KR101393281B1 - Polyamide resin composition having the good heat-resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to a polyamide resin produced by polymerizing an aliphatic diamine monomer mixture (A) and a polyester resin (B), wherein the aliphatic diamine monomer mixture (A) is an aliphatic diamine monomer having 2 to 6 carbon atoms (a1) and an aliphatic diamine monomer (a2) having 6 to 12 carbon atoms as a monomer having a different carbon number from the aliphatic diamine monomer (a1), and a process for producing the same. The polyamide resin of the present invention has excellent heat resistance, low hygroscopicity and excellent color.

Description

TECHNICAL FIELD The present invention relates to a polyamide resin having excellent heat resistance and a method for preparing the same.

More particularly, the present invention relates to a polyamide resin having excellent heat resistance including a polyester resin and an aliphatic diamine monomer mixture composed of two aliphatic diamine monomers having different carbon numbers, and a method for producing the same .

In general, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are best known as polyester resins. This type of polyester resin is processed in various ways and is widely used in everyday life such as films, fibers, bottles, and packing materials. Such a polyester resin is discarded after use and is separated and collected as a primary product, but it is almost impossible to properly recycle it. For this reason, there is a need for a method of recycling an enormous amount of waste polyester resin by an appropriate method. As a method of recycling such a waste polyester resin, a method of converting a polyester resin containing a low-priced recycled polyester resin into a heat-resistant polyamide resin of high added value through an appropriate reaction is proposed. Such heat-resistant polyamide resins are widely used in automobile parts, electric appliances, electronic products, and machine parts, which require high heat resistance.

Examples of the method for converting such a polyester resin into a polyamide resin are disclosed in U.S. Patent Nos. 6,383,181, 5,837,803, 4,317,615, and 3,664,577, and have an intrinsic viscosity of 0.2 dl / g or more of a linear polyester resin and a diamine compound to prepare a polyester amide resin substituted with a polyamide resin or a partially amide group. In the process for producing such polyamides, a carboxylic acid activator or an inorganic salt is used as a reaction catalyst in the reaction step to promote the reaction, or methylpyrrolidone (NMP ), Normal dodecylbenzene, orthodichlorobenzene, sulfolane, or the like, or the type of amine to be reacted is limited to hexamethylenediamine or paraphenylenediamine. Particularly, since the above methods proceed with the amidation reaction in the solvent, there is a disadvantage that the solvent used together with the reactant after the reaction must be recovered.

Korean Patent No. 2002-70589 includes a batch reaction process for reacting a polyester resin with a diamine compound in the presence of an organic solvent and an esterification reaction catalyst, and a semi-batch reaction process for polycondensing a batch reaction product while removing glycol components. At this time, instead of providing a high vacuum for promoting evaporation and removal of the glycol component, nitrogen gas is introduced into the reactor to remove the glycol component. However, this method is a method for producing polyarylpolyphenylene terephthalamide as a wholly aromatic polyamide by using an esterification reaction catalyst on n-decylbenzene, and it has a high heat resistance but poor workability, There is a limit to use as automobile parts, electric, electronic products, and machine parts.

An object of the present invention is to provide a polyamide resin excellent in heat resistance.

Another object of the present invention is to provide a polyamide resin having low hygroscopicity and excellent color.

It is still another object of the present invention to provide a method for producing a polyamide resin having excellent heat resistance.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention relates to an aliphatic diamine monomer (a1) having 2 to 6 carbon atoms and an aliphatic diamine monomer (a1) having 6 to 12 carbon atoms and having a different carbon number from the aliphatic diamine monomer (A) an aliphatic diamine monomer mixture comprising a diamine monomer (a2); And a polyester resin (B).

As an embodiment of the present invention, the present invention provides a polyester resin (B) wherein the ester group of the polyester resin (B) reacts with the aliphatic diamine monomer (a1) or (a2) A polyamide resin is provided.

(A / B) of the total molar number of the aliphatic diamine monomer mixture (A) and the total molar number of the polyester resin (B) is from 0.90 to 1.50, as another embodiment of the present invention. do.

In another embodiment of the present invention, the polyamide resin of the present invention further comprises an endcapping agent, which is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, But are not limited to, monocarboxylic acids such as acetic acid, acetic acid, propionic acid, glycolic acid, glycolic acid, lactic acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutylic acid, An aliphatic ester compound selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, 2-ethoxy ethyl acetate, and mixtures thereof, or a mixture of methyl benzoate, ethyl benzoate, Polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetramethylene glycol,

(A1) having a carbon number of 2 to 6 or less, and a monomer having a carbon number different from that of the aliphatic diamine monomer (a1) (A) an aliphatic diamine monomer mixture comprising not more than 12 aliphatic diamine monomers (a2); And a polyester resin (B), a terminal sealing agent (C), and a phosphorous-based catalyst in a reactor and stirring at 120 to 140 ° C for 2 hours; And

Maintaining the temperature for 2 to 4 hours while increasing the temperature to 140 to 180 DEG C and then performing the decompression step for 3 to 22 hours at a temperature of 180 to 200 DEG C and a pressure of 2 to 10 mbar to evaporate the ethylene glycol component as a by- And a second step of removing the polyamide resin from the polyamide resin.

The polyamide resin of the present invention has excellent heat resistance, low hygroscopicity, and excellent color.

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

The process for producing a heat-resistant polyamide resin according to the present invention comprises reacting a finely pulverized polyester resin with a compound containing at least one diamine monomer, without using an organic solvent, so that the ester group in the polyester is completely or partially amidated Based on the weight of the polyamide resin.

The present invention relates to an aliphatic diamine monomer (a1) having an aliphatic diamine monomer (a1) having a good reactivity and having 2 to 6 carbon atoms and an aliphatic diamine monomer (a1) having a carbon number different from that of the aliphatic diamine monomer a2), and at the same time, a polyester resin (B) is used to obtain a polyamide resin having an ester group reacted with a diamine to completely or partially amidify the polyamide resin with excellent heat resistance and low water absorption properties.

In an embodiment of the present invention, the polyester resin (B) is polyethylene terephthalate, and the aliphatic diamine monomer mixture (A) comprises an aliphatic diamine monomer (al) and an aliphatic diamine monomer (a2). The aliphatic diamine monomer (a1) has 2 to 6 carbon atoms and the other aliphatic diamine monomer (a2) has 6 to 12 carbon atoms. The aliphatic diamine monomers (a1) and (a2) selected within the above-mentioned carbon number range are mixed so that the carbon numbers are different from each other. Is contained in an amount of 30 to 70 mol% based on the polyamide resin as the aliphatic diamine monomer mixture (A).

The ratio A / B of the total molar number of the diamine monomer mixture (A) to the total molar number of the polyester resin (B) (calculated on the basis of the repeating unit) is 0.90 to 1.50.

The aliphatic diamine monomers (a1) and (a2) may have a linear or branched structure.

The aliphatic diamine monomer (a1) specifically includes 1,2-ethanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, , 5-pentanediamine, and the like.

The aliphatic diamine monomer (a2) specifically includes 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl- (Ethylamine), bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether (EGBA), 1,6- Diamino-3,5-dioxoheptane, 1,10-diamino-4,7-dioxo-undecane, 1,10-diamino-4,7- -Undecanediamine, 1,12-dodecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine and the like.

The polyester resin (B) can be used without limitation if it is an aromatic or aliphatic polyester resin, but it is preferable to use an aromatic polyester resin, more preferably a polyethylene terephthalate resin.

The polyamide resin of the present invention may further comprise an end capping agent (C). By controlling the amount of the end capping agent (C) to be used and the timing of introduction thereof, the viscosity of the polyamide resin after the amidation reaction, The number of amide ends, and the degree of amidation (DA-degree of amidation).

The intrinsic viscosity [?] Of the polyamide resin of the present invention is preferably (0.2 dL / g) to (4.0 dL / g), and the number of amine terminals is preferably 30 μeq / g to 1,000 μeq / g.

The end-capping agent used in the present invention may be an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic ester compound, or an aromatic ester compound. More specifically, aliphatic carboxylates such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, And aromatic carboxylic acids such as acid or benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and the like. The end-capping agents listed above may be used alone or in combination of two or more. Also, aliphatic ester compounds such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, 2-ethoxy ethyl acetate and the like, and aliphatic ester compounds such as methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate and the like The same aromatic ester compound may be used, or two or more of the above-mentioned examples may be used in combination.

The end-capping agent used in the production of the polyamide resin of the present invention may contain 0.01 to 10.0 parts by weight, preferably 0.01 to 5.0 parts by weight, based on 100 parts by weight of the polyester resin (B).

Manufacturing method

The process for producing a polyamide resin of the present invention is a process for producing a polyamide resin having excellent chemical resistance by applying solid-state polymerization in which a polar solvent for reaction is used without any polar solvent, . The conditions for producing the polyamide resin of the present invention are as follows.

First, an aliphatic diamine monomer mixture (A) and (B) containing an aliphatic diamine monomer having different numbers of carbon atoms from each other are initially introduced into a reactor, and an end capping agent, a catalyst, Lt; 0 > C for 2 hours. And the temperature is maintained for 2-4 hours while increasing to 140-180 ° C. Thereafter, the step of decompressing is switched to evaporate off components such as ethylene glycol, which is a by-product of the reaction. At this time, the temperature is preferably 180-200 DEG C, and the reaction by-products are removed while maintaining the pressure within 10 mbar, more preferably within 2 mbar for 3 to 20 hours.

The polyamide thus obtained can be solid-phase-polymerized at a temperature between its glass transition temperature (T _g ) and its melting temperature (T _m ) under vacuum for 10 to 30 hours to increase the amidation reaction rate and viscosity of the polymer. The polymerization temperature at this time is preferably 180 to 250 ° C, more preferably 200 to 230 ° C.

The catalyst used in the present invention may be a phosphorus-based catalyst. Specifically, phosphonic acid, phosphorous acid, hypophosphorous acid or a salt or derivative thereof may be used. As a more specific example, phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphonate and the like can be used.

The catalyst used for producing the polyamide resin of the present invention is preferably used in an amount of 0.01 to 3.0 parts by weight, preferably 0.01 to 1.0 part by weight, more preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the polyester resin .

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

A 1-liter autoclave was charged with 100 parts by weight of PET, 13.1 parts by weight of 1,2-ethanediamine, 38.1 parts by weight of 1,6-hexanediamine, 6.36 parts by weight of benzoic acid, and 0.16 part by weight of sodium high- And purged several times to remove oxygen. Thereafter, the reactor was sealed, stirred at 120 ° C for 2 hours, heated at 140 ° C for 30 minutes, and reacted at this temperature for 2 hours. Thereafter, the temperature was raised at 180 DEG C for 60 minutes, and the temperature was reduced to a reduced pressure while maintaining the temperature at this temperature for 4 hours. Ethylene glycol was removed under a reduced pressure of 2 mbar or less to recover 30 parts by weight of ethylene glycol. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.20 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.0 dL / g.

Example 2

Except that 100 parts by weight of PET, 19.1 parts by weight of 1,4-butane diamine, 37.7 parts by weight of 1,6-hexane diamine, 5.1 parts by weight of benzoic acid, and 0.16 part by weight of sodium high- A polyamide prepolymer was prepared. After completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.23 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.05 dL / g.

Example 3

Except that 100 parts by weight of PET, 37.3 parts by weight of 1,6-hexanediamine, 31.0 parts by weight of 1,8-octanediamine, 3.8 parts by weight of benzoic acid, and 0.17 parts by weight of sodium hyphaphosphinate was used A polyamide prepolymer was prepared. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.22 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.98 dL / g.

Example 4

Except that 100 parts by weight of PET, 43.1 parts by weight of 1,6-hexane diamine, 27.5 parts by weight of 1,10-decane diamine, 2.5 parts by weight of benzoic acid, and 0.17 part by weight of sodium hyphaphosphinate were used A polyamide prepolymer was prepared. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.20 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.02 dL / g.

Example 5

Except that 100 parts by weight of PET, 42.7 parts by weight of 1,6-hexane diamine, 31.6 parts by weight of 1,12-dodecanediamine, 1.27 parts by weight of benzoic acid, and 0.18 part by weight of sodium high- To prepare a polyamide prepolymer. After completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.23 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.01 dL / g.

Example 6

Example 1 was repeated except that 100 parts by weight of PET, 13.1 parts by weight of 1,2-ethanediamine, 38.1 parts by weight of 1,6-hexanediamine, 7.1 parts by weight of methylbenzoate and 0.16 part by weight of sodium high- To prepare a polyamide prepolymer. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.22 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 DEG C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.04 dL / g.

Example 7

A 1-liter autoclave was charged with 100 parts by weight of PET, 13.1 parts by weight of 1,2-ethanediamine, 38.1 parts by weight of 1,6-hexanediamine, 6.36 parts by weight of benzoic acid, and 0.16 part by weight of sodium high- And purged several times to remove oxygen. After sealing the reactor, the mixture was stirred at 140 ° C for 2 hours, heated at 160 ° C for 30 minutes, and reacted at this temperature for 2 hours. Thereafter, the temperature was raised at 180 DEG C for 60 minutes, and the temperature was reduced to a reduced pressure while maintaining the temperature at this temperature for 4 hours. Ethylene glycol was recovered under reduced pressure of 2 mbar or less. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.28 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 DEG C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.08 dL / g.

Example 8

A polyamide prepolymer was obtained in the same manner as in Example 1, except that 100 parts by weight of PET, 43.1 parts by weight of 1,6-hexane diamine, 27.5 parts by weight of 1,10-decane diamine, and 0.17 part by weight of sodium high- . After the completion of the reaction, the polyamide prepolymer having an intrinsic viscosity of 0.25 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.24 dL / g.

Comparative Example 1

A polyamide prepolymer was prepared in the same manner as in Example 1, except that 100 parts by weight of PET, 62.2 parts by weight of 1,6-hexane diamine, 3.8 parts by weight of benzoic acid, and 0.17 part by weight of sodium highphosphonate was used. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.15 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.35 dL / g.

Comparative Example 2

Except that 100 parts by weight of PET, 13.1 parts by weight of 1,2-ethanediamine, 28.9 parts by weight of 1,4-butane diamine, 6.4 parts by weight of benzoic acid, and 0.15 parts by weight of sodium high- A polyamide prepolymer was prepared. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.10 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.21 dL / g.

Comparative Example 3

A polyamide prepolymer was prepared in the same manner as in Example 7, except that the reactor was sealed, stirred at 80 ° C for 2 hours, heated at 100 ° C for 30 minutes, and reacted at this temperature for 2 hours. After the completion of the reaction, a polyamide prepolymer having an intrinsic viscosity of 0.05 dL / g was recovered.

The polyamide prepolymer obtained by the above method was further subjected to solid state polymerization at 230 캜 for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.15 dL / g.

Property evaluation

The polyamide resin prepared in the Examples and Comparative Examples was measured for thermal properties, intrinsic viscosity and end groups of the sample obtained before and after the solid-phase polymerization. Thermal properties were measured by different scanning calorimeter (DSC) and thermogravimetric analyzer (TGA). The intrinsic viscosity was determined by dissolving the polyamide in a concentrated sulfuric acid solution (98%) and then measuring the intrinsic viscosity using a Ubbelodhde viscometer at 25 ° C. Acid end-of-term measurement was completely dissolved in o -cresol and measured with a 0.1 N KOH solution in a potential difference meter. The amine end-of-term measurement was completely dissolved in hexafluoroisopropanol and measured using a potentiometer using 0.1 N HCl solution .

Moisture absorption rate was 100mm in length, 100mm in width and 3mm in thickness. After the dried weight (W ₀ ) was measured, the specimens were treated at 80 ° C and 90% RH for 48 hours in a thermostat, and the weight (W ₁ ) was measured.

Water absorption rate (%) = [(W ₁ -W ₀ ) / W ₀ ] * 100

The L * value was measured using a colorimeter based on the criteria defined in ASTM D 1209 for the brightness measurement.

Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 PET 100 100 100 100 100 100 100 100 100 100 100 1,2- Ethanediamine 13.1 - - - - 13.1 13.1 - - 13.1 13.1 1,4- Butanediamine - 19.1 - - - - - - - 28.9 - 1,6- Hexanediamine 38.1 37.7 37.3 43.1 42.7 38.1 38.1 43.1 62.2 - 38.1 1,8- Octanediamine - - 31.0 - - - - - - - - 1,10- Decane diamine - - - 27.5 - - - 27.5 - - - 1,12- Dodecanediamine - - - - 31.6 - - - - - - Benzoic acid 6.36 5.1 3.8 2.5 1.27 - 6.36 - 3.8 6.4 6.36 Methyl benzoate - - - - - 7.1 - - - - - Sodium hypo
Phosphinate 0.16 0.16 0.17 0.17 0.18 0.16 0.16 0.17 0.17 0.15 0.16 Melting temperature (캜) 300 295 290 320 318 303 305 310 Fail Fail Fail Crystallization temperature (캜) 260 263 265 298 297 261 265 280 Fail Fail Fail Pyrolysis temperature (℃) 430 435 440 444 445 435 435 440 418 420 417 Intrinsic viscosity (dL / g) 1.00 1.05 0.98 1.02 1.01 1.04 1.08 1.24 0.35 0.21 0.15 Acid end group
(μeq / g) 80 85 75 60 50 83 75 65 100 105 Fail Amine end group
(μeq / g) 150 130 100 65 40 130 121 150 500 1000 Fail Moisture absorption rate (%) 4.5 4.2 2.8 2.0 1.5 4.4 4.2 2.4 4.0 5.9 6.5 Brightness (L *) 80 85 88 92 95 82 84 90 65 67 63

(Component unit: parts by weight)

It can be confirmed that the polyamide resins of Examples 1 to 8 of the present invention have excellent melting temperature, crystallization temperature and thermal decomposition temperature and excellent heat resistance. It can be seen that the whiteness is excellent and the moisture absorption rate is low, which means that excellent color development is possible in place. Also, it can be seen that the number of terminal groups of Acid and Amin is lower than that of Comparative Example.

In Comparative Example 1, an aliphatic diamine monomer of 1, 6 hexane diamine having 6 carbon atoms was used. Due to low reactivity, the melting temperature and the crystallization temperature were not measured, and thus heat resistance could not be secured. Also in Comparative Example 2, two kinds of aliphatic monomers having less than 6 carbon atoms were used, and heat resistance was not secured as in Comparative Example 1. [

Comparative Example 3 was conducted in the solid phase polymerization step after obtaining the polyamide prepolymer, but as experimental examples deviating from the preferable polymerization temperature and polymerization time range in the solid phase polymerization step of the present invention, the melting temperature, crystallization Temperature, and acid and amin end groups can not be measured.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (17)

A polyamide resin produced by polymerizing an aliphatic diamine monomer mixture (A) and a polyester resin (B)
Wherein the aliphatic diamine monomer mixture (A) comprises an aliphatic diamine monomer (a1) having 2 to 6 carbon atoms and an aliphatic diamine monomer (a1) having 6 to 12 carbon atoms and having a different carbon number from the aliphatic diamine monomer And contains monomer (a2)
The aliphatic diamine monomer (a1) having the number of carbon atoms of 2 to 6 or less and the aliphatic diamine monomer (a2) having 6 to 12 carbon atoms may be used in an amount of 10 to 60 By weight of the polyamide resin.
delete The poly (arylene ether) resin composition according to claim 1, wherein the ester group of the polyester resin (B) reacts with the aliphatic diamine monomer (a1) or (a2) to have an amine terminal number of 30 μeq / g to 1,000 μeq / Amide resin.
The polyamide resin composition according to claim 1, wherein the ratio A / B of the total molar number of the aliphatic diamine monomer mixture (A) to the total molar number (based on the repeating unit) of the polyester resin (B) is 0.90 to 1.50 .
The polyimide resin composition according to claim 1, wherein the aliphatic diamine monomer (a1) having 2 to 6 carbon atoms is 1,2-ethanediamine, 1,4-butanediamine, 1,5- Pentane diamine, 3-methyl-1,5-pentane diamine, and mixtures thereof.
The aliphatic diamine monomer (a2) according to claim 1, wherein the aliphatic diamine monomer having 6 to 12 carbon atoms is 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, Diamine, 1,11-undecanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6- hexanediamine, 1,6-hexanediamine, 5-methyl-1,9-nonanediamine, 2,2-oxybis (ethylamine), bis (3-aminopropyl) ether, ethylene glycol bis (EGBA), 1,7-diamino-3,5-dioxoheptane, 1,10-diamino-4,7-dioxo-undecane, 1,10-diamino-4,7- Wherein the polyamide resin is selected from the group consisting of methylenebisacrylamide, methyldecane, 1,11-undecane diamine, 1,12-dodecane diamine, 2-butyl- .
The polyamide resin according to claim 1, wherein the polyester resin (B) is an aliphatic polyester resin or an aromatic polyester resin.
The polyamide resin according to claim 7, wherein the polyester resin (B) is a polyethylene terephthalate (PET) resin.
The method of claim 1, wherein the polyamide resin further comprises an endcapping agent (C), wherein the endblocking agent is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, methyl acetate, stearic acid, stearic acid, pivalic acid, isobutylic acid, benzoic acid, toluic acid, -naphthalenecarboxylic acid, , Aliphatic ester compounds selected from the group consisting of ethyl acetate, propyl acetate, butyl acetate, amyl acetate, 2-ethoxy ethyl acetate, and mixtures thereof, or aliphatic ester compounds such as methyl benzoate, Pentyl benzoate, and mixtures thereof. ≪ RTI ID = 0.0 > 11. < / RTI >
The polyamide resin according to claim 9, wherein the amine terminal number of the polyamide resin is 30 μeq / g to 200 μeq / g.
The polyamide resin according to claim 9, wherein the end sealant (C) is contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the polyester resin (B).
The polyamide resin according to claim 1, wherein the polyamide resin has an intrinsic viscosity of 0.2 dL / g to 4.0 dL / g.
An aliphatic diamine monomer (a1) having 2 to 6 carbon atoms and an aliphatic diamine monomer (a2) having 6 to 12 carbon atoms as a monomer having a different carbon number from the aliphatic diamine monomer (a1) Monomer mixture (A); A polyester resin (B); An end encapsulant (C); And a phosphorous-based catalyst into a reactor and stirring the mixture at 120 to 140 DEG C for 2 hours; And
Maintaining the temperature for 2 to 4 hours while increasing the temperature to 140 to 180 DEG C and then performing the decompression step for 3 to 22 hours at a temperature of 180 to 200 DEG C and a pressure of 2 to 10 mbar to evaporate the ethylene glycol component as a by- And a second step of removing the polyamide resin.
14. The polyamide resin according to claim 13, wherein after the second step, solid phase polymerization is carried out at a polymerization temperature of 180 to 250 DEG C and a vacuum state for 10 to 30 hours to increase amidation degree and viscosity of the polyamide resin Gt;
14. The process according to claim 13, wherein the catalyst is selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite, sodium hyphaphosphonate and mixtures thereof .
14. The toner according to claim 13, wherein the aliphatic diamine monomer (a1) having 2 to 6 carbon atoms relative to 100 parts by weight of the polyester resin (B) is 10 to 60 parts by weight, the aliphatic group having 6 to 12 carbon atoms Wherein the diamine monomer (a2) is contained in an amount of 10 to 60 parts by weight, and the end capping agent (C) is contained in an amount of 0.01 to 10.0 parts by weight.
14. The method for producing a polyamide resin according to claim 13, wherein the catalyst is contained in an amount of 0.01 to 3.0 parts by weight based on 100 parts by weight of the polyester resin (B).