阅读说明：本技术 使用具有双活性基团的分子量调节剂的聚酰胺制备方法及由此制备的聚酰胺 (Method for preparing polyamide using molecular weight regulator having double active groups and polyamide prepared thereby ) 是由 金杜耿 李镇瑞 权庆浩 都*会 李惠连 林京元 金大鹤 于 2018-10-29 设计创作，主要内容包括：本发明提供使用具有双活性基团的分子量调节剂的聚酰胺制备方法及由此制备的聚酰胺,在聚酰胺的阴离子开环共聚中,使用含有双活性基团的分子量调节剂,从而可通过所述分子量调节剂的加成反应来控制分子量。(The present invention provides a method for producing a polyamide using a molecular weight modifier having a double active group, and a polyamide produced thereby, wherein the molecular weight modifier having a double active group is used in an anionic ring-opening copolymerization of a polyamide, whereby the molecular weight can be controlled by an addition reaction of the molecular weight modifier.)

1. A process for producing a polyamide, which comprises a molecular weight modifier and produces the polyamide by anionic polymerization, characterized in that,

using a lactam, and using 0.01 to 20 parts by weight of an alkali metal as an initiator, 0.01 to 5.0 parts by weight of a compound represented by the following chemical formula 2 as a molecular weight regulator having a double active group, and 0.01 to 5.0 parts by weight of an activator, with respect to 100 parts by weight of the total amount of the lactam,

the polyamide comprises a compound represented by the following chemical formula 1,

chemical formula 1:

wherein n and m are each independently a rational number satisfying n ═ m or n > m, k is a rational number satisfying the weight average molecular weight (Mw) of the compound represented by chemical formula 1 of 20,000 to 100,000g/mol,

chemical formula 2:

2. the method for producing polyamide using a molecular weight modifier with dual reactive groups according to claim 1,

the lactam comprises at least one selected from the group consisting of caprolactam, laurolactam, pyrrolidone, piperidone, and mixtures thereof.

3. The method for producing polyamide using a molecular weight modifier with dual reactive groups according to claim 2,

the ratio of (1) to (20-80): 80 to 20 wt% of a lactam selected from the group consisting of two lactams.

4. The method for producing polyamide using a molecular weight modifier with dual reactive groups according to claim 1,

the activator comprises a compound 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 laurolactam), octadecyl isocyanate (SIC), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and mixtures thereof.

5. The process for producing polyamide comprising amide-based molecular weight modifier according to claim 1, characterized in that,

the alkali metal includes at least one selected from metal hydride, metal hydroxide, and metal alkoxide.

6. The method for producing polyamide using a molecular weight modifier with dual reactive groups according to claim 1,

the polymerization temperature is 160-300 ℃.

7. A polyamide, characterized in that,

prepared by the method for preparing polyamide as claimed in any one of claims 1 to 6.

8. Polyamide according to claim 7, characterized in that,

the polyamide has a molecular weight distribution index of 4 or less.

9. Polyamide according to claim 7, characterized in that,

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

10. Polyamide according to claim 7, characterized in that,

the polyamide has a linear, branched, hyperbranched (hyperbranched) or dendritic (dendritic) structure.

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

the polyamide is selected from the group consisting of materials for vehicles, electronic devices, industrial pipes, civil engineering materials, 3D printer materials, fibers, covering materials, machine tool materials, medical materials, aviation materials, solar materials, battery materials, sports materials, home appliances materials, household materials, and cosmetics materials, and comprises the polyamide according to claim 7.

Technical Field

The present invention relates to a method for preparing polyamide using a molecular weight modifier having a double active group and polyamide prepared thereby. More particularly, the present invention relates to a method for producing a polyamide using a molecular weight modifier having a double active group, which uses a molecular weight modifier having a double active group in anionic ring-opening copolymerization of a polyamide, and can control the molecular weight by addition reaction of the molecular weight modifier, and a polyamide produced thereby.

Background

Polyamide resins are linear polymers bonded via amide (-NHCO-) bonds, have high toughness and excellent properties such as abrasion resistance, wear resistance, oil resistance, and solvent 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 can be classified by their molecular structure into aliphatic polyamides, also known as Nylon (Nylon), aromatic polyamides, also known as Aramid (Aramid).

These polyamides are prepared by various 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 formed by the polycondensation of aminocarboxylic acids. Further, so-called copolymerized nylons such as copolycondensates of caprolactam and 6, 10-nylon salts (hexamethylenediamine and sebacic acid salt) 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 utilizes 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.

EP 1091991 (BASF AG) discloses a composition comprising as component a polyisocyanurate having an average of more than 3.5 NCO-functional groups and a process for preparing a top-coating composition using said composition.

US 3423372 uses a polyisocyanate that is not blocked (thus, significantly reducing reactivity), and the activator concentration in this example is very low (1/200-1/50 moles). Therefore, the polymerization time is significantly delayed.

In EP 0156129, rubber (i.e. an elastomeric polymer) is used as a precursor for the multifunctional activator, and therefore the PA produced ultimately is not rigid, up to 1.12 GPa. The activators have a high Mw, wherein a large amount of activator (20% or more) is required. A mixture of a bifunctional activator and a multifunctional activator is used, and therefore the resulting polyamide is not a crosslinked species.

Further, as an anionic polymerization technique of lactam using an extruder in U.S. Pat. No. 4,067,861 (1978), in order to obtain a prescribed discharge amount (output) and uniform viscosity and physical properties, it is proposed to mechanically solve the unevenness of viscosity by a method of providing a metering pump (metering pump) between an extruder body (body) and an extruder die (die), but this is not a fundamental solution.

U.S. Pat. No. 3,878,173 (1975) points out the problem of viscosity instability due to thermal decomposition and the formation of structurally disordered branched structures, but this is merely to prevent decomposition (decomposition) of the synthesized polymer and attempts to solve the problem with more acidic additives have not been made at all to mention a solution to solve the heterogeneous branched structure. For reference, the branching side reactions occurring upon anionic Polymerization of polyamides are mentioned in detail in m.p. stevens, 'polymer chemistry',2nd ed., Oxford University Press, p 429(1990) and g.odian, 'Principlesof Polymerization',2nd ed., John Wiley & Sons, p541 (1981).

U.S. Pat. No. 5,747,634 (1998) describes the introduction of a solution liquid system (solution liquid system) containing both catalyst and initiator (reaction promoter) to obtain a more homogeneous 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 applied to a reactive extrusion method, efficiency is low due to a solvent removal problem or the like.

In particular, the conventional method relies on a method of inducing high molecular weight by additional side reaction or the like, such as polyamide 12 or polyamide 612 polymerized at high temperature, and since the reaction proceeds rapidly at high polymerization temperature, an uneven reaction occurs before the polymer chains are generated by sufficient reaction.

Disclosure of Invention

Technical problem

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

An object of the present invention is to provide a method for producing a polyamide using a molecular weight modifier having a double active group, which uses a molecular weight modifier having a double active group in an anionic ring-opening copolymerization of a polyamide, thereby controlling the molecular weight by an addition reaction of the molecular weight modifier, and a polyamide produced thereby.

Technical scheme

In order to achieve the above object, the present invention provides a method for preparing a polyamide using a molecular weight regulator having a double active group, the method comprising preparing a polyamide containing a compound represented by the following chemical formula 1 by anionic polymerization using a molecular weight regulator, using a lactam, and using 0.01 to 20 parts by weight of an alkali metal as an initiator, 0.01 to 5.0 parts by weight of a compound represented by the following chemical formula 2 as a molecular weight regulator having a double active group, and 0.01 to 5.0 parts by weight of an activator, relative to 100 parts by weight of the total amount of the lactam.

Chemical formula 1:

wherein n and m are each independently a rational number satisfying n ═ m or n > m, and k is a rational number satisfying a weight average molecular weight (Mw) of the compound represented by chemical formula 1 of 20,000 to 100,000 g/mol.

Chemical formula 2:

in a preferred embodiment of the present invention, the lactam may comprise at least one selected from caprolactam, laurolactam, pyrrolidone, piperidone, and a mixture thereof.

In a preferred embodiment of the present invention, the ratio of the total weight of the composition is 20 to 80: 80 to 20 wt% of a lactam selected from the group consisting of two lactams.

In a preferred embodiment of the present invention, the activator may comprise a compound selected from carbon dioxide (CO)₂) Benzoyl chloride (benzoyl chloride)At least one of N-acetyl caprolactam, N-acetyl laurolactam, octadecyl isocyanate (SIC), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), and a mixture thereof.

In a preferred embodiment of the present invention, the activator may contain a double reactive group and is Toluene Diisocyanate (TDI).

In a preferred embodiment of the present invention, the melting temperature (Tm) of the molecular weight regulator may be 160 to 180 ℃.

In a preferred embodiment of the present invention, the alkali metal may include at least one selected from metal hydride (metal hydride), metal hydroxide (metal hydroxide), and metal alkoxide (metal alkoxide).

In a preferred embodiment of the present invention, the polymerization temperature may be 160 to 300 ℃. Wherein, according to the present invention, the polymerization reaction can be performed within 0.5 to 120 minutes based on the experimental reactor. In particular, the polymerization reaction time is not particularly limited and may be appropriately adjusted depending on the weight of the compound to be added or the size and kind of the reactor.

In addition, the present invention provides a polyamide produced by the production method.

In a preferred embodiment of the present invention, the polyamide may have a molecular weight distribution index of 4.0 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 g/mol.

In a preferred embodiment of the present invention, the polyamide may have a linear, branched, hyperbranched (hyperbranched) or dendritic (dendritic) structure.

In another aspect, the present invention provides a part material selected from 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 material of the part 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 catheter, a slurry, a gear, a medical catheter, a flame retardant for an aircraft, a solar battery protection sheet, a cosmetic, a high hardness film, a ski boot, a headphone, a glasses frame, a toothbrush, a water bottle, or an outsole, but is not limited thereto.

Effects of the invention

As described above, the present invention enables the production of a polyamide whose molecular weight can be controlled by addition reaction of a molecular weight modifier by using the molecular weight modifier having a double active group in anionic ring-opening copolymerization of a polyamide.

Drawings

FIG. 1 is a schematic representation of a molecular weight regulator prepared according to the present invention¹³And C-NMR analysis results.

FIG. 2 is a graph showing the results of DSC analysis of molecular weight regulators prepared according to the present invention.

Detailed Description

The following description of the invention refers to particular embodiments capable of carrying out the invention. 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 understood not to be necessarily mutually exclusive. For example, a particular shape, structure, and characteristic described in connection with one embodiment of the present invention may be implemented within 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, as appropriately interpreted.

In addition, in the present specification, unless otherwise specified, "substituted" or "substituted" in the present invention means that one or more hydrogen atoms in the functional group of the present invention are substituted with at least one substituent 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 hydrazino 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, which may also 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 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. The term "heterocyclic group" as used herein refers to a group containing 1 to 3 heteroatoms selected from O, S, N, P, Si and combinations thereof in one ring, and includes, but is not limited to, pyridine, thiophene, pyrazine and the like.

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

As described above, the activators for the existing anionic polymerization have a limitation in obtaining a high molecular weight polyamide since they have only one carbonyl group for opening a ring structure in a molecular structure.

In view of the above, the present invention provides a method for producing a polyamide by anionic copolymerization using a molecular weight modifier having a double reactive group in an anionic polymerization reaction. Solutions to the aforementioned problems are thus sought.

Specifically, according to the present invention, a method for preparing a polyamide comprising a compound represented by the following chemical formula 1, which comprises a molecular weight modifier, by anionic polymerization using a lactam, and using 0.01 to 20 parts by weight of an alkali metal as an initiator, 0.01 to 5.0 parts by weight of a compound represented by the following chemical formula 2 as a molecular weight modifier having a double active group, and 0.01 to 5.0 parts by weight of an activator, relative to 100 parts by weight of the total amount of the lactam.

Chemical formula 1:

wherein n and m are each independently a rational number satisfying n ═ m or n > m, and k is a rational number satisfying a weight average molecular weight (Mw) of the compound represented by chemical formula 1 of 20,000 to 100,000 g/mol.

Chemical formula 2:

hereinafter, the composition involved in the production of the polyamide comprising an amide-based molecular weight modifier of the present invention will be specifically described.

First, the lactam of the present invention may preferably use laurolactam as a monomer for preparing polyamide, but is not limited thereto, and as lactam having 4 to 12 carbon atoms contained in the ring, for example, caprolactam, piperidone, pyrrolidone, enantholactam and capryllactam may be included, and as the case may be, butyrolactam, 2-pyrrolidone (2-pyrollidone), valerolactam (valrolactam), caprolactam (caprolactam), enantholactam (heptanolctam), caprylolactam (octanolactam), nonalactam (nonanolactam), decanolactam (decanolactam), undecanolactam and dodecalactam (dodelactam).

The alkali metal catalyst of the present invention is an initiator for producing polyamide, and the compound that allows the formation of the laurolactam anion may include at least one selected from the group consisting of metal hydride (metal hydride), metal hydroxide (metal hydroxide), and metal alkoxide (metal alkoxide).

In an embodiment, the metal hydride may include sodium hydride (sodium hydride) and potassium hydride (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 is not limited thereto.

For example, a surfactant selected from sodium caprolactam or potassium caprolactam; caprolactam alkaline earth metals, for example, caprolactam magnesium bromide, caprolactam magnesium chloride or biscaprolactam magnesium; alkali metals, e.g., sodium or potassium; alkali metal-containing bases, for example, sodium-containing bases such as sodium hydride, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium propoxide, or sodium butoxide, or potassium-containing bases such as potassium hydride, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide; or a mixture thereof. Preferably, the composition comprises more than one selected from caprolactam sodium, caprolactam potassium, caprolactam magnesium bromide, caprolactam magnesium chloride, biscaprolactam magnesium, sodium hydride, sodium hydroxide, sodium ethoxide, sodium methoxide, sodium propoxide, sodium butoxide, potassium hydride, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide or a mixture thereof. In addition, one or more selected from sodium hydride, sodium caprolactam and mixtures thereof may be included.

These metal catalysts may be used in the form of a solid or a solution, and the catalysts are preferably used in the form of a solid. Preferably, the catalyst is added to a laurolactam melt which is capable of dissolving the catalyst. These catalysts bring about particularly rapid reactions, which can increase the efficiency of the polyamide preparation process of the invention.

Wherein, according to the present invention, the content of the alkali metal 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, the above range is preferable because there is a possibility that the polymerization is not carried out or the reaction rate is decreased when the content of the alkali metal catalyst added is less than 0.01 part by weight, and there is a possibility that the molecular weight is decreased when the content of the alkali metal catalyst added is more than 20 parts by weight.

Next, the molecular weight regulator of the present invention may preferably include a compound represented by the following chemical formula 2 and contain a double active group.

Chemical formula 2:

according to circumstances, ethylene-bis-stearamide (EBS) may be preferable, 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 0.01 to 5 parts by weight, preferably 0.01 to 2 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, the above range is preferable because there is a possibility that gelation (crosslinking, branching reaction) occurs when the content of the molecular weight modifier added is less than 0.01 part by weight, and there is a possibility that the molecular weight decreases when the content of the molecular weight modifier added is more than 5 parts by weight.

In connection therewith, as shown in FIG. 1, from the molecular weight regulator prepared as described above¹³As a result of C-NMR and DSC analyses, it was confirmed that the melting temperature (Tm) of the molecular weight modifier was increased. Thus, when the molecular weight modifier is added, it is expected that the molecular weight is changedThe regulator has long chain structure or ring structure to control the fast reaction speed between polymer chains during polymerization and regulate the molecular weight.

Finally, the activator is not particularly limited, for example, selected from the group consisting of N-substituted lactams, aliphatic diisocyanates, aromatic diisocyanates, polyisocyanates having more than 2 isocyanate groups, and aliphatic and aromatic dicarboxylic acid halides due to the electrophilic moiety. Alternatively, as the activator (C), at least one selected from mixtures thereof may be contained.

In particular, according to the invention, the activator may preferably be 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 (toluene diisocyanate, TDI, Hexamethylene Diisocyanate (HDI), and a mixture thereof may be included.

Wherein the carbon dioxide may be contained in an amount of 0.002 to 1.0 part by weight, preferably 0.005 to 0.5 part by weight, and more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the total amount of the lactam.

In this case, when the content of the carbon dioxide added is less than 0.002 parts by weight, there is a possibility that the polymerization is not carried out or the reaction rate is decreased, and when the content of the carbon dioxide added is more than 1.0 part by weight, there is a possibility that gelation (gelation) or depolymerization (depolymerization) is caused, so that the above range is preferable.

Hereinafter, preferred examples (examples) are provided to facilitate understanding of the present invention. However, the following examples are only for the purpose of facilitating understanding of the present invention, and the present invention is not limited to the following examples.

Preparation example

IBL (isophthaloyl-bis-laurolactam) molecular weight regulator Preparation of

Refluxing the stirrerThe condenser tube and the dropping funnel are arranged in the three-neck flask. At this time, all glasses were previously dried under a nitrogen atmosphere in consideration of moisture-sensitive reactants. To the flask, 1mol equivalent of laurolactam (197.32g) as a monomer, 1mol of triethylamine (triethylamine), and 500mL of THF were added and stirred. Among them, triethylamine (triethylamine) functions as a capturing agent for capturing hydrochloric acid generated by the reaction of laurolactam and isophthaloyl chloride (isophtaloyl chloride). The prepared mixture was stirred, cooled on ice, and a solution of 0.5mol equivalent of isophthaloyl chloride (isophtaloyl chloride) dissolved in 150mL of THF was slowly dropped for 40 minutes. After completion of the addition, the reaction mixture was stirred at normal temperature for 30 minutes and then filtered. After drying the white solid in air, to remove the reaction by-product Et₃NH⁺Cl^-And added to 200mL of water and stirred. The filter paper was washed with 100mL of distilled water 2 times. Drying the white powder in a vacuum oven at 80 deg.C, and performing DSC¹³The material was confirmed by C-NMR.