阅读说明：本技术 通过配位阴离子开环聚合制备聚酰胺的方法及由此制备的聚酰胺 (Method for preparing polyamide by ring-opening polymerization of coordinated anions and polyamide prepared thereby ) 是由 李惠连 金大鹤 都*会 李镇瑞 权庆浩 林京元 金杜耿 于 2018-10-29 设计创作，主要内容包括：本发明提供一种通过配位阴离子开环聚合制备聚酰胺的方法及由此制备的聚酰胺,该方法通过添加作为引发剂的金属醇盐(Metal alkoxide)及作为催化剂的金属氢化物(metal hydride),与现有的聚合方法相比,无需额外的真空工序,就能够在低温、较短的聚合反应时间内,聚合分子量分布窄且分子量均匀的高分子。(The present invention provides a method for preparing polyamide by ring-opening polymerization of coordinated anions, which can polymerize polymers having a narrow molecular weight distribution and a uniform molecular weight at a low temperature in a shorter polymerization reaction time without an additional vacuum process by adding a Metal alkoxide (Metal alkoxide) as an initiator and a Metal hydride (Metal hydride) as a catalyst, as compared with the conventional polymerization methods, and a polyamide prepared thereby.)

1. A process for preparing a polyamide by ring-opening polymerization of a coordinating anion, comprising:

a lactam;

the amount of the Metal alkoxide (Metal alkoxide) as an initiator is 0.01 to 20 parts by weight and the amount of the Metal hydride as a catalyst is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the lactam.

2. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

the Metal alkoxide (Metal alkoxide) includes at least one selected from the group consisting of compounds represented by the following chemical formulas,

the chemical formula is as follows:

in the chemical formula, R₁～R₄Each independently represents a hydrogen atom, an aryl group having 5 to 24 carbon atoms or an alkyl group having 10 or less carbon atoms, and M represents a group 3 or 4 metal or a transition metal.

3. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

the catalyst comprises at least one metal hydride selected from sodium hydride (sodium hydride) and potassium hydride (potassium hydride).

4. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

further comprises a molecular weight regulator which is at least one selected from the group consisting of Ethylene Bis Stearamide (EBS), amine (amine) compounds, urea (urea) compounds and bis urea (di-urea) compounds.

5. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

further comprising an activator selected from carbon dioxide (CO)₂) At least one of benzoyl chloride (benzoyl chloride), N-acetyl caprolactam (N-acetyl caprolactam), N-acetyl laurolactam (N-acetyl lauractam), octadecyl isocyanate (SIC), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and mixtures thereof.

6. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

the polymerization reaction is carried out within 0.5 to 120 minutes.

7. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

the polymerization reaction is carried out at 180-300 ℃.

8. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

in the polymerization reaction, the lactam has a conversion of 95% or more.

9. The process for producing a polyamide by ring-opening polymerization of a coordinated anion as claimed in claim 1,

the polymerization reaction is carried out in a manner that does not require a vacuum process.

10. A polyamide, characterized in that,

prepared by the process for the preparation of polyamides by ring-opening polymerization of a coordinating anion as claimed in any of claims 1 to 9.

11. Polyamide according to claim 10, characterized in that,

the polyamide has a molecular weight distribution index of 3.0 or less.

12. Polyamide according to claim 10, characterized in that,

the polyamide has a weight average molecular weight (Mw) of 20,000 to 100,000.

13. A material for a part, characterized in that,

the material for parts is selected from the group consisting of materials for vehicles, electronic devices, industrial pipes, civil engineering materials, 3D printers, fibers, coverings, machine tools, medical materials, aviation materials, solar materials, batteries, sports materials, household electric appliances, and cosmetics materials, and comprises the polyamide according to claim 10.

Technical Field

The present invention relates to a method for preparing polyamide by ring-opening polymerization of complex anion and polyamide prepared thereby, and more particularly, to a method for preparing polyamide by ring-opening polymerization of complex anion, which can polymerize high polymer having a narrow molecular weight distribution and a uniform molecular weight without an additional vacuum step compared to conventional polymerization methods by adding Metal alkoxide (Metal alkoxide) as an initiator and Metal hydride (Metal hydride) as a catalyst, and polyamide prepared thereby.

Background

Polyamide resins are linear polymers bonded via amide (-NHCO-) bonds, have high toughness, excellent physical properties such as friction resistance, wear resistance, oil resistance, and solubility resistance, and are easily melt-molded, and therefore, they are widely used as clothing materials, fibers for industrial materials, engineering plastics, and the like. Polyamides are classified into aliphatic polyamides, aromatic polyamides and alicyclic polyamides according to their molecular structures, wherein the aliphatic polyamides are also called Nylon (Nylon) and the aromatic polyamides are also called Aramid (Aramid).

Such polyamides are prepared by a variety of polymerization processes, roughly classified into: such as nylon 6, by ring-opening polymerization of lactams; such as nylon 6, nylon 6,10 and nylon 4,6, by polycondensation of diamines with diacids; such as nylon 11 and nylon 12, are produced by polycondensation of aminocarboxylic acids. Further, so-called copolymerized nylons such as a copolycondensate of caprolactam and a 6, 10-nylon salt (hexamethylenediamine and sebacate) are industrially produced, and various polyamides containing functional groups such as side chains and hydroxyl groups, aromatic rings and heterocyclic rings in the molecule have been studied.

Lactams, such as caprolactam, can undergo anionic polymerization. The process generally uses a catalyst and an initiator (also referred to as an activator) (activated anionic polymerization). Hitherto, commonly used initiators or activators include diisocyanates or derivatives thereof.

US 4,754,000 (Bayer AG) describes activated anionic polymerization of lactams, wherein polyisocyanates containing biuret groups (biuret groups) and derived from non-aromatic diisocyanates are used as activators to prepare polyamides.

In addition, in U.S. Pat. No. 5,747,634 (1998), it is described to introduce a solution liquid system (solution liquid system) containing both a catalyst and an initiator (reaction accelerator) to obtain a more uniform product. Therein, it is described that by introducing a solution system, a homogeneous product with defined quality is obtained, and results with high reproducibility are obtained. However, when used in a reactive extrusion process, the efficiency is low due to solvent removal problems and the like.

In particular, coordination polymerization of lactams can have a narrow molecular weight distribution, but has problems in that a metal initiator forms an amine (amine) as a weak base through a coordination bond with a monomer, and the polymerization speed is slow, resulting in the formation of a low molecular weight polymer.

Prior art documents

Patent document

(patent document 1) US 2016-0102175

(patent document 2) US 5,519,097

(patent document 3) US 3,883,608

(patent document 4) US 7,135,428

(patent document 5) US 5,362,448

Disclosure of Invention

Technical problem

The present invention is directed to solving the above-mentioned problems of the prior art and the technical problems that have been conventionally proposed.

An object of the present invention is to provide a method for preparing polyamide by ring-opening polymerization of a coordinated anion, which can polymerize a polymer having a narrow molecular weight distribution and a uniform molecular weight at a low temperature in a shorter polymerization reaction time without an additional vacuum step by adding a Metal alkoxide (Metal alkoxide) as an initiator and a Metal hydride (Metal hydride) as a catalyst, as compared with the conventional polymerization methods, and a polyamide prepared thereby.

Technical scheme

To achieve these objects, the method for preparing a polyamide by ring-opening polymerization of a coordinated anion of the present invention may comprise: a lactam; the amount of the metal alkoxide (Metalalkoxide) as an initiator is 0.01 to 20 parts by weight and the amount of the metal hydride (metal hydride) as a catalyst is 0.01 to 20 parts by weight based on 100 parts by weight of the total lactam.

Therefore, a decrease in the polymerization rate occurring during anionic polymerization of lactams is suppressed, and the formation of a low-molecular-weight polymer is effectively regulated, thereby enabling polymerization of a polymer having a uniform molecular weight.

In a preferred embodiment of the present invention, the method for producing a polyamide by ring-opening polymerization of a coordinated anion is characterized in that the Metal alkoxide (Metal alkoxide) contains at least one selected from the group consisting of compounds represented by the following chemical formulae as the initiator.

The chemical formula is as follows:

or

In the chemical formula, R₁～R₄Each independently represents a hydrogen atom, an aryl group having 5 to 24 carbon atoms or a group having 10 or less carbon atomsAnd M is a group 3, group 4 metal or transition metal.

In a preferred embodiment of the present invention, the metal hydride may include sodium hydride (sodium hydride) and potassium hydride (potassium hydride) as the catalyst, but is not limited thereto.

In a preferred embodiment of the present invention, the resin composition may further comprise a molecular weight regulator, wherein the molecular weight regulator is at least one selected from the group consisting of Ethylene Bis Stearamide (EBS), an amine compound, a urea compound and a bis urea compound.

In a preferred embodiment of the present invention, the activator may further comprise carbon dioxide (CO)₂) But not limited thereto, for example, at least one selected from the group consisting of benzoyl chloride (benzoyl chloride), N-acetyl caprolactam (N-acetyl caprolactam), N-acetyl lauryllactam (N-acetyl laurolactam), octadecyl isocyanate (SIC), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and a mixture thereof may be included.

In a preferred embodiment of the present invention, the polymerization reaction can be performed within 0.5 to 120 minutes. The polymerization reaction time is not particularly limited, and may be appropriately adjusted depending on the weight of the compound to be charged, the size of the reactor, and the type of the reactor.

In a preferred embodiment of the present invention, the polymerization reaction can be performed at 180 to 300 ℃.

In a preferred embodiment of the present invention, the lactam can have a conversion of 95% or more in the polymerization reaction.

In a preferred embodiment of the present invention, the polymerization reaction does not produce water or alcohol, and thus can be performed without an additional vacuum process.

In another aspect, the present invention provides a polyamide produced by the above production method, the polyamide being capable of having a molecular weight distribution index (PDI: polydispersity index) of 3.0 or less.

In a preferred embodiment of the present invention, the weight average molecular weight (Mw) of the polyamide may be 20,000 to 100,000.

The present invention also provides a part material selected from the group consisting of a material for vehicles, a material for electronic devices, an industrial pipe, a material for civil engineering, a material for 3D printers, a material for fibers, a covering material, a material for machine tools, a medical material, an aviation material, a solar light material, a material for batteries, a material for sports, a material for home appliances, a material for household use, and a material for cosmetics, and including the polyamide.

In a specific example, the product including the part material may be an air duct for a vehicle, a plastic/rubber compound, an adhesive, a lamp, a polymer optical fiber, a fuel filter cap, a wiring system, a cable for an electronic device, a reflector, a cable sheath, an optical fiber, a wire protection tube, a control unit, a lamp, a tube for a pipe, a gasket, a pipe coating agent, an oil drilling hose, a 3D printer, a multifilament, a spray hose, a valve, a conduit, a paste, a gear, a medical conduit, a flame retardant agent for an aircraft, a solar battery protection sheet, a cosmetic, a high hardness film, a ski boot, a headset, a glasses frame, a toothbrush, a water bottle, or an outsole, but is not limited thereto.

Advantageous effects

As described above, in the present invention, by adding a Metal alkoxide (Metal alkoxide) as an initiator and a Metal hydride (Metal hydride) as a catalyst, a polymer having a narrow molecular weight distribution and a uniform molecular weight can be polymerized at a lower temperature and in a shorter polymerization reaction time than in the conventional polymerization method.

In addition, the present invention does not generate alcohol or water during the polymerization process, and thus can omit an additional vacuum process, thereby improving process efficiency.

Drawings

FIG. 1 is a reaction scheme showing the ring-opening polymerization process of a coordinated anion of the present invention.

Detailed Description

The following description of the invention will refer to specific embodiments, which are shown by way of example, and in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. The various embodiments of the invention are distinct from each other, but are not necessarily mutually exclusive. For example, the specific shape, structure, and characteristics described herein are related to one embodiment, and may be implemented in other embodiments without departing from the technical spirit and scope of the present invention.

The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims and equivalents thereof.

In addition, in the present specification, unless otherwise specified, "substituted" or "substituted" means that one or more hydrogen atoms in the functional group 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 hydroxyl 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, and the plurality of substituents may also be linked to each other to form a ring.

In the present invention, unless otherwise specified, "substituted" means that a hydrogen atom is substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like.

In addition, unless otherwise specified, the "hydrocarbon group" means a saturated or unsaturated hydrocarbon group of a linear, branched or cyclic type, and the alkyl group, alkenyl group, alkynyl group and the like may be of a linear, branched or cyclic type.

In addition, in the present specification, unless otherwise specified, "alkyl" means an alkyl group of C1 to C30, and "aryl" means an aryl group of C6 to C30. In the present description, "heterocyclic group" means a group containing 1 to 3 heteroatoms selected from O, S, N, P, Si and combinations thereof in one ring, and for example, represents pyridine, thiophene, pyrazine and the like, but is not limited thereto.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

As described above, the conventional coordination polymerization of lactam can have a narrow molecular weight distribution, but has problems in that metal and monomer form amine (amine) as a weak base through coordination bond, and the polymerization speed is slow, and a high polymer having a low molecular weight is generated.

In contrast, in the present invention, by adding a Metal alkoxide (Metal alkoxide) as an initiator and a Metal hydride (Metal hydride) as a catalyst, a polymer having a narrow molecular weight distribution and a uniform molecular weight can be polymerized at a low temperature in a shorter polymerization reaction time without an additional vacuum step than in the conventional polymerization method, and thus a solution to the above-mentioned problems has been sought.

According to the present invention, there is provided a process for preparing a polyamide by ring-opening polymerization of a coordinated anion, which comprises: a lactam; the amount of the Metal alkoxide (Metal alkoxide) as an initiator is 0.01 to 20 parts by weight and the amount of the Metal hydride (Metal hydride) as a catalyst is 0.01 to 20 parts by weight based on 100 parts by weight of the total lactam.

Specifically, the composition involved in the preparation of the polyamide ring-opening polymerized by a coordinated anion of the present invention is explained below.

First, the lactam of the present invention may be preferably used as a monomer for preparing a polyamide, but is not limited thereto, and for example, laurolactam, caprolactam, piperidone, pyrrolidone, enantholactam, and caprylolactam, and according to circumstances, may include propionolactam (propiolactam), 2-pyrrolidone (2-pyrollidone), valerolactam (valrolactam), caprolactam (caprolactam), enantholactam (heptanolactam), caprylolactam (octanolactam), nonalactam (nonalactom), decanolactam (decanolactam), undecanolactam, and dodecanolactam.

In addition, according to the present invention, as the initiator, the Metal alkoxide (Metal alkoxide) may include at least one selected from the group consisting of compounds represented by the following chemical formulas, but is not limited thereto.

The chemical formula is as follows:

or

In the chemical formula, R₁～R₄Each independently represents a hydrogen atom, an aryl group having 5 to 24 carbon atoms, or an alkyl group having 10 or less carbon atoms. Further, M is a group 3 or group 4 metal or a transition metal.

Wherein, according to the present invention, the initiator may be contained in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5.0 parts by weight, relative to 100 parts by weight of the total amount of the lactam.

In this case, when the amount of the initiator is less than 0.01 part by weight, there is a problem of non-polymerization, and when the amount of the initiator is more than 20 parts by weight, there is a problem of generation of low molecular weight and high molecular weight or discoloration, and thus the above range is preferable.

Among them, according to the present invention, the catalyst is, for example, a metal hydride, and in order to solve the problem of the decrease in the polymerization rate caused by the formation of an amine as a weak base, which occurs in the conventional lactam polymerization, the content of the metal hydride as a catalyst may be 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the total amount of the lactam.

In this case, when the catalyst is added in an amount of less than 0.01 part by weight, there are problems such as non-polymerization and a decrease in reaction rate, and when the catalyst is added in an amount of more than 20 parts by weight, low molecular weight and high molecular weight are generated, so that the above range is preferable.

These metal catalysts may be used in the form of a solid or a solution, and it is preferable to use the catalysts in the form of a solid. The catalyst is preferably added to the laurolactam melt which is capable of dissolving the catalyst. These catalysts enable the reaction to proceed particularly rapidly and thus increase the efficiency of the polyamide production process of the invention.

On the other hand, according to circumstances, the present invention may include a molecular weight regulator, and may preferably be ethylene-bis-stearamide (EBS), but is not limited thereto, and may include at least one selected from amine (amine) compounds, urea (urea) compounds, and bis-urea (di-urea) compounds.

Wherein, according to the present invention, the content of the molecular weight modifier may be 0.3 to 10 parts by weight, preferably 0.4 to 7.0 parts by weight, and more preferably 0.5 to 3.0 parts by weight, relative to 100 parts by weight of the total amount of the lactam.

In this case, the above range is preferable because the addition of less than 0.3 part by weight of the molecular weight modifier causes problems such as the formation of high molecular weight or gelation, and the addition of more than 10 parts by weight of the molecular weight modifier causes problems such as the formation of low molecular weight or non-polymerization.

Finally, according to the invention, carbon dioxide (CO) is preferred₂) As the activator, for example, but not limited thereto, at least one selected from the group consisting of benzoyl chloride (benzoyl chloride), N-acetyl caprolactame (N-acetyl caprolactam), N-acetyl laurolactam (N-acetyl laurolactam), octadecyl isocyanate (SIC), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and a mixture thereof may be included.

The content of the activating agent may be 0.002 to 20 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the total amount of the lactam. In this case, when the amount of the activator is less than 0.002 parts by weight, there are problems such as the generation of a low molecular weight polymer due to non-polymerization and the reduction of the reaction rate, and when the amount of the activator is more than 20 parts by weight, gelation (gelation) occurs, and thus the above range is preferable.

In the following, preferred embodiments (examples) are presented to aid in understanding the present invention. However, the following examples are only for the purpose of helping understanding of the present invention, and the present invention is not limited to the following experimental examples.