 측정에 의한 융점은 267℃이고, 유리전이온도는 104℃이고, 결정화 온도는 218℃이며, YI는 9로 내열성, 결정성이 떨어지는 폴리아미드 수지였다.A lower order condensate and a polyamide resin were prepared in the same manner as in Example 2 except that the polymerization temperature of the lower order condensate was 250 ° C. and the reaction pressure was controlled to 3.2 MPa. The obtained lower order condensate had an IV of 0.18 dL / g and a melting point of 264 ° C. In addition, IV of the obtained polyamide resin was 0.95 dL / g and Mn did not satisfy Formula 2 at 7,435 g / mol. Melting | fusing point by DSC measurement was 267 degreeC, glass transition temperature was 104 degreeC, crystallization temperature was 218 degreeC, YI was 9, and it was a polyamide resin inferior to heat resistance and crystallinity.
얻어진 폴리아미드 수지를 사출성형해서 시험편을 제작하여 기계적 물성을 평가하였다. 시험편에 이물질이 존재하였고, 굴곡강도는 106 MPa이고, 굴곡탄성률은 4.2 GPa이며, 하중변형온도는 110℃로 굴곡강도가 떨어지는 것을 확인할 수 있었다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The foreign material was present in the test piece, the flexural strength was 106 MPa, the flexural modulus was 4.2 GPa, and the load deflection temperature was 110 ° C.
비교예 3Comparative Example 3
원료 투입량을 실시예 1과 동일하게 하고, 저차 축합물의 중합온도를 240℃, 반응압력을 2.9 MPa로 제어하고 고상중합온도를 212℃로 한 것을 제외하고는 실시예 2와 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.18 dL/g이며, 융점은 262℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 1.15 dL/g이고, Mn은 12,821 g/mol로 식 2를 만족하지 않는 것이었다. DSC 측정에 의한 융점은 269℃이고, 유리전이온도는 103℃이고, 결정화 온도는 220℃이며, YI는 8로 내열성, 결정성이 약간 떨어지는 폴리아미드 수지였다.The lower condensate was made in the same manner as in Example 2 except that the amount of the raw material was adjusted in the same manner as in Example 1, the polymerization temperature of the lower condensate was controlled to 240 ° C., the reaction pressure was controlled to 2.9 MPa, and the solid phase polymerization temperature was 212 ° C. And polyamide resins. The obtained lower order condensate had an IV of 0.18 dL / g and a melting point of 262 ° C. In addition, IV of the obtained polyamide resin was 1.15 dL / g and Mn was 12,821 g / mol and did not satisfy Formula 2. Melting | fusing point by DSC measurement was 269 degreeC, glass transition temperature was 103 degreeC, crystallization temperature was 220 degreeC, and YI was 8, and polyamide resin was inferior to heat resistance and crystallinity slightly.
얻어진 폴리아미드 수지를 사출성형해서 시험편을 제작하여 기계적 물성을 평가하였다. 시험편에 이물질이 존재하였고, 굴곡강도는 142 MPa이고, 굴곡탄성률은 4.2 GPa이며, 하중변형온도는 110℃로 굴곡강도가 떨어지는 것을 확인할 수 있었다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. The foreign material was present in the test piece, the flexural strength was 142 MPa, the flexural modulus was 4.2 GPa, and the load deflection temperature was 110 ° C.
비교예 4Comparative Example 4
원료 투입량을 실시예 1과 동일하게 하고, 저차 축합물의 중합온도를 230℃, 반응압력을 2.7MPa, 반응시간을 5시간으로 한 것을 제외하고는 실시예 2와 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.18 dL/g이며, 융점은 260℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.85 dL/g이며, Mn은 9,217 g/mol로 식 2를 만족하지 않는 것이었다. DSC 측정에 의한 융점은 268℃이고, 유리전이온도는 102℃이고, 결정화 온도는 218℃이며, YI는 6으로 내열성, 결정성이 약간 떨어지는 폴리아미드 수지였다.The lower condensate and the polyamide were prepared in the same manner as in Example 2, except that the amount of starting materials was the same as in Example 1, and the polymerization temperature of the lower condensate was 230 ° C., the reaction pressure was 2.7 MPa, and the reaction time was 5 hours. Resin was prepared. IV of the obtained lower condensate was 0.18 dL / g, and melting | fusing point was 260 degreeC. In addition, IV of the obtained polyamide resin was 0.85 dL / g and Mn was 9,217 g / mol and it did not satisfy Formula 2. Melting | fusing point by DSC measurement was 268 degreeC, glass transition temperature was 102 degreeC, crystallization temperature was 218 degreeC, YI was 6, and it was a polyamide resin inferior to heat resistance and crystallinity slightly.
얻어진 폴리아미드 수지를 사출성형해서 시험편을 제작하여 기계적 물성을 평가하였다. 시험편에 이물질이 존재하였고, 굴곡강도는 138 MPa이고, 굴곡탄성률은 4.2 GPa이며, 하중변형온도는 110℃로 굴곡강도가 떨어지는 것을 확인할 수 있었다.The obtained polyamide resin was injection molded to prepare a test piece, and the mechanical properties were evaluated. Foreign matter was present in the specimen, flexural strength was 138 MPa, flexural modulus was 4.2 GPa, and the load deformation temperature was 110 ° C.
비교예 5Comparative Example 5
저차 축합물의 중합온도를 230℃로 하고, 고상중합의 최고온도를 234℃로 한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물, 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.18 dL/g이며 융점은 262℃였다. 또한, 얻어진 폴리아미드 수지는 진한 황산 등의 분석용매에 녹지 않는 겔상 화합물이 많이 존재하여 분석할 수 없었으며, DSC 측정에 의한 융점은 250℃이고, 유리전이온도는 101℃이고, 결정화 온도는 168℃이며, YI는 16으로 내열성 및 색상이 불량이었다.The lower condensate and the polyamide resin were prepared in the same manner as in Example 1 except that the polymerization temperature of the lower condensate was 230 ° C. and the maximum temperature of the solid phase polymerization was 234 ° C. The obtained lower order condensate had an IV of 0.18 dL / g and a melting point of 262 ° C. In addition, the obtained polyamide resin could not be analyzed due to the presence of many gel-like compounds which were insoluble in an analytical solvent such as concentrated sulfuric acid.The melting point was 250 ° C, the glass transition temperature was 101 ° C, and the crystallization temperature was 168 by DSC measurement. ℃, YI was 16, poor heat resistance and color.
얻어진 폴리아미드 수지는 겔상 화합물을 많이 포함하여 시험편을 얻을 수 없었다.The obtained polyamide resin contained many gel-like compounds, and the test piece was not obtained.
비교예 6Comparative Example 6
원료로서, 아디프산 192.92 g(1.320 몰=100 몰%) 및 메타크실리렌디아민 179.08 g(1.3148 몰=100 몰%)을 사용하고, 수분량을 61 g(투입 원료 100 중량부에 대하여, 14 중량부)으로 조절하고, 저차 축합물의 중합온도를 210℃로 하고 고상중합의 최고온도를 195℃로 한 것을 제외하고는 실시예 1과 동일한 방법으로 저차 축합물 및 폴리아미드 수지를 제조하였다. 얻어진 저차 축합물의 IV는 0.20 dL/g이며, 융점은 236℃였다. 또한, 얻어진 폴리아미드 수지의 IV는 0.84 dL/g이며, Mn은 12,143 g/mol으로 상기 식 1 및 2를 만족하는 성상을 나타냈다. DSC 측정에 의한 융점은 238℃이고, 유리전이온도는 86℃이고, 결정화 온도는 181℃이며, YI는 5였다.As a raw material, 192.92 g (1.320 mol = 100 mol%) of adipic acid and 179.08 g (1.3148 mol = 100 mol%) of metaxylene diamine were used, and the water content was 61 g (with respect to 100 parts by weight of the input raw material). The lower condensate and the polyamide resin were prepared in the same manner as in Example 1, except that the polymerization temperature of the lower condensate was 210 ° C and the maximum temperature of the solid phase polymerization was 195 ° C. IV of the obtained lower condensate was 0.20 dL / g, and melting | fusing point was 236 degreeC. In addition, IV of the obtained polyamide resin was 0.84 dL / g, Mn showed 12,143 g / mol and the said Formulas 1 and 2 were satisfied. Melting | fusing point by DSC measurement was 238 degreeC, glass transition temperature was 86 degreeC, crystallization temperature was 181 degreeC, and YI was 5.
얻어진 폴리아미드 수지를 사출성형에 의해 시험편으로 제작하여 기계적 물성을 평가하였다. 굴곡강도는 151 MPa이고, 굴곡탄성률은 4.6 GPa이며, 하중변형온도는 95℃로 고강성이지만 내열성이 떨어지는 것을 확인할 수 있었다.The obtained polyamide resin was produced into test pieces by injection molding, and mechanical properties were evaluated. The flexural strength was 151 MPa, the flexural modulus was 4.6 GPa, and the load deflection temperature was 95 ° C.
상기 실시예 및 비교예의 평가 결과를 정리하여 하기 표 3 및 4에 나타내었다.The evaluation results of the Examples and Comparative Examples are summarized in Tables 3 and 4 below.
표 3
실시예 1 실시예 2 실시예 3 실시예 4 실시예 5 실시예 6
원료디카르복시산 CHDA 30mol% 30mol% 20mol% 20mol% 30mol% 40mol%
AdA 70mol% 70mol% 80mol% 80mol% 70mol% 60mol%
원료디아민 PXDA 30mol% 40mol% 50mol% 70mol% 30mol% 30mol%
MXDA 70mol% 60mol% 50mol% 30mol% 70mol% 70mol%
촉매 SHM 0.1중량부 ← ← ← ← ←
투입수 18wt% 40wt% 18wt% ← ← ←
반응온도 (℃) 220 220 220 220 225 220
반응압력 (MPa) 1.9 1.9 1.9 1.9 2.5 1.9
반응시간 (hr) 2 2 2 2 2 2
배출 시 반응계 수분 (wt%) 28 28 28 28 21 28
배출 용기 압력 대기압 ← ← ← ← ←
산소농도 (vol%) 0.1 ← ← ← ← ←
배출후 온도 (℃) 81 82 81 81 85 81
배출후 수분 (wt%) 2.2 2.3 2.2 2.3 1.8 2.3
저차 중합물 IV (dL/g) 0.15 0.15 0.16 0.19 0.21 0.17
융점 (℃) 267 278 278 310 269 277
최고 반응온도 (℃) 203 204 200 200 224 204
반응시간 (hr) 4 4 4 4 4 4
IV (dL/g) 0.85 0.93 0.78 0.72 1.21 0.81
[NH2] (μeq/g) 51 47 63 69 44 56
[COOH] (μeq/g) 121 119 142 126 72 130
Mn (g/mol) 11640 12063 9751 10251 17316 10753
Mn/IV 13694 12971 12501 14238 14311 13275
융점 (℃) 283 288 286 314 282 295
유리전이온도 (℃) 105 103 101 101 106 112
결정화 온도 (℃) 229 231 238 242 231 246
YI 4 5 5 5 5 4
굴곡강도 (MPa) 181 176 182 185 195 190
굴곡탄성률 (GPa) 4.4 4.4 4.3 4.3 4.4 4.4
CHDA: 1,4-시클로헥산디카르복시산, AdA: 아디프산, PXDA: 파라크실리렌디아민, MXDA: 메타크실리렌디아민, SHM: 차아인산나트륨1수화물
TABLE 3
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Raw material dicarboxylic acid CHDA 30mol% 30mol% 20mol% 20mol% 30mol% 40mol%
AdA 70 mol% 70 mol% 80 mol% 80 mol% 70 mol% 60mol%
Raw material diamine PXDA 30mol% 40mol% 50 mol% 70 mol% 30mol% 30mol%
MXDA 70 mol% 60mol% 50 mol% 30mol% 70 mol% 70 mol%
catalyst SHM 0.1 parts by weight ← ← ← ← ←
Input 18wt% 40wt% 18wt% ← ← ←
Reaction temperature (℃) 220 220 220 220 225 220
Reaction pressure (MPa) 1.9 1.9 1.9 1.9 2.5 1.9
Reaction time (hr) 2 2 2 2 2 2
Reaction system moisture at discharge (wt%) 28 28 28 28 21 28
Discharge vessel pressure Atmospheric pressure ← ← ← ← ←
Oxygen concentration (vol%) 0.1 ← ← ← ← ←
Post discharge temperature (℃) 81 82 81 81 85 81
Moisture after discharge (wt%) 2.2 2.3 2.2 2.3 1.8 2.3
Lower polymer IV (dL / g) 0.15 0.15 0.16 0.19 0.21 0.17
Melting point (℃) 267 278 278 310 269 277
Reaction temperature (℃) 203 204 200 200 224 204
Reaction time (hr) 4 4 4 4 4 4
IV (dL / g) 0.85 0.93 0.78 0.72 1.21 0.81
NH 2 (μeq / g) 51 47 63 69 44 56
[COOH] (μeq / g) 121 119 142 126 72 130
Mn (g / mol) 11640 12063 9751 10251 17316 10753
Mn / IV 13694 12971 12501 14238 14311 13275
Melting point (℃) 283 288 286 314 282 295
Glass transition temperature (℃) 105 103 101 101 106 112
Crystallization temperature (℃) 229 231 238 242 231 246
YI 4 5 5 5 5 4
Flexural strength (MPa) 181 176 182 185 195 190
Flexural modulus (GPa) 4.4 4.4 4.3 4.3 4.4 4.4
CHDA: 1,4-cyclohexanedicarboxylic acid, AdA: adipic acid, PXDA: paraxylylenediamine, MXDA: metaxylylenediamine, SHM: sodium hypophosphite monohydrate
표 4
비교예 1 비교예 2 비교예 3 비교예 4 비교예 5 비교예 6
원료디카르복시산 CHDA 50mol% 30mol% 30mol% 30mol% 30mol% 0mol%
AdA 50mol% 70mol% 70mol% 70mol% 70mol% 100mol%
원료디아민 PXDA 0mol% 40mol% 30mol% 30mol% 30mol% 0mol%
MXDA 100mol% 60mol% 70mol% 70mol% 70mol% 100mol%
촉매 SHM 0.1중량부 ← ← ← ← ←
투입수 18wt% 40wt% ← ← 18wt% 14wt%
반응온도 (℃) 220 250 240 230 230 210
반응압력 (MPa) 1.9 3.2 2.9 2.7 2.7 1.4
반응시간 (hr) 2 2 2 5 2 2
배출 시 반응계 수분 (wt%) 28 28 28 28 28 21
배출 용기 압력 대기압 ← ← ← ← ←
산소농도 (vol%) 0.1 ← ← ← ← ←
배출후 온도 (℃) 81 95 88 85 83 76
배출후 수분 (wt%) 2.2 1.2 1.5 2.2 2.1 4.3
저차 중합물 IV (dL/g) 0.16 0.18 0.18 0.18 0.18 0.20
융점 (℃) >340 264 262 260 262 236
최고 반응온도 (℃) 201 202 212 202 234 195
반응시간 (hr) 4 4 4 4 4 4
IV (dL/g) 0.69 0.95 1.15 0.85 겔화로 인해 측정 불가 0.84
[NH2] (μeq/g) 68 66 88 56 114
[COOH] (μeq/g) 137 203 68 161 51
Mn (g/mol) 9799 7435 12821 9217 12143
Mn/IV 14201 7826 11148 10843 14456
융점 (℃) 351 267 269 268 250 238
유리전이온도 (℃) 110 104 103 102 101 86
결정화 온도 (℃) - 218 220 218 168 181
YI 5 9 8 6 16 5
굴곡강도 (MPa) - 106 142 138 - 151
굴곡탄성률 (GPa) - 4.2 4.2 4.2 - 4.6
하중변형온도 (℃) - 110 110 103 - 95
CHDA: 1,4-시클로헥산디카르복시산, AdA: 아디프산, PXDA: 파라크실리렌디아민, MXDA: 메타크실리렌디아민, SHM: 차아인산나트륨1수화물
Table 4
Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6
Raw material dicarboxylic acid CHDA 50 mol% 30mol% 30mol% 30mol% 30mol% 0mol%
AdA 50 mol% 70 mol% 70 mol% 70 mol% 70 mol% 100 mol%
Raw material diamine PXDA 0mol% 40mol% 30mol% 30mol% 30mol% 0mol%
MXDA 100 mol% 60mol% 70 mol% 70 mol% 70 mol% 100 mol%
catalyst SHM 0.1 parts by weight ← ← ← ← ←
Input 18wt% 40wt% ← ← 18wt% 14wt%
Reaction temperature (℃) 220 250 240 230 230 210
Reaction pressure (MPa) 1.9 3.2 2.9 2.7 2.7 1.4
Reaction time (hr) 2 2 2 5 2 2
Reaction system moisture at discharge (wt%) 28 28 28 28 28 21
Discharge vessel pressure Atmospheric pressure ← ← ← ← ←
Oxygen concentration (vol%) 0.1 ← ← ← ← ←
Post discharge temperature (℃) 81 95 88 85 83 76
Moisture after discharge (wt%) 2.2 1.2 1.5 2.2 2.1 4.3
Lower polymer IV (dL / g) 0.16 0.18 0.18 0.18 0.18 0.20
Melting point (℃) > 340 264 262 260 262 236
Reaction temperature (℃) 201 202 212 202 234 195
Reaction time (hr) 4 4 4 4 4 4
IV (dL / g) 0.69 0.95 1.15 0.85 Not measurable due to gelation 0.84
NH 2 (μeq / g) 68 66 88 56 114
[COOH] (μeq / g) 137 203 68 161 51
Mn (g / mol) 9799 7435 12821 9217 12143
Mn / IV 14201 7826 11148 10843 14456
Melting point (℃) 351 267 269 268 250 238
Glass transition temperature (℃) 110 104 103 102 101 86
Crystallization temperature (℃) - 218 220 218 168 181
YI 5 9 8 6 16 5
Flexural strength (MPa) - 106 142 138 - 151
Flexural modulus (GPa) - 4.2 4.2 4.2 - 4.6
Load deflection temperature (℃) - 110 110 103 - 95
CHDA: 1,4-cyclohexanedicarboxylic acid, AdA: adipic acid, PXDA: paraxylylenediamine, MXDA: metaxylylenediamine, SHM: sodium hypophosphite monohydrate
상기 표 3 및 4의 결과로부터, 실시예 1∼6에서 얻어진 본 발명의 폴리아미드 수지는 기계적 강도, 내열성, 색조 등의 물성 발란스(균형)이 우수한 것을 알 수 있다. 또한, 본 발명의 제조방법에 의해 제조된 폴리아미드 수지는 겔화 등 제조상의 문제가 생기지 않음을 알 수 있다.From the results of Tables 3 and 4 above, it can be seen that the polyamide resin of the present invention obtained in Examples 1 to 6 has excellent physical balance (balance) such as mechanical strength, heat resistance and color tone. In addition, it can be seen that the polyamide resin produced by the production method of the present invention does not cause manufacturing problems such as gelation.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (7)

1,4-시클로헥산디카르복시산을 함유하는 디카르복시산 성분; 및Dicarboxylic acid components containing 1,4-cyclohexanedicarboxylic acid; And
파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민을 함유하는 디아민 성분;을 포함하는 단량체 혼합물의 중합체이며,A diamine component containing xyleneylene diamine having a content of paraxylenediamine component of about 10 to about 100 mol%;
진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도(IV) 및 적정법으로 구한 수평균분자량(Mn)이 하기 식 1 및 식 2를 만족하는 것을 특징으로 하는 폴리아미드 수지:Polyamide resin characterized in that the logarithmic viscosity (IV) and the number average molecular weight (Mn) determined by titration method at a concentration of about 0.5 g / dL in concentrated sulfuric acid satisfy the following formulas (1) and (2). :
[식 1][Equation 1]
약 0.4 ≤ IV ≤ 약 1.5About 0.4 ≤ IV ≤ about 1.5
[식 2][Equation 2]
약 12,000 ≤ Mn/IVAbout 12,000 ≤ Mn / IV
제1항에 있어서, 상기 디카르복시산 성분은 상기 1,4-시클로헥산디카르복시산 약 5 내지 약 50 몰%, 및 1,4-시클로헥산디카르복시산 이외의 디카르복시산 약 50 내지 약 95 몰%를 함유하며, 상기 디아민 성분은 상기 크실리렌디아민 약 50 내지 약 100 몰%와 크실리렌디아민 이외의 디아민 약 0 내지 약 50 몰%를 함유하는 것을 특징으로 하는 폴리아미드 수지.The dicarboxylic acid component of claim 1, wherein the dicarboxylic acid component contains about 5 to about 50 mole percent of the 1,4-cyclohexanedicarboxylic acid and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid. Wherein said diamine component contains from about 50 to about 100 mole percent of said xyleneylene diamine and from about 0 to about 50 mole percent of diamines other than xylylenediamine.
제1항에 있어서, 상기 폴리아미드 수지는 융점이 약 270℃ 이상이고 유리전이온도가 약 100℃ 이상이며, 굴곡탄성률이 약 4 GPa 이상인 것을 특징으로 하는 폴리아미드 수지.The polyamide resin of claim 1, wherein the polyamide resin has a melting point of about 270 ° C. or more, a glass transition temperature of about 100 ° C. or more, and a flexural modulus of about 4 GPa or more.
제1항에 있어서, 상기 크실리렌디아민은 메타크실리렌디아민 성분을 약 10 내지 약 90 몰% 포함하는 것을 특징으로 하는 폴리아미드 수지.The polyamide resin of claim 1 wherein the xylylenediamine comprises about 10 to about 90 mole percent of a metaxylenediamine component.
1,4-시클로헥산디카르복시산을 함유하는 디카르복시산 성분과 파라크실리렌디아민 성분의 함유량이 약 10 내지 약 100 몰%인 크실리렌디아민을 함유하는 디아민 성분을 약 200℃ 이상 약 230℃ 미만의 반응온도 및 약 0.5 내지 약 3 MPa의 반응압력 하에서 약 0.5 내지 약 4시간 동안 반응시키고, 반응 종료 후, 반응계 내의 수분량이 약 15 내지 약 35 중량%인 조건으로 중축합 반응을 실시하여, 저차 축합물을 제조하는 공정;The diamine component containing 1,4-cyclohexanedicarboxylic acid and the diamine component containing xylylenediamine having a content of about 10 to about 100 mol% of the dicarboxylic acid component and the paraxylenediamine component are about 200 ° C or more and less than about 230 ° C. At a reaction temperature of about 0.5 to about 3 MPa and a reaction pressure of about 0.5 to about 4 hours, and after completion of the reaction, the polycondensation reaction is carried out under the condition that the amount of water in the reaction system is about 15 to about 35% by weight. Preparing a condensate;
불활성가스 분위기 하, 대기압 이하의 압력으로 상기 저차 축합물을 배출 및 냉각하는 공정; 및Discharging and cooling the lower order condensate under an inert gas atmosphere at a pressure below atmospheric pressure; And
상기 배출 및 냉각한 저차 축합물을 고상중합하는 공정;을 포함하며,And solid-phase polymerizing the discharged and cooled lower condensates.
상기 배출 및 냉각한 저차 축합물은 진한 황산 중 약 0.5 g/dL의 농도로 온도 약 25℃에서 측정한 대수점도가 약 0.07 내지 약 0.40 dL/g인 것을 특징으로 하는 폴리아미드 수지의 제조방법.Wherein said discharged and cooled lower condensate has a logarithmic viscosity measured at a temperature of about 25 ° C. at a concentration of about 0.5 g / dL in concentrated sulfuric acid at about 0.07 to about 0.40 dL / g.
제5항에 있어서, 상기 디카르복시산 성분은 상기 1,4-시클로헥산디카르복시산 약 5 내지 약 50 몰%, 및 1,4-시클로헥산디카르복시산 이외의 디카르복시산 약 50 내지 약 95 몰%를 함유하며, 상기 디아민 성분은 상기 크실리렌디아민 약 50 내지 약 100 몰%와 크실리렌디아민 이외의 디아민 약 0 내지 약 50 몰%를 함유하는 것을 특징으로 하는 폴리아미드 수지의 제조방법.The dicarboxylic acid component of claim 5, wherein the dicarboxylic acid component contains about 5 to about 50 mole percent of the 1,4-cyclohexanedicarboxylic acid and about 50 to about 95 mole percent of dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid. Wherein the diamine component contains about 50 to about 100 mol% of the xyleneylene diamine and about 0 to about 50 mol% of diamines other than xyleneylene diamine.
제5항에 있어서, 상기 고상중합의 최고 반응온도는, 약 230℃ 및 상기 저차 축합물의 융점보다 약 20℃ 낮은 온도 중 낮은 쪽 온도 이하인 것을 특징으로 하는 폴리아미드 수지의 제조방법.The method for producing a polyamide resin according to claim 5, wherein the maximum reaction temperature of the solid phase polymerization is equal to or lower than the lower temperature of about 230 ° C and about 20 ° C lower than the melting point of the lower condensate.
PCT/KR2013/009383 2012-11-29 2013-10-21 Polyamide resin, and method for preparing same WO2014084504A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001192A (en) * 1971-11-16 1977-01-04 Hoechst Aktiengesellschaft Transparent polyamides from bis(aminomethyl)-norbornanes
KR20090021132A (en) * 2007-08-24 2009-02-27 이엠에스-패턴트 에이지 High-temperature polyamide molding compounds reinforced with flat glass fibers
KR20110084158A (en) * 2008-09-18 2011-07-21 미츠비시 가스 가가쿠 가부시키가이샤 Polyamide resin
KR20120060216A (en) * 2009-09-14 2012-06-11 미츠비시 가스 가가쿠 가부시키가이샤 Polyamide resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001192A (en) * 1971-11-16 1977-01-04 Hoechst Aktiengesellschaft Transparent polyamides from bis(aminomethyl)-norbornanes
KR20090021132A (en) * 2007-08-24 2009-02-27 이엠에스-패턴트 에이지 High-temperature polyamide molding compounds reinforced with flat glass fibers
KR20110084158A (en) * 2008-09-18 2011-07-21 미츠비시 가스 가가쿠 가부시키가이샤 Polyamide resin
KR20120060216A (en) * 2009-09-14 2012-06-11 미츠비시 가스 가가쿠 가부시키가이샤 Polyamide resin composition

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