A method for producing polyamides by multi-component copolymerization, a polyamide produced thereby, and a composition containing the same.

Abstract

The present invention relates to a method for producing a polyamide by multi-component copolymerization, a polyamide produced thereby, and a composition containing the same. The copolymerized polyamide and a composition containing the same according to the embodiment of the present invention can exhibit excellent mechanical properties, low temperature properties, and gas barrier properties.

Description

Technical Field

[0001] The present invention relates to a method for producing polyamide by polycondensation copolymerization, the polyamide produced thereby, and a composition containing the same. Specifically, the present invention relates to a method for producing polyamide by copolymerization of a low molecular weight polyamide salt and lactam or α,ω-aminocarboxylic acid, the polyamide produced thereby, and a composition containing the same.

Background Art

[0002] Polyamide refers to a polymer containing amide (-CO-NH-) units in the main chain. Polyamide can be produced from two different bifunctional monomer units each containing two identical reactive groups (e.g., -NH2 or -COOH), or from a single bifunctional monomer unit containing one amino group and one carboxyl group each, or from a single bifunctional monomer unit capable of forming these groups. For example, polyamide can be produced by a condensation polymerization reaction of diamine and dicarboxylic acid, a condensation polymerization reaction of aminocarboxylic acid, or a ring-opening polymerization reaction of lactam.

[0003] Polyamide is classified into aliphatic polyamide, aromatic polyamide, and alicyclic polyamide according to its molecular structure, and is excellent in physical properties such as rigidity, friction resistance, abrasion resistance, oil resistance, and solvent resistance due to its molecular structure.

[0004] On the other hand, there has been an attempt to blend two polyamides having different characteristics from each other to complement their respective physical properties. For example, in Korean Patent Publication No. 10-2012-0034742, two polyamides of PA MXD.10 and PA 6.10 were mixed in an extruder to produce a molded product having an excellent elastic modulus. However, since the two polyamides are not chemically completely bonded, there is a limit to reducing the processing temperature and improving the low-temperature characteristics.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Korean Published Patent No. 10-2012-0034742 [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a method for producing polyamides by multi-component copolymerization, copolymerized polyamides produced thereby that exhibit excellent physical properties, and compositions containing the same. [Means for solving the problem]

[0007] To achieve the above objective, the present invention comprises (1) the step of producing a polyamide salt by condensation polymerization of a diamine and a dicarboxylic acid, and (2) the step of copolymerizing a lactam or α,ω-aminocarboxylic acid with a polyamide salt, wherein the equivalent ratio of dicarboxylic acid to diamine is 1.05 to 1.0, and the lactam or α,ω-aminocarboxylic acid and, Polyamide salt Repeating units derived from diamines and dicarboxylic acids The present invention provides a method for producing copolymerized polyamides in which the molar ratio is 96:4 to 50:50.

[0008] In embodiments of the present invention, in step (1) above, the dicarboxylic acid may comprise at least one of the following: aliphatic dicarboxylic acids selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanediic acid; alicyclic dicarboxylic acids selected from the group consisting of cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Preferably, the dicarboxylic acid is sebacic acid.

[0009] In embodiments of the present invention, in step (1) above, the diamine is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminoteto Aliphatic diamines selected from the group consisting of radecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, and 2-methyl-1,5-diaminopentane; alicyclic diamines selected from the group consisting of cyclohexanediamine and bis-(4-aminocyclohexyl)methane; and xyl Ri It may contain at least one of the aromatic diamines that are rediamines. Preferably, the diamine is m-xy Ri Rediamine (m-xy ly It could be lenediamine.

[0010] In embodiments of the present invention, the condensation polymerization in step (1) above can be carried out at a temperature of 150 to 200°C for 1 to 3 hours.

[0011] In embodiments of the present invention, the polyamide salt obtained in step (1) above may have a relative viscosity (sulfuric acid) of 1 to 2.

[0012] In embodiments of the present invention, in step (2) above, the lactam may include at least one selected from the group consisting of laurolactam, caprolactam, piperidone, pyrrolidone, enantholactam, capryllactam, propiolactam, valerolactam, heptanolactam, octanolactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam. Preferably, the lactam is caprolactam.

[0013] In embodiments of the present invention, in step (2) above, the α,ω-aminocarboxylic acid may include at least one selected from the group consisting of aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0014] In embodiments of the present invention, the copolymerization in step (2) above can be carried out in the presence of a phosphorus-based compound as a heat stabilizer and catalyst. More specifically, the phosphorus-based compound may be a hypophosphite compound or a phosphite compound.

[0015] In embodiments of the present invention, the copolymerization in step (2) above may include a primary copolymerization carried out at a pressure of 1 to 5 bar and a temperature of 250 to 300°C for 1 to 3 hours, and a secondary copolymerization carried out at a pressure of 0.001 to 0.5 bar and a temperature of 200 to 300°C for 0.1 to 12 hours.

[0016] In another embodiment of the present invention, a copolymerized polyamide is provided which is produced by the above-described manufacturing method and comprises (a) a first structural unit derived from a lactam or α,ω-aminocarboxylic acid; (b) a second structural unit derived from an aromatic diamine or aromatic dicarboxylic acid; and (c) a third structural unit derived from an aliphatic or alicyclic diamine having 10 or more carbon atoms or an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms, wherein the content of the first structural unit is 50 to 96 mol%, and the total content of the second and third structural units is 4 to 50 mol%.

[0017] In embodiments of the present invention, the copolymerized polyamide may further comprise (d) a fourth structural unit derived from a C2-C9 aliphatic or alicyclic diamine or a C2-C9 aliphatic or alicyclic dicarboxylic acid.

[0018] In embodiments of the present invention, the copolymerized polyamide may have a relative viscosity (sulfuric acid) of 2.0 to 5.0.

[0019] In yet another embodiment of the present invention, a copolymerized polyamide composition is provided comprising (A) 4 to 50% by weight of copolymerized polyamide according to an embodiment of the present invention; (B) 50 to 96% by weight of homopolyamide produced from lactam or α,ω-aminocarboxylic acid; and (C) 0 to 20% by weight of an impact reinforcer.

[0020] In embodiments of the present invention, the impact reinforcement agent (C) may include at least one selected from the group consisting of ethylene-propylene rubber grafted with maleic anhydride, ethylene-1-butene rubber, ethylene-butylene rubber, ethylene-1-pentene rubber, ethylene-1-hexene rubber, ethylene-1-heptene rubber, ethylene-1-octene rubber, and ethylene-4-methyl-1-pentene rubber. Preferably, the impact reinforcement agent (C) is ethylene-butylene rubber grafted with maleic anhydride.

[0021] In an embodiment of the present invention, the polyamide composition may further contain an additive (D) in a content of 3 parts by weight or less based on 100 parts by weight of components (A) to (C).

[0022] At this time, the additive (D) may contain at least one selected from the group consisting of an antioxidant, a heat stabilizer, a neutralizing agent, a weather stabilizer, an antistatic agent, a lubricant, a slip agent, a pigment, and a dye.

[0023] In a specific embodiment, the additive (D) is a primary antioxidant selected from phenol antioxidants, BHT (butylated Hydroxytoluene), (N,N'-Hexane-1,6-diyrbis(3-(3,5-di-tert.-butyl-4-hydroxyphenylpropionamide))) , Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate , Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and 1,3,5-Tris(3,5-di-tert.-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione , a secondary antioxidant which is Tris(2,4-di-tert-butylphenyl) phosphite , and a heat stabilizer which is sodium hypophosphite (Na2H2PO2).

[0024] In still another embodiment of the present invention, there is provided a molded article of the copolymer polyamide or the copolymer polyamide composition produced by molding the copolymer polyamide.

[0025] In an embodiment of the present invention, the molded article of the copolymer polyamide can be used for automotive parts, environmental materials, tank liners, containers, building materials, electrical and electronic parts, space / aerospace, doralon, food and functional packaging, housings, and energy materials.

Effects of the Invention

[0026] The copolymer polyamide and the composition containing the same according to the embodiment of the present invention can exhibit excellent mechanical properties, low-temperature properties, and gas barrier properties.

Modes for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in more detail.

[0028] Method for Producing Copolymer Polyamide A method for producing copolymerized polyamide according to embodiments of the present invention comprises the steps of (1) condensing a diamine and a dicarboxylic acid to produce a polyamide salt, and (2) copolymerizing a lactam or α,ω-aminocarboxylic acid with a polyamide salt, wherein the equivalent ratio of dicarboxylic acid to diamine is 1.05 to 1.0, and the lactam or α,ω-aminocarboxylic acid and, Polyamide salt Repeating units derived from diamines and dicarboxylic acids The present invention provides a method for producing copolymerized polyamides in which the molar ratio is 96:4 to 50:50.

[0029] Stage (1) In step (1) above, a polyamide salt is produced by condensation polymerization of a diamine and a dicarboxylic acid.

[0030] First, the dicarboxylic acid, one of the monomers for the production of the polyamide salt, is either filled into the reactor in a solid state and then melted, or it is pre-melted in a separate melting tank and then a predetermined amount is filled into the reactor.

[0031] Here, the reactor used for the production of the polyamide salt is not particularly limited, but may be a stirred tank reactor equipped with a stirrer. Here, the type of stirrer is not particularly limited, as long as it can adequately stir the reaction mixture of the diamine and dicarboxylic acid. In one embodiment of the present invention, the stirrer may be of the helical ribbon type or anchor type.

[0032] Examples of dicarboxylic acids used in the production of polyamide salts in embodiments of the present invention include, but are not limited to, aliphatic dicarboxylic acids selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanediic acid; alicyclic dicarboxylic acids selected from the group consisting of cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Preferably, the dicarboxylic acid is sebacic acid.

[0033] While stirring the molten dicarboxylic acid in the reactor with a stirrer, an inert gas such as nitrogen is supplied through the purge line to thoroughly purge the reactor.

[0034] Subsequently, the temperature inside the reactor is heated to 150-200°C, the temperature at which the amidation reaction substantially takes place. Specifically, the temperature inside the reactor is set so that the polyamide salt, which is the product, remains in a molten state during the addition of the diamine, in order to ensure uniform fluidity throughout the reaction system.

[0035] Next, a diamine, which is another monomer for the production of the polyamide salt, is added to the reactor continuously or intermittently. At this time, the diamine flows into the reactor from a diamine supply tank using a metering pump. Here, the specific type and configuration of the diamine supply tank and metering pump are not particularly limited, as long as they can supply a metered amount of diamine to the reactor.

[0036] Examples of diamines used in the production of polyamide salts in embodiments of the present invention include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, and 1,14-diamine. Aliphatic diamines selected from the group consisting of minotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, and 2-methyl-1,5-diaminopentane; alicyclic diamines selected from the group consisting of cyclohexanediamine and bis-(4-aminocyclohexyl)methane; and xyl Ri Examples include, but are not limited to, aromatic diamines of rediamine. Preferably, the diamine is m-xyl Ri Rediamine (m-xy ly It is lenediamine.

[0037] It is preferable to add the diamine over 0.5 to 4 hours while maintaining the reaction mixture in a molten state, so that the reaction proceeds gradually.

[0038] In the embodiments of the present invention, in step (1) above, the equivalent ratio of dicarboxylic acid to diamine is 1.05 to 1.0. Condensation polymerization can be carried out appropriately when the equivalent ratio of dicarboxylic acid to diamine is within the above range.

[0039] It is preferable to adjust the temperature inside the reactor so that the temperature inside the reactor is between 150 and 250°C when all of the diamine has been added. At this time, the rate of temperature rise inside the reactor is determined by the heat of the amidation reaction, the latent heat of condensation vaporization, the amount of heat supplied, etc., so it is preferable to adjust the rate of diamine addition so that the temperature inside the reactor is within the above range when all of the diamine has been added.

[0040] In embodiments of the present invention, the condensation polymerization in step (1) above can be carried out at a temperature of 150 to 250°C for 1 to 3 hours.

[0041] In embodiments of the present invention, the polyamide salt obtained in step (1) may have a relative viscosity (sulfuric acid) of 1 to 2. When the relative viscosity of the polyamide salt is within the above range, copolymerization can be carried out appropriately in step (2).

[0042] The polyamide salt obtained in step (1) above can be thoroughly washed with ethanol solvent to remove unreacted monomers, filtered using filter paper or a filter mesh, and then dried in a vacuum oven at approximately 50°C.

[0043] Stage (2) In step (2) above, a copolymerized polyamide is produced by copolymerizing a lactam or α,ω-aminocarboxylic acid with a polyamide salt.

[0044] The polyamide salt produced in step (1) is packed into the reactor together with a lactam or α,ω-aminocarboxylic acid monomer and a phosphorus-based compound that selectively acts as a heat stabilizer and catalyst.

[0045] The copolymerization in step (2) can be carried out in the reactor used in step (1) or in a separate reactor.

[0046] In embodiments of the present invention, the lactam used in the production of copolymerized polyamides may be a lactam having 3 to 20 carbon atoms. Examples of such lactams include, but are not limited to, laurolactam, caprolactam, piperidone, pyrrolidone, enantholactam, capryllactam, propiolactam, valerolactam, heptanolactam, octanolactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam. Preferably, the lactam is caprolactam.

[0047] In embodiments of the present invention, α,ω-aminocarboxylic acids can be used instead of lactams in the production of copolymerized polyamides. Examples of α,ω-aminocarboxylic acids include, but are not limited to, aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0048] In embodiments of the present invention, in step (2) above, the molar ratio of the polyamide salt to the lactam or α,ω-aminocarboxylic acid is 96:4 to 50:50. and, Polyamide salt Repeating units derived from diamines and dicarboxylic acids When the molar ratio is within the above range, the copolymerized polyamide can exhibit excellent physical properties.

[0049] In embodiments of the present invention, the copolymerization in step (2) above can be carried out in the presence of a phosphorus compound as both a heat stabilizer and a catalyst. Here, the phosphorus compound acts as a heat stabilizer to prevent discoloration of the copolymerized polyamide produced, while also acting as a catalyst to increase the degree of polymerization of the copolymerized polyamide produced.

[0050] Phosphorus compounds may be, but are not limited to, hypophosphite compounds (also called phosphinate compounds or phosphonic acid compounds) or phosphite compounds (also called phosphonic acid compounds). Phosphorus compounds may be metal salts or alkali metal salts.

[0051] Examples of hypophosphorous compounds include hypophosphorous acid; hypophosphorous metal salts such as sodium hypophosphorous acid, potassium hypophosphorous acid, and lithium hypophosphorous acid; hypophosphorous compounds such as ethyl hypophosphorous acid, dimethylphosphinic acid, phenylmethylphosphinic acid, phenylphosphonic acid, and ethyl phenylphosphonic acid; and phenylphosphonic acid metal salts such as sodium phenylphosphonic acid, potassium phenylphosphonic acid, and lithium phenylphosphonic acid.

[0052] Specific examples of phosphite compounds include phosphorous acid, pyrophosphorous acid; metal phosphite salts such as sodium hydrogen phosphite and sodium phosphite; phosphite compounds such as triethyl phosphite, triphenyl phosphite, ethylphosphonic acid, phenylphosphonic acid, and diethyl phenylphosphonate; and metal phenylphosphonate salts such as sodium ethylphosphonate, potassium ethylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, and lithium phenylphosphonate.

[0053] Preferably, the phosphorus compound is sodium hypophosphate (N aH It is 2PO2).

[0054] The phosphorus-based compound content is 0.3 to 1.0% by weight, preferably 0.5 to 0.7% by weight, based on the total weight of the theoretical polymer obtained after polymerization.

[0055] After filling the reactor with all the copolymerization raw materials, the reactor is thoroughly purged by supplying an inert gas such as nitrogen through the purge line.

[0056] In embodiments of the present invention, the copolymerization in step (2) above may include a primary copolymerization and a secondary copolymerization.

[0057] In this stage, the first copolymerization is a condensation polymerization that takes place while the reactants are molten, yielding a low-viscosity polyamide.

[0058] Specifically, the primary copolymerization can be carried out at a pressure of 1-5 bar and a temperature of 250-300°C for 1-3 hours.

[0059] Secondary copolymerization is a step in which a low-viscosity polyamide is polymerized in a molten or solid state under reduced pressure to obtain a higher-viscosity polyamide.

[0060] Specifically, the secondary copolymerization can be carried out at a pressure of 0.001 to 0.5 bar and a temperature of 200 to 300°C for 0.1 to 12 hours.

[0061] Copolymerized polyamide The copolymerized polyamide according to the embodiment of the present invention is produced by the above-described manufacturing method and comprises (a) a first structural unit derived from a lactam or α,ω-aminocarboxylic acid; (b) a second structural unit derived from an aromatic diamine or aromatic dicarboxylic acid; and (c) a third structural unit derived from an aliphatic or alicyclic diamine having 10 or more carbon atoms or an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms, with the content of the first structural unit being 50 to 96 mol%, and the total content of the second and third structural units being 4 to 50 mol%.

[0062] In embodiments of the present invention, since the copolymerized polyamide is produced by the production method according to embodiments of the present invention, it may contain all structural units formed by the condensation polymerization of diamine and dicarboxylic acid in step (1) of the production method according to embodiments of the present invention, and all structural units formed by the polymerization of lactam or α,ω-aminocarboxylic acid in step (2).

[0063] Specifically, the first structural unit of the copolymerized polyamide is derived from lactam or α,ω-aminocarboxylic acid. Here, lactam and α,ω-aminocarboxylic acid are as described in the section on the method for producing the copolymerized polyamide.

[0064] In copolymerized polyamides, the content of the first structural unit is 50 to 96 mol%. When the content of the first structural unit is within this range, the copolymerized polyamide can exhibit excellent physical properties.

[0065] Furthermore, the second structural unit of the copolymerized polyamide is derived from an aromatic diamine or aromatic dicarboxylic acid. Here, aromatic diamines and aromatic dicarboxylic acids are as described in the section on the method for producing the copolymerized polyamide. Specifically, aromatic diamines are xylamines. Ri It may contain a didiamine, and the aromatic dicarboxylic acid may include phthalic acid, isophthalic acid, terephthalic acid, or naphthalenedicarboxylic acid.

[0066] Furthermore, the third structural unit of the copolymerized polyamide is derived from an aliphatic or alicyclic diamine having 10 or more carbon atoms, or from an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms. Here, the aliphatic or alicyclic diamine having 10 or more carbon atoms and the aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms are as described in the section on the method for producing the copolymerized polyamide.

[0067] Specifically, aliphatic or alicyclic diamines with 10 or more carbon atoms include 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, and 1,19-diaminono The compounds may include nadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, or bis-(4-aminocyclohexyl)methane, and the aliphatic or alicyclic dicarboxylic acids having 10 or more carbon atoms may include sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, or octadecanedioic acid.

[0068] In copolymerized polyamides, the total content of the second and third structural units is 4 to 50 mol%. When the total content of the second and third structural units is within this range, the copolymerized polyamide can exhibit excellent physical properties.

[0069] In embodiments of the present invention, the copolymerized polyamide may further comprise (d) a fourth structural unit derived from a C2-C9 aliphatic or alicyclic diamine or a C2-C9 aliphatic or alicyclic dicarboxylic acid. Here, the C2-C9 aliphatic or alicyclic diamine and the C2-C9 aliphatic or alicyclic dicarboxylic acid are as described in the section on the method for producing the copolymerized polyamide.

[0070] Specifically, aliphatic or alicyclic diamines having 2 to 9 carbon atoms may include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, or cyclohexanediamine, and aliphatic or alicyclic dicarboxylic acids having 2 to 9 carbon atoms may include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or cyclohexanedicarboxylic acid.

[0071] The content of the fourth structural unit in the copolymerized polyamide may be 20 mol% or less.

[0072] In embodiments of the present invention, the copolymerized polyamide may have a relative viscosity (sulfuric acid) of 2.0 to 5.0. When the relative viscosity of the copolymerized polyamide is within the above range, it can exhibit excellent physical properties.

[0073] Copolymerized polyamide composition A copolymerized polyamide composition according to an embodiment of the present invention comprises (A) 4 to 50% by weight of a copolymerized polyamide according to an embodiment of the present invention; (B) 50 to 96% by weight of a homopolyamide produced from a lactam or α,ω-aminocarboxylic acid; and (C) 0 to 20% by weight of an impact reinforcer.

[0074] The copolymerized polyamide composition according to an embodiment of the present invention comprises copolymerized polyamide (A) according to an embodiment of the present invention. Here, copolymerized polyamide (A) is as described in the section on copolymerized polyamide.

[0075] The content of copolymerized polyamide (A) in the copolymerized polyamide composition is 4 to 50% by weight. When the content of copolymerized polyamide (A) is within the above range, the composition can exhibit excellent physical properties.

[0076] The copolymerized polyamide composition according to the embodiment of the present invention comprises a homopolyamide (B) produced from a lactam or an α,ω-aminocarboxylic acid. Here, the type and method of production of the homopolyamide (B) are not particularly limited, as long as it is produced from a lactam or an α,ω-aminocarboxylic acid. The lactam and α,ω-aminocarboxylic acid are as described in the section on the method of producing the copolymerized polyamide.

[0077] The homopolyamide (B) content in the copolymerized polyamide composition is 50 to 96% by weight. When the homopolyamide (B) content is within the above range, the composition can exhibit excellent physical properties.

[0078] Furthermore, the copolymerized polyamide composition according to the embodiment of the present invention may contain an impact reinforcement agent (C).

[0079] In embodiments of the present invention, the impact reinforcer (C) may be a thermoplastic elastic body grafted with maleic anhydride. More specifically, the impact reinforcer (C) may comprise at least one selected from the group consisting of ethylene-propylene rubber, ethylene-1-butene rubber, ethylene-butylene rubber, ethylene-1-pentene rubber, ethylene-1-hexene rubber, ethylene-1-heptene rubber, ethylene-1-octene rubber, and ethylene-4-methyl-1-pentene rubber, all grafted with maleic anhydride. Preferably, the impact reinforcer (C) is ethylene-butylene rubber grafted with maleic anhydride.

[0080] The maleic anhydride content in a thermoplastic elastomer grafted with maleic anhydride may be 0.1 to 1% by weight.

[0081] The content of impact reinforcement agent (C) in the copolymerized polyamide composition is 0 to 20% by weight.

[0082] In embodiments of the present invention, the copolymerized polyamide composition may further contain additive (D) in an amount of 3 parts by weight or less per 100 parts by weight of components (A) to (C). In this case, additive (D) may include at least one selected from the group consisting of antioxidants, heat stabilizers, neutralizing agents, weather stabilizers, antistatic agents, lubricants, slip agents, pigments, and dyes.

[0083] In one exemplary embodiment, additive (D) is a phenolic (phenol) antioxidant, BHT (butylated hydroxytoluene), which is a primary antioxidant that removes radicals and improves processing thermal stability. (N,N'-Hexane-1,6-diyrbis(3-(3,5-di-tert.-butyl-4-hydroxyphenylpropionamide))) , Octadecyl-3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate , Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) , 1,3,5-Tris(3,5-di-tert.-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione As a phosphorus-based antioxidant, which is a secondary antioxidant that decomposes peroxides generated by the primary antioxidant. Tris(2,4-di-tert-butylphenyl) phosphiteIt may contain at least one antioxidant selected from among the following.

[0084] In an exemplary embodiment, additive (D) is sodium hypophosphate (N), which is a phosphorus-based heat stabilizer. aH It may include 2PO2.

[0085] The method for producing the copolymerized polyamide composition according to the embodiments of the present invention is not particularly limited, and methods for producing polyamide compositions known in the art to which the present invention belongs can be used as is or with appropriate modifications. The resin components and compounds described above can be freely selected and mixed in any desired order without any particular order restrictions.

[0086] Specifically, for example, the aforementioned resins and additives can be melted and extruded in the required amounts using a single-screw / twin-screw extruder at a temperature of 160-230°C to produce a copolymerized polyamide composition in pellet form.

[0087] Furthermore, according to yet another embodiment of the present invention, a molded article of a copolymerized polyamide produced by molding the copolymerized polyamide or copolymerized polyamide composition of the present invention is provided.

[0088] The method for producing molded articles from copolymerized polyamide or copolymerized polyamide compositions according to embodiments of the present invention is not particularly limited, and methods known in the art to which the present invention belongs can be used. For example, copolymerized polyamide molded articles can be produced by molding copolymerized polyamide or copolymerized polyamide compositions according to embodiments of the present invention using conventional methods such as injection molding, extrusion molding, casting, blow molding, rotational molding, and film molding.

[0089] Molded articles of copolymerized polyamide according to embodiments of the present invention exhibit excellent mechanical properties, low-temperature properties, and gas barrier properties. Therefore, these copolymerized polyamide molded articles can be usefully used in automotive parts, environmental materials, tank liners such as hydrogen tank liners, containers, building materials, electrical and electronic components, aerospace, drones, food and functional packaging, housings, and energy materials (batteries, wind / solar power). [Examples]

[0090] Example 1-1 340 g of sebacic acid was packed into a reactor equipped with a stirrer, and the reactor was heated to 150°C while purging with nitrogen to melt the sebacic acid. The molten sebacic acid was stirred, and while the vaporizing components were distilled, m-xyl was added using a dropping funnel. Ri 204 g of rediamine (m-XDA) was added dropwise over 2 hours, and the reaction mixture was stirred for 1 hour. The reaction product was washed with 2 liters of ethanol, filtered, and dried to obtain the polyamide salt. The relative viscosity (in sulfuric acid) of the obtained polyamide salt was 1.5.

[0091] In a reactor equipped with a stirrer, add 160 g of the polyamide salt obtained above, 1,440 g of caprolactam, and sodium hypophosphate (N aH 12.43g of 2PO2 was added, and the reaction mixture was heated at 240°C while purging the reactor with nitrogen until it melted.

[0092] The reaction mixture was heated at 260°C for 3 hours while stirring at a speed of 10 rpm or more, with the reactor pressure maintained at 4 bar or less. Next, the reaction mixture was reacted at 260°C for 1 hour while maintaining the reactor pressure at 0.01 bar using a vacuum pump. After the reaction was complete, the reactor was purged with nitrogen and cooled to obtain the copolymerized polyamide. The relative viscosity (sulfuric acid) of the obtained copolymerized polyamide was 3.7.

[0093] Examples 1-2 A copolymerized polyamide was obtained in the same manner as in Example 1-1, except that 1,181 g of the polyamide salt obtained in Example 1-1 and 418 g of caprolactam were used. The relative viscosity (sulfuric acid) of the obtained copolymerized polyamide was 4.0.

[0094] Comparative Example 1-1 The flask was maintained at 70°C under vacuum to remove moisture. After releasing the vacuum from the flask, 500g of caprolactam (Cl), 0.318g of sodium hydride (NaH), and 18.85g of ethylene bis-stearamide were added, and the temperature was raised to 165°C under vacuum. The reaction temperature was set to 240°C, and hydrogen gas generated as the raw materials melted was removed while nitrogen gas was added. 2.30g of toluene diisocyanate (TDI) was added, and the reaction was allowed to proceed for 20 minutes. After 20 minutes, 50ml of formic acid aqueous solution (formic acid:distilled water = 1:1, v / v) was added to the flask to terminate the reaction, yielding 485g of polymerized polyamide. The relative viscosity (sulfuric acid) of the obtained polyamide was 2.9.

[0095] Test example The physical properties of the polyamide resins obtained in the above examples and comparative examples were measured by the following method, and the results are shown in Table 1.

[0096] The relative viscosity of each polyamide resin or composition was measured at 25°C using a UVS basic instrument manufactured by UFIT AG. Specifically, 1 g of the resin or composition was dissolved in 100 ml of 96% H2SO4. The falling time in a specific section of the viscometer was measured, and after measuring the falling time t0 of the H2SO4 standard solution and the falling time t of each sample, the relative viscosity (RV) of the resin was determined by t / t0.

[0097] Furthermore, test specimens were prepared by injection molding each polyamide resin or composition, and their tensile properties were measured according to ISO 527, while their impact properties were measured according to ISO 179 / 1eA.

[0098] [Table 1]

[0099] Example 2-1 10 g of copolymerized polyamide obtained in Example 1-1, 72.5 g of polyamide (PA6, relative viscosity 2.9) produced from caprolactam, and 17.5 g of ethylene-butylene rubber (Mitsubishi Chemical, MH5020C) grafted with maleic anhydride were used to add 0.1 g of Irganox 1098 as a primary antioxidant and as a secondary antioxidant. Tris(2,4-di-tert-butylphenyl) phosphite After adding 0.5 g and 0.25 g of a phosphorus-based heat stabilizer (NaH2PO2), the copolymerized polyamide composition was produced by extruding it at 250°C using an extruder.

[0100] Example 2-2 A copolymerized polyamide composition was prepared in the same manner as in Example 2-1, except that a polyamide produced from the copolymerized polyamide obtained in Example 1-2 and caprolactam was used.

[0101] The physical properties of the copolymerized polyamide compositions obtained in the above examples were measured using the method described above, and the results are shown in Table 2.

[0102] [Table 2] [Industrial applicability]

[0103] As can be seen from Tables 1 and 2 above, copolymerized polyamides according to embodiments of the present invention and compositions containing the same exhibit excellent mechanical properties such as tensile properties and impact resistance.

Claims

1. (A) Copolymerized polyamide 4-50% by weight; (B) 50 to 96% by weight of homopolyamide produced from lactam or α,ω-aminocarboxylic acid; and (C) Impact reinforcement agent 0-20% by weight A copolymerized polyamide composition comprising, Copolymerized polyamides are - The process includes (1) the step of condensing a diamine and a dicarboxylic acid to produce a polyamide salt, and (2) the step of copolymerizing a lactam or α,ω-aminocarboxylic acid with a polyamide salt. The equivalent ratio of dicarboxylic acid to diamine is 1.05 to 1.0, and the molar ratio of lactam or α,ω-aminocarboxylic acid to repeating units derived from the diamine and dicarboxylic acid of the polyamide salt is 96:4 to 50:

50. In step (1) above, the dicarboxylic acid is sebaic acid and the diamine is m-xylylenediamine, and the product is manufactured by the manufacturing method described above. A copolymer polyamide composition comprising: (a) a first structural unit derived from a lactam or α,ω-aminocarboxylic acid; (b) a second structural unit derived from m-xylylenediamine, an aromatic diamine; and (c) a third structural unit derived from sebacic acid, an aliphatic dicarboxylic acid having 10 or more carbon atoms, wherein the content of the first structural unit is 50 to 96 mol%, and the total content of the second and third structural units is 4 to 50 mol%.

2. The copolymerized polyamide composition according to claim 1, wherein the polyamide salt obtained in step (1) of the method for producing the copolymerized polyamide has a relative viscosity of 1 to 2 (sulfuric acid).

3. In step (2) of the method for producing the copolymerized polyamide, the lactam is laurolactam, caprolactam, piperidone, pyrrolidone, enantholactam, capryllactam, propiolactam, valerolactam. The copolymer polyamide composition according to claim 1, comprising at least one selected from the group consisting of olactam, heptanolactam, octanolactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam.

4. The copolymerized polyamide composition according to claim 1, wherein in step (2) of the method for producing the copolymerized polyamide, the α,ω-aminocarboxylic acid comprises at least one selected from the group consisting of aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

5. The copolymerization in step (2) of the method for producing the copolymerized polyamide is carried out in the presence of a phosphorus-based compound as a heat stabilizer and a catalyst, according to claim 1.

6. The copolymerized polyamide composition according to claim 5, wherein in step (2) of the method for producing the copolymerized polyamide, the phosphorus compound is a hypophosphite compound or a phosphite compound.

7. The copolymer polyamide composition according to claim 1, wherein the impact reinforcing agent (C) comprises at least one selected from the group consisting of ethylene-propylene rubber, ethylene-1-butene rubber, ethylene-butylene rubber, ethylene-1-pentene rubber, ethylene-1-hexene rubber, ethylene-1-heptene rubber, ethylene-1-octene rubber, and ethylene-4-methyl-1-pentene rubber, to which maleic anhydride is grafted.

8. The copolymer polyamide composition according to claim 1, further comprising additive (D) in an amount of 3 parts by weight or less per 100 parts by weight of components (A) to (C).

9. The copolymer polyamide composition according to claim 8, wherein additive (D) comprises at least one selected from the group consisting of antioxidants, heat stabilizers, neutralizing agents, weather stabilizers, antistatic agents, lubricants, slip agents, pigments, and dyes.

10. Additive (D) is a phenolic antioxidant, BHT (butylated hydroxytoluene), N,N'-hexane-1,6-diirbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and 1,3,5-tris(3,5-di-tert. A primary antioxidant selected from (-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, a secondary antioxidant which is tris(2,4-di-tert-butylphenyl) phosphite, and sodium hypophosphate (NaH) ２ PO ２ The copolymer polyamide composition according to claim 9, comprising a heat-resistant stabilizer.

11. A molded article of copolymerized polyamide, produced by molding the copolymerized polyamide composition described in claim 1.

12. A copolymer polyamide molded article according to claim 11, for use in automotive parts, environmental materials, tank liners, containers, building materials, electrical and electronic components, aerospace, drones, food and functional packaging, housings, and energy materials.

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