Patent ID: 12215194

BEST MODE

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.

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.

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.

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 C1-C20hydrocarbon group, a C1-C20alkoxy group, and a C6-C20aryloxy group.

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.

In addition, unless otherwise specified in the present specification, the term “alkyl group” refers to a C1-C30alkyl group and the term “aryl group” refers to a C6-C30aryl 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.

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.

As described above, in a conventional anionic polymerization, there is a limitation in solving a high viscosity phenomenon of a polymer due to an increase in molecular weight due to a basic intermediate produced in anionic polymerization and a side reaction such as a branching reaction or a cross-linking reaction generated under a high-temperature polymerization condition.

There present invention provides a method for producing a polyamide including an amide-based molecular weight controller by an anionic polymerization reaction.

In the method, lactam, and based on 100 parts by weight of the entire lactam, 0.01 to 20 parts by weight of an alkali metal as an initiator, 0.3 parts by weight to 10 parts by weight of an amide-based compound represented by Formula 1 as a molecular weight controller, and 0.002 parts by weight to 7.0 parts by weight of carbon dioxide as an activator are included.

R1and R2may be identical to or different from each other, may be a substituent containing a hetero atom, or may each be hydrogen, a C1-C10linear or branched alkyl, a C2-C10linear or branched alkenyl, a C6-C20aryl, a C7-C21alkylaryl, a C7-C21arylalkyl, a C3-C10cycloalkyl, a C1-C10alkoxy, a C6-C20aryloxy, a C1-C10alkylsilyl, a C6-C20arylsilyl, or halogen, and n is each independently a rational number of 0 to 20.

According to the present invention, the molecular weight controller represented by Formula 1 may be produced by the following Reaction Scheme 1.

In addition, according to the present invention, the molecular weight controller may include a urea-based compound represented by Formula 2.

R1and R2may be identical to or different from each other, may be a substituent containing a hetero atom, or may each be hydrogen, a C1-C10linear or branched alkyl, a C2-C10linear or branched alkenyl, a C6-C20aryl, a C7-C21alkylaryl, a C7-C21arylalkyl, a C3-C10cycloalkyl, a C1-C10alkoxy, a C6-C20aryloxy, a C1-C10alkylsilyl, a C6-C20arylsilyl, or halogen, and n is each independently a rational number of 0 to 20.

According to the present invention, the molecular weight controller represented by Formula 2 may be produced by the following Reaction Scheme 2.

In addition, according to the present invention, the molecular weight controller may include a urea-based compound represented by Formula 3.

R1and R2may be identical to or different from each other, may be a substituent containing a hetero atom, or may each be hydrogen, a C1-C10linear or branched alkyl, a C2-C10linear or branched alkenyl, a C6-C20aryl, a C7-C21alkylaryl, a C7-C21arylalkyl, a C3-C10cycloalkyl, a C1-C10alkoxy, a C6-C20aryloxy, a C1-C10alkylsilyl, a C6-C20arylsilyl, or halogen, and n is each independently a rational number of 0 to 20.

According to the present invention, the molecular weight controller represented by Formula 3 may be produced by the following Reaction Scheme 3.

In addition, according to the present invention, the molecular weight controller may include a urea-based compound represented by Formula 4.

R1and R2may be identical to or different from each other, may be a substituent containing a hetero atom, or may each be hydrogen, a C1-C10linear or branched alkyl, a C2-C10linear or branched alkenyl, a C6-C20aryl, a C7-C21alkylaryl, a C7-C21arylalkyl, a C3-C10cycloalkyl, a C1-C10alkoxy, a C6-C20aryloxy, a C1-C10alkylsilyl, a C6-C20arylsilyl, or halogen, and n is each independently a rational number of 0 to 20.

According to the present invention, the molecular weight controller represented by Formula 4 may be produced by the following Reaction Scheme.

Specifically, compositions included in the preparation of the polyamide, including the amide-based molecular weight controller according to the present invention, will be described below.

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

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 laurolactam anion.

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.

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.

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 laurolactam 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.

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 laurolactam. 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 5.0 parts by weight.

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 molecular weight reduction problem may occur. Therefore, the above range is preferable.

Next, the molecular weight controller according to the present invention may preferably include at least one selected from the group consisting of compounds represented by Formulae 1 to 4.

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 0.7 parts by weight, and more preferably 0.5 parts by weight to 3.0 parts by weight.

In this case, when the molecular weight controller is added in an amount of less than 0.3 parts by weight, a gelation (crosslinking or branching reaction) problem may occur. When the amount of the molecular weight controller exceeds 10 parts by weight, a molecular weight reduction problem may occur. Therefore, the above range is preferable.

In this regard, as shown inFIG.1, it was confirmed from the rheometer measurement result of the polymerization sample produced as described above that the viscosity is reduced in the case of the polymerization sample including the molecular weight controller. From this, when the molecular weight controller is included in the above range, the molecular weight can be effectively controlled.

Finally, according to the invention, the activator may preferably be 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.

An amount of the carbon dioxide may be in a range of 0.002 parts by weight to 7.0 parts 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 0.5 parts by weight, and more preferably 0.01 parts by weight to 0.1 parts by weight.

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 7.0 parts by weight, a gelation or depolymerization problem may occur. Therefore, the above range is preferable.

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

Production of Polymerization Sample Using Acetanilide as Molecular Weight Controller

In order to remove moisture from a flask, a vacuum was released from the flask that was maintained at 60° C. in a vacuum state. 20 g of laurolactam, 0.14 g of acetanilide, and 0.02 g of NaH were added to the flask and the temperature was raised to 160° C. under vacuum. Then, the reaction temperature was set to 230° C. and nitrogen gas was added thereto. Hydrogen gas generated while the materials were molten was removed. 3.4 ml of carbon dioxide was injected and reacted for 30 minutes. Finally, after 30 minutes, an aqueous formic acid solution (formic acid:distilled water=1:1) was added to the flask to terminate the reaction. A sample having content shown in Table 1 was collected. Using this, a molecular weight and a polydispersity index (PDI) were confirmed and the results thereof are shown in Table 2 below.

TABLE 1AlkaliMolecular weightAmountLaurolactammetalcontrollerof CO2(g)(g)(g)(ml)Example 1200.020.143.4Example 2200.020.123.4Example 3200.020.183.4Example 4200.020.243.4Example 5200.020.273.4Example 6200.020.053.4Example 7200.020.63.4Example 8200.020.93.4Example 9200.020.150.2Example 10200.020.156Example 11200.020.151000Comparative200.02—1.7Example 1Comparative200.020.151.7Example 2

Example 2

Production of Polymerization Sample Using Urea as Molecular Weight Controller

A reaction was performed in the same manner as in Example 1, except that 0.12 g of urea was used as a molecular weight controller.

Example 3

Production of Polymerization Sample Using Urea as Molecular Weight Controller

A reaction was performed in the same manner as in Example 1, except that 0.18 g of urea was used as a molecular weight controller.

Example 4

Production of Polymerization Sample Using Urea as Molecular Weight Controller

A reaction was performed in the same manner as in Example 1, except that 0.24 g of urea was used as a molecular weight controller.

Example 2

Production of Polymerization Sample Using Urea as Molecular Weight Controller

A reaction was performed in the same manner as in Example 1, except that 0.27 g of urea was used as a molecular weight controller.

Examples 6 to 11

Polymerization samples were produced in the same manner as in Example 1, except that the content ratios of the compositions were different as shown in Table 1.

Examples 12 and 13

Polymerization samples were produced in the same manner as in Example 1, except that the content ratios and types of the compositions were different and the polymerization conditions were set as shown in Table 2.

TABLE 2AlkaliMolecular weightAmount of NAC (N-PolymerizationLaurolactammetalcontrolleracetylcaprolactam)temperature(g)(g)(g)(ml)(° C.)Example 12200.120.24(Urea)0.80230Example 13200.120.14(Urea)0.80180

Comparative Examples

Comparative Example 1

A reaction was performed in the same manner as in Example 1, except that no molecular weight controller was added.

Comparative Example 2

A reaction was performed in the same manner as in Example 1, except that 0.15 g of EBS was used as a molecular weight controller.

TABLE 3Molecular weightPolydispersity index(g/mol)(PDI)PolymerizationExample 195,0002.5PolymerizationExample 2120,0006.2GelationExample 360,0002.3PolymerizationExample 434,0002.4PolymerizationExample 536,0002.4PolymerizationExample 664,0002.2PolymerizationExample 721,0002.5PolymerizationExample 815,0002.5PolymerizationExample 93,0006.2UnpolymerizationExample 1085,0002.5PolymerizationExample 11>160,0005.7GelationExample 1285,0002.5PolymerizationExample 1393,0002.4PolymerizationComparative>160,0006.5GelationExample 1Comparative73,5002.5PolymerizationExample 2

As shown in Table 3, Comparative Example 1 in which no molecular weight controller was added showed a high molecular weight deviating from a target molecular weight and a high molecular weight distribution, as compared with Example 1. However, Comparative Example 2 in which EBS was used as the molecular weight controller showed a relatively low molecular weight, as compared with Example 1, but showed a target molecular weight distribution range in a molecular weight distribution.

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.