METHOD FOR PRODUCING POLYAMIDE USING TERMINAL ENCAPSULANT AND POLYAMIDE PRODUCED THEREBY

Abstract

Provided are a method for producing a polyamide using an end-capping agent and a polyamide produced thereby, wherein the method is an eco-friendly process method without using a solvent as a catalyst and may prepare, by using an end-capping agent for suppressing side reaction, a polymer having a uniform molecular weight and a high conversion rate at a low temperature within a short polymerization time in comparison with a conventional polymerization method.

Claims

1. A method for producing a polyamide by an anionic polymerization reaction using an end-capping agent, wherein lactam, and based on 100 parts by weight of the entire lactam, 0.01 parts by weight to 20 parts by weight of an alkali metal as an initiator, 0.002 parts by weight to 1.0 part by weight of an activator, and 0.1 parts by weight to 100 parts by weight of an amine-based, urea-based, or alcohol-based end-capping agent are included.

2. The method of claim 1, wherein the end-capping agent comprises at least one selected from the group consisting of compounds represented by Formulae 1 and 2:
R.sub.1(CH.sub.2).sub.xR.sub.2(CH.sub.2).sub.yR.sub.3[Formula 1] wherein R.sub.1, R.sub.2, and R.sub.3 are each independently a primary, secondary, tertiary, or quaternary amine, alcohol, amide, ether, alkyl, or aryl, and x, y, or z is an integer from 1 to 20,
R.sub.1(CH.sub.2).sub.xR.sub.2(CH.sub.2).sub.yR.sub.3(CH.sub.2).sub.zR.sub.4[Formula 2] wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently a primary, secondary, tertiary, or quaternary amine, alcohol, amide, ether, alkyl, or aryl, and x, y, or z is an integer from 1 to 20.

3. The method of claim 1, wherein the polymerization is performed in a temperature range of 140 C. to 250 C.

4. The method of claim 1, wherein the activator comprises at least one selected from the group consisting of carbon dioxide (CO.sub.2), benzoyl chloride, N-acetyl caprolactam, N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and any mixture thereof.

5. The method of claim 1, wherein the end-capping agent comprises at least one selected from the group consisting of aliphatic amine, aromatic amine, aliphatic urea, aromatic urea, aliphatic alcohol, and aromatic alcohol-based compounds.

6. The method of claim 5, wherein the end-capping agent comprises 0.001 mol % to 1.0 mol % relative to 1 mol of the lactam.

7. The method of claim 1, wherein an N/C ratio of the amine-based or urea-based end-capping agent is in a range of 0.05 to 1.0.

8. The method of claim 1, wherein an O/C ratio of the alcohol-based end-capping agent is in a range of 0.05 to 1.0.

9. The method of claim 1, wherein the alkali metal comprises at least one selected from the group consisting of metal hydride, metal hydroxide, and metal alkoxide.

10. The method of claim 1, wherein at least one selected from the group consisting of ethylene-bis-stearamide (EBS), an amine compound, a urea compound, and a di-urea compound, which are a molecular weight controller, is further included.

11. The method of claim 1, wherein the polymerization reaction is performed in a range of 0.5 minutes to 120 minutes.

12. The method of claim 1, wherein the lactam in the polymerization reaction has a conversion rate of 95% or more.

13. A polyamide produced by the method of claim 1.

14. The polyamide of claim 13, wherein the polyamide has a polydispersity index (PDI) of 3.0 or less.

15. The polyamide of claim 13, wherein a weight average molecular weight (Mw) of the polyamide is in a range of 20,000 to 80,000.

16. A parts material selected from the group consisting of a vehicle material, an electronic device material, an industrial pipe material, a construction engineering material, a 3D printer material, a textile material, a cladding material, a machine tool material, a medical material, an aviation material, a photovoltaic material, a battery material, a sports material, a household appliance material, a household material, and a cosmetic material, which each include the polyamide of claim 13.

Description

BRIEF DESCRIPTION OF DRAWING

[0039] FIG. 1 is a reaction formula showing a process of converting an unstable structure of an end-capping agent and a polymer according to the present invention into a stable structure.

BEST MODE

[0040] The present invention will be described with reference to specific embodiments and the accompanying drawings. The embodiments will be described in detail in such a manner that the present invention may be carried out by those of ordinary skill in the art. It should be understood that various embodiments of the present invention are different, but need not be mutually exclusive. For example, certain shapes, structures, and features described herein may be implemented in other embodiments without departing from the spirit and scope of the present invention in connection with one embodiment.

[0041] Therefore, the following detailed description is not to be taken in a limiting sense, and the scope of the present invention is to be limited only by the appended claims and the entire scope of equivalents thereof, if properly explained.

[0042] In addition, unless otherwise specified in the present specification, the term substitution or substituted means that one or more hydrogen atoms in the functional groups of the present invention are substituted with one or more substituents selected from the group consisting of a halogen atom (F, Cl, Br, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, an ester group, a ketone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group. These substituents may be linked to each other to form a ring.

[0043] In the present invention, unless otherwise specified, the term substituted means that a hydrogen atom is substituted with a substituent such as a halogen atom, a C.sub.1-C.sub.20 hydrocarbon group, a C.sub.1-C.sub.20 alkoxy group, and a C.sub.6-C.sub.20 aryloxy group.

[0044] In addition, unless otherwise specified, the term hydrocarbon group refers to a linear, branched, or cyclic saturated or unsaturated hydrocarbon group. The alkyl group, the alkenyl group, the alkynyl group, and the like may be linear, branched, or cyclic.

[0045] In addition, unless otherwise specified in the present specification, the term alkyl group refers to a C.sub.1-C.sub.30 alkyl group and the term aryl group refers to a C.sub.6-C.sub.30 aryl group. In the present specification, the term heterocyclic group refers to a group in which one to three heteroatoms selected from the group consisting of O, S, N, P, Si, and any combination thereof are contained in one ring. Examples of the heterocyclic group may include pyridine, thiophene, and pyrazine, but the present invention is not limited thereto.

[0046] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings, so that those of ordinary skill in the art can easily carry out the present invention.

[0047] As described above, there have been limitations in limiting the inefficiency of the processing, which is caused by the problems occurring in hydrolytic polymerization, catalytic ring-opening polymerization, and anionic ring-opening polymerization among the conventional polyamide polymerization methods, and the increase in viscosity due to side reactions at high temperature polymerization.

[0048] The present invention is an eco-friendly processing method that uses an amine-based or alcohol-based end-capping agent to control side reaction occurring at the time of producing polyamide anion and uses carbon dioxide (CO2) instead of a solvent as a catalyst, and can prepare a polymer having a uniform molecular weight with a high conversion rate within a short polymerization reaction time at a low temperature in comparison with an existing polymerization method, thereby providing the solution to the above-described problems.

[0049] The present invention provides a method for producing a polyamide by an anionic polymerization reaction using an end-capping agent, wherein lactam, and based on 100 parts by weight of the entire lactam, 0.01 parts by weight to 20 parts by weight of an alkali metal as an initiator, 0.002 parts by weight to 10 parts by weight of carbon dioxide as an activator, and 0.1 parts by weight to 50 part by weight of an amine-based, urea-based, or alcohol-based end-capping agent are included.

[0050] Specifically, compositions included in the production of the polyamide using the end-capping agent according to the present invention will be described below.

[0051] First, the lactam according to the present invention may be preferably used as a monomer for producing the polyamide. However, the present invention is not limited thereto. For example, the lactam may include laurolactam, caprolactam, piperidone, pyrrolidone, enantolactam, and caprylactam. In some cases, the lactam may include propiolactam, 2-pyrroli done, valerolactam, caprolactam, heptanolactam, octanolactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam.

[0052] In addition, the alkali metal catalyst according to the present invention is an initiator for producing the polyamide and may include at least one selected from the group consisting of metal hydride, metal hydroxide, and metal alkoxide as a compound that allows the formation of the lactam anion.

[0053] In a specific example, the metal hydride may include sodium hydride and potassium hydride, the metal hydroxide may include sodium hydroxide and potassium hydroxide, and the metal alkoxide may include potassium tert-butoxide and aluminum isopropoxide, but the present invention is not limited thereto.

[0054] For example, the metal alkoxide may include sodium caprolactamate or potassium caprolactamate, alkaline earth metal caprolactamate, for example, magnesium bromide caprolactamate, magnesium chloride caprolactamate, or magnesium biscaprolactamate, an alkali metal, for example, sodium or potassium, alkali metal base, for example, sodium base, for example sodium hydride, sodium, sodium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, or sodium butanolate, or at least one selected from the group consisting of potassium base, for example potassium hydride, potassium, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium propanolate, potassium butanolate, or any mixture thereof, preferably at least one selected from the group consisting of sodium caprolactate, potassium caprolactate, magnesium bromide caprolactate, magnesium chloride caprolactate, magnesium biscaprolactate, sodium hydride, sodium, sodium hydroxide, sodium ethanolate, sodium methanolate, sodium propanolate, sodium butanolate, potassium hydride, potassium, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium propanolate, potassium butanolate, and any mixture thereof. In addition, at least one selected from the group consisting of sodium hydride, sodium, sodium caprolactamate, and any mixture thereof may be included.

[0055] The metal catalyst may be used in the form of a solid or a solution, and the catalyst is preferably used in the form of a solid. The catalyst is preferably added to a caprolactam melt in which the catalyst can be dissolved. These catalysts lead to particularly rapid reactions, thereby increasing the efficiency of the process of producing the polyamide according to the present invention.

[0056] According to the present invention, an amount of the alkali metal catalyst may be in a range of 0.01 parts by weight to 20 parts by weight based on 100 parts by weight of the entire lactam. The amount of the alkali metal catalyst may be in a range of preferably 0.03 parts by weight to 10 parts by weight, and more preferably 0.05 parts by weight to 2 parts by weight.

[0057] In this case, when the alkali metal catalyst is added in an amount of less than 0.01 parts by weight, unpolymerization may occur or a reaction rate may decrease. When the amount of the alkali metal catalyst exceeds 20 parts by weight, a low-molecular-weight polymer may be generated. Therefore, the above range is preferable.

[0058] In addition, according to the present invention, the end-capping agent is added so as to suppress side reaction generated by anionic polymerization and prevent a gelation phenomenon and includes at least one selected from the group consisting of compounds represented by Formulae 1 and 2.

R.sub.1(CH.sub.2).sub.xR.sub.2(CH.sub.2).sub.yR.sub.3[Formula 1]

[0059] R.sub.1, R.sub.2, and R.sub.3 are each independently a primary, secondary, tertiary, or quaternary amine, alcohol, amide, ether, alkyl, or aryl, and x, y, or z is an integer from 1 to 20.

R.sub.1(CH.sub.2).sub.xR.sub.2(CH.sub.2).sub.yR.sub.3(CH.sub.2).sub.zR.sub.4[Formula 2]

[0060] R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently a primary, secondary, tertiary, or quaternary amine, alcohol, amide, ether, alkyl, or aryl, and x, y, or z is an integer from 1 to 20.

[0061] According to the present invention, the end-capping agent may be included at a molar ratio of 0.001 to 0.5 based on 1 mole of the entire lactam. The end-capping agent may be included at a molar ratio of preferably 0.001 to 0.3, and more preferably 0.001 to 0.25.

[0062] In this case, when the catalyst is added at a molar ratio of less than 0.001, a gelation problem caused by side reaction may occur. When the molar ratio of the catalyst exceeds 0.5, polymerization may not be performed, or a conversion rate may be extremely low even though the polymerization is performed. Therefore, the above range is preferable.

[0063] According to the present invention, when the end-capping agent is an amine-based material, an N/C ratio may be in a range of 0.05 to 1.0. The N/C ratio may be in a range of preferably 0.1 to 0.75, and more preferably 0.15 to 0.7.

[0064] When the end-capping agent is a urea-based material, an N/C ratio may be in a range of 0.05 to 1.0. The N/C ratio may be in a range of preferably 0.1 to 0.8, and more preferably 0.15 to 0.75.

[0065] When the end-capping agent is an alcohol-based material, an O/C ratio may be in a range of 0.05 to 1.0. The 0/C ratio may be in a range of preferably 0.1 to 0.8, and more preferably 0.15 to 0.75.

[0066] In some cases, according to the present invention, a molecular weight controller may be included. The molecular weight controller may be preferably ethylene-bis-stearamide (EBS), but the present invention is not limited thereto. The molecular weight controller may include at least one selected from the group consisting of an amine compound, a urea compound, and a di-urea compound.

[0067] According to the present invention, an amount of the molecular weight controller may be in a range of 0.3 parts by weight to 10 parts by weight based on 100 parts by weight of the entire laurolactam. The amount of the molecular weight controller may be in a range of preferably 0.4 parts by weight to 7.0 parts by weight, and more preferably 0.5 parts by weight to 3.0 parts by weight.

[0068] In this case, when the molecular weight controller is added in an amount of less than 0.3 parts by weight, a high-molecular-weight polymer may be generated or a gelation problem may occur. When the amount of the molecular weight controller exceeds 10 parts by weight, a low-molecular-weight polymer may be generated or unpolymerization may occur. Therefore, the above range is preferable.

[0069] Finally, according to the present invention, the activator may be preferably carbon dioxide (CO2), but the present invention is not limited thereto. For example, the activator may include at least one selected from the group consisting of benzoyl chloride, N-acetyl caprolactam, N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and any mixture thereof.

[0070] In this case, when carbon dioxide is used as the activator, a very high reactivity may cause overpolymerization or side reaction. Therefore, as shown in FIG. 1, the reaction does not occur when the end-capping agent according to the present invention is introduced, thereby preventing side reaction and the like from occurring during anionic polymerization of lactam and making it possible to produce a uniform product.

[0071] According to the present invention, an amount of the carbon dioxide may be in a range of 0.002 parts by weight to 1.0 part by weight based on 100 parts by weight of the entire laurolactam. The amount of the carbon dioxide may be in a range of preferably 0.005 parts by weight to 5 parts by weight, and more preferably 0.01 parts by weight to 0.1 parts by weight.

[0072] In this case, when the carbon dioxide is added in an amount of less than 0.002 parts by weight, unpolymerization may occur or a reaction rate may decrease. When the amount of the carbon dioxide exceeds 1.0 part by weight, a gelation problem may occur. Therefore, the above range is preferable.

[0073] Hereinafter, preferred examples are presented so as to help the understanding of the present invention. However, the following examples are for illustrative purposes only and the present invention is not limited by the following examples.

EXAMPLES

Example 1

[0074] Production of Polymerization Sample Using Hexamethylenediamine as End-Capping Agent (ECA)

[0075] 1 mol % of a conventional initiator NaH was mixed with 20 g of lactam and added to an RB flask. The mixture was heated to 165 C. in a nitrogen atmosphere and sufficiently kneaded for 30 minutes. Then, 0.25 mol % of hexamethylenediamine, which was previously melted using a syringe, was injected and heated to a reaction temperature while kneading. When the reaction temperature was reached, nitrogen was cut off and carbon dioxide (CO2) was injected as an activator to perform the reaction. When the reaction was completed, a solution in which formic acid and distilled water were mixed at a ratio of 1:1 (v) was injected to remove activated anion. Then, a sample having content shown in Table 1 was collected. The sample prepared as above was washed with distilled water and dried in a vacuum oven at 100 C. for 24 hours. Then, a weight of polyamide was measured. and it was put in ethanol as a solvent for 8 hours. Then, after re-drying, a weight was measured to obtain a conversion rate. A result thereof is shown in Table 2.

TABLE-US-00001 TABLE 1 Alkali End-capping Activator Lactam metal agent Amount of Amount of (g) (mol %) (mol %) CO.sub.2 (ml) NAC (ml) Example 1 20 1 0.25 1.7 Example 2 20 1 0.125 1.7 Example 3 20 1 0.125 1.7 Example 4 20 1 0.25 0.14 Comparative 20 1 1.7 Example 1

Example 2

[0076] A polyamide was produced in the same manner as in Example 1, except that dodecylamine was used as an end-capping agent.

Example 3

[0077] A polyamide was produced in the same manner as in Example 1, except that dodecanol was used as an end-capping agent.

Example 4

[0078] A polyamide was produced in the same manner as in Example 1, except that 1 mol % of N-acetyl caprolactam was used as an activator.

COMPARATIVE EXAMPLE

Comparative Example 1

[0079] A polyamide was produced in the same manner as in Example 1, except that an end-capping agent (ECA) was not used. A conversion rate was obtained, and a result thereof is shown in Table 2.

TABLE-US-00002 TABLE 2 Molecular weight Polydispersity Conversion (g/mol) index (PDI) rate (%) Example 1 73,500 2.2 98.4 Example 2 69,700 2.2 98.1 Example 3 71,800 2.3 98.9 Example 4 77,300 2.3 98.4 Comparative 1,254,000 No Gelation Example 1 measurement

[0080] As shown in Table 2, Example 4 in which the end-capping agent was included with respect to the lactam and NAC was used as the activator had a slightly lower molecular weight and a wide molecular weight distribution, compared with Examples 1, 2, and 3.

[0081] In addition, Comparative Example in which the end-capping agent was not included with respect to the lactam exhibited a gelation phenomenon such that a very high molecular weight and a molecular weight distribution could not be measured, compared with Example 1.

[0082] Although the present invention has been described with reference to the drawings according to embodiments of the present invention, it will be understood by those of ordinary skill in the art that various applications and modifications can be made thereto without departing from the scope of the present invention.