KR102375504B1 - Polyamide based polymer compositions comprising hyperbranched polyamide having enhanced flowability and preparation method thereof - Google Patents

Abstract

The present invention relates to a polyamide-based polymer composition having improved flowability and a method for preparing the same. Particularly, the polyamide-based polymer composition having improved flowability includes a hyperbranched polyamide that can be used as a flow modifier for a polyamide-based resin, wherein the hyperbranched polyamide is prepared by carrying out amide formation between a linear diamine compound and a polyhydric organic acid or organic acid salt compound and converting the remaining organic acid group into an alkyl ester group. The polyamide-based resin composition according to the present invention allows effective dispersion of reinforcing fibers in the subsequent process for manufacturing a composite material using reinforcing fibers, such as glass fibers or carbon fibers, and thus is an effective material in the compounding or extrusion and injection molding of polyamide-based engineering plastics containing a high content of glass fibers by virtue of its improved flowability.

Description

Polyamide based polymer compositions comprising hyperbranched polyamide having enhanced flowability and preparation method thereof

The present invention relates to a polyamide-based polymer composition having improved fluidity and a method for preparing the same.

More specifically, the hyperbranched polyamide, which can be used as a flow control agent in a polyamide-based resin, comprises a hyperbranched polyamide in which the residual organic acid group is converted to an alkylester group after the amide formation reaction between the linear diamine compound and the polyvalent organic acid or organic acid chloride. To a polyamide-based polymer composition having improved fluidity and a method for manufacturing the same

Recently, as governments around the world tighten regulations on fuel efficiency and exhaust gas, automakers are making continuous efforts to reduce the weight of automobiles. Methods for reducing vehicle weight include reducing the number of parts through optimal design and maximizing component performance, and applying lightweight alternative materials such as aluminum, magnesium, engineering plastics, fiber-reinforced plastics, and fiber-reinforced composites. Among these, the application of lightweight alternative materials not only reduces the weight of parts, but also enables optimal design and parts integration, thereby maximizing the effect of weight reduction.

Fiber-reinforced plastic or fiber-reinforced composite material is a generic term for composite materials that use plastic as a matrix and reinforced with glass fiber, carbon fiber, and aramid fiber. is widely used in In addition, as automobiles and industrial products gradually become high-performance and light-weight, components are also required to have a more precise shape than before, and performances such as high heat resistance and high rigidity are required.

Polyamide-based composite material is a material with excellent rigidity, toughness and chemical resistance. It has excellent light weight, impact resistance, thermal expansion coefficient and economic feasibility, so it can be used as an alternative material to aluminum and steel. % or more, so not only for automotive exteriors. When applied to internal parts including housing, it is possible to present a solution using advanced materials to the automobile market that requires weight reduction, design flexibility, and ease of molding.

Korean Patent Application Laid-Open No. 10-2009-0063382, which is a prior art related to the polyamide-based composite material as described above, relates to a polyamide-reinforced resin composition, and in more detail, weight reduction as a result of TGA analysis at 300 °C (after 10 minutes) is 5% or less, the fluidity according to ASTM evaluation method D1238 is 20 g/10 min or more, and the gray scale after irradiating 126 MJ/m2 with 65 W/m2 irradiation intensity by a xenon arc is 3 or more, ASTM evaluation method D790 It relates to a polyamide-reinforced resin composition having a flexural strength of 1,300 to 3,000 kg/m 2 .

However, in order to realize the high function of polyamide-based composite materials, compounding technology with various reinforcing materials is essential. When high content of glass fiber is added, fluidity is not good, and when physical properties are satisfied, processability is poor. However, it is difficult to mold through the injection process. Since there is a limit to improving the processability of polymers through monomer change, molecular weight control, and molecular structure change, flow control agents such as lubricants that affect the viscous behavior of the melt as well as selection of processing equipment should be used to improve processability. do.

Therefore, while the present inventors were researching a polymer composition having excellent fluidity, when hyperbranched polyamide is added as a fluidity regulator to a polyamide-based resin, the fluidity of the polymer composition is improved as well as mixing with reinforcing fibers through this. It was found that mechanical strength can also be improved when manufacturing a polymer composite material through , and the present invention has been completed.

Republic of Korea Patent Publication No. 10-2009-0063382.

It is an object of the present invention to provide a hyperbranched polyamide flow control agent with further improved thermal stability.

In addition, the present invention improves the fluidity of the composition in the processing and molding step of the polymer resin mixed with the reinforcing fibers in the production of a thermoplastic polymer composite material containing reinforcing fibers, thereby reducing friction between the molten resin and the processing equipment, and It aims to enable effective dispersion of resin and glass fibers.

Accordingly, an object of the present invention is to provide an effective flow control agent capable of lowering the viscosity of a polyamide-based resin, and to provide a polyamide-based composition with improved fluidity using the same, and a method for preparing the same.

In order to achieve the above object, the present invention provides a polyamide-based resin as a flow control agent to form an amide between a linear diamine compound represented by the following formula (A), a linear amine compound represented by formula (B), and a polyvalent organic acid or an organic acid chloride represented by the following formula (C) Provided is a polyamide-based polymer composition having improved fluidity, characterized in that it comprises a hyperbranched polyamide in which the residual organic acid group is converted to an alkylester group after the reaction.

<Formula A>

However, in Formula A, R is one of an alkylene group having 1 to 15 carbon atoms,

<Formula B>

However, in Formula B, R 'is one of the alkyl group having 2 to 4 carbon atoms,

<Formula C>

However, in Formula C, X is -OH or -Cl.

In addition, the present invention is a polyamide-based resin flow control agent hyperbranching by amide formation between a linear diamine compound represented by the following formula (A), a linear amine compound represented by formula (B), and a polyvalent organic acid or organic acid chloride represented by the following formula (C) Hyper-branched polyamide manufacturing step of preparing polyamide; A modified hyperbranched polyamide manufacturing step of converting the residual organic acid group of the hyperbranched polyamide into an alkylester group; a melt-kneading step of mixing and heating the modified hyperbranched polyamide with a polyamide-based resin to prepare a melt-kneaded product; And a method for producing a polyamide-based composition having improved fluidity, characterized in that it comprises a molding manufacturing step of molding the melt-kneaded product:

<Formula A>

However, in Formula A, R is one of an alkylene group having 1 to 15 carbon atoms,

<Formula B>

However, in Formula B, R 'is one of the alkyl group having 2 to 4 carbon atoms,

<Formula C>

However, in Formula C, X is -OH or -Cl.

The hyperbranched polyamide in which the residual organic acid group is converted to an alkylester group according to the present invention not only removes HCl derived from the organic acid chloride group during the manufacturing reaction, but also converts the organic acid group to an alkylester group, thereby exhibiting excellent uniformity and thermal stability.

In addition, when the hyperbranched polyamide prepared in this way is used as a flow control agent, the compatibility or compatibility with the polyamide-based polymer is very good, HCl derived from the organic acid chloride group is removed, and the organic acid group is converted into an alkylester group to process equipment This polyamide-based resin composition can prevent the corrosion of the molten resin and the processing equipment and greatly improves the fluidity by reducing the friction between the molten resin and the processing equipment. It has the effect of effectively dispersing and greatly reducing the torque applied to the processing equipment.

In addition, the polymer composition according to the present invention is a very effective material due to improved fluidity in compounding or extrusion and injection molding of polyamide-based engineering plastics containing high content of glass fibers.

In addition, according to the present invention, a polyamide-based composite material with excellent mechanical strength even under relatively mild processing conditions is produced by induced even mixing of reinforcing fibers and polymer resin as flowability is greatly improved during processing by the addition of a flow control agent. can do.

1 shows FT-IR spectra of hyperbranched polyamides HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ which are flow control agents prepared according to an embodiment of the present invention.
2 shows the differential scanning calorimetry (DSC) results of hyperbranched polyamides HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ which are flow control agents prepared according to an embodiment of the present invention.
3 shows the thermogravimetric analysis (TGA) results of hyperbranched polyamides HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ which are flow control agents prepared according to an embodiment of the present invention.
4 is data confirming the reproducibility of hyperbranched polyamide HBPA_OCH ₃ , which is a flow control agent prepared according to an embodiment of the present invention.
5 is a result of measuring the viscosity of a polymer composition prepared by adding 0 phr, 1 phr, and 3 phr of HBPA_OCH ₃ prepared according to an embodiment of the present invention to PA6 and PA66, respectively.
6 is a view of a spiral specimen prepared to confirm the flowability of a polymer composition prepared by adding 0 phr, 1 phr, and 3 phr of HBPA_OCH ₃ prepared according to an embodiment of the present invention to PA6 and PA66, respectively.

In the specification of the present invention, in order to describe the invention in the best way, the concept of terms or words used in the detailed description and claims of the invention may be appropriately defined, and the terms or words correspond to the spirit of the invention. should be interpreted so that In addition, the configurations shown in the embodiments described in this specification are specific embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, at the time of filing of the present invention, there may be various equivalents and modifications that can be substituted for them within the scope of the object of the present invention.

As used herein, the term “polyamide-based resin” may be a homopolymer or a copolymer. The present invention may use one or more linear or branched polyamides as polyamides. Linear polyamides can be prepared from dicarboxylic acids and diamines, branched polyamides from amines and carboxylic acids whose monomers can contain more than two acid groups or amine groups, and thus branching points can occur. that can be manufactured.

Examples of polyamides are polycaprolactams, polycaprylolactams and polylaurolactams derived from lactams having 7 to 13 ring members, or polyamides obtained through reaction of dicarboxylic acids with diamines.

Dicarboxylic acids which can be used in particular are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms, and aromatic dicarboxylic acids, preferably adipic acid, azelaic acid, sebacic acid, dodecanedi penic acid, and terephthalic acid and/or isophthalic acid, etc., preferred diamines being alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms, and also m-xylylenediamine, di(4-aminophenyl)methane, di (4-aminocyclohexyl)methane, 2,2-di(4-aminophenyl)propane, 2,2-di(4-aminocyclohexyl)propane or 1,5-diamino-2-methylpentane; .

Preferred polyamides are therefore polyhexamethyleneadipamide, polyhexamethylenesebacamide and polycaprolactam, and also especially nylon-6/6,6 copolyamides having a caprolactam unit content of 5 to 95% by weight. Other suitable polyamides are those obtainable through a mixture of a plurality of polyamides in any desired mixing ratio or copolymerization of two or more of the aforementioned monomers.

Hereinafter, the polyamide-based polymer composition according to the present invention will be described in detail.

In order to achieve the above object, the present invention provides a polyamide-based resin as a flow control agent to form an amide between a linear diamine compound represented by the following formula (A), a linear amine compound represented by formula (B), and a polyvalent organic acid or an organic acid chloride represented by the following formula (C) Provided is a polyamide-based polymer composition having improved fluidity, characterized in that it comprises a hyperbranched polyamide in which the residual organic acid group is converted to an alkylester group after the reaction.

<Formula A>

However, in Formula A, R is one of an alkylene group having 1 to 15 carbon atoms,

<Formula B>

However, in Formula B, R 'is one of the alkyl group having 2 to 4 carbon atoms,

<Formula C>

However, in Formula C, X is -OH or -Cl.

In the polyamide-based polymer composition according to an embodiment of the present invention, the equivalent weight of the linear diamine compound, the linear amine compound, and the polyvalent organic acid or organic acid chloride used in the preparation of the hyperbranched polyamide is preferable. In this case, the equivalent means that each compound is administered to the reaction in substantially the same mole (mol). That is, since the compound of Formula C is a polyvalent organic acid or an organic acid chloride, it contains three organic acid or organic acid chloride groups per molecule, and the linear diamine compound represented by Formula A contains two amine groups per molecule, and the linear represented by Formula B Since the amine compound contains one amine group per molecule, dosing substantially the same mole (mol) of each compound to the reaction means that the organic acid or organic acid chloride group in the reaction system and the amine group of the linear diamine compound and the linear amine compound are equivalent to each other. It is preferable that it is added to achieve a reaction. In the reaction between these compounds, if the input amount of the amine compound exceeds the amount of the organic acid or organic acid chloride group, effective interfacial polymerization is impossible due to a non-uniform reaction, so it may be difficult to prepare a hyperbranched polyamide having a desired structure.

In addition, the linear diamine compound to be introduced is a compound suitable for a linking reaction between polyvalent organic acids or organic acid chlorides, and it is preferable to use the linear amine compound as a compound for forming the terminal of the hyperbranched polyamide. A two-step reaction in which the chloride is reacted first and the linear amine compound is reacted later is preferable, but even if they are reacted simultaneously, there may be substantially no significant difference in that the resultant linear amine compound forms the ends of the hyperbranched polyamide. .

In the polyamide-based polymer composition having improved fluidity according to the present invention, the polyamide-based resin is selected from the group consisting of lactam-derived polyamide, polyamide obtained through reaction of dicarboxylic acid with diamine, and copolyamide. It may be one or more polyamides selected.

The hyperbranched polyamide flow control agent used in the present invention preferably has a molecular weight in the range of 0.01 to 0.60 dL/g based on intrinsic viscosity. When the molecular weight of the flow control agent exceeds 0.60 dL/g, the viscosity of the flow control agent becomes high and is not suitable for improving flowability. This is not preferable because the physical properties of the final molded product are deteriorated.

The hyperbranched polyamide flow control agent used in the present invention has very excellent miscibility or compatibility with the polyamide-based resin compared to the conventional flow control agent, and also has very excellent flowability when mixed with the polyamide-based resin. can indicate

In the polyamide-based polymer composition having improved fluidity according to the present invention, the hyperbranched polymer, which is the flow control agent, may exhibit excellent fluidity by including 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide-based resin.

If the flow control agent contains less than 0.1 parts by weight based on the polyamide-based resin, there is a problem in that excellent fluidity that can be obtained by adding the flow control agent cannot be obtained. There is a problem in that the mechanical strength of the composite material prepared from the mixture of the resin and the reinforcing fiber is inferior.

When manufacturing a composite material from a polymer composition exhibiting excellent fluidity, it can be usefully applied to compounding, extrusion, and injection molding of a polyamide-based engineering plastic containing a high content of glass fiber.

Specifically, the polymer composition according to the present invention exhibits an effect of lowering the viscosity toward the high-speed shearing region, which improves the fluidity under actual extrusion and injection conditions, thereby reducing the load on the equipment and increasing the life of the equipment. , it has a great effect in lowering the overall production cost by lowering the production power or output energy. At the same time, since the polymer composition according to the present invention has excellent mechanical strength, it can be applied to various fields.

In the polyamide-based polymer composition having improved flowability according to the present invention, the hyperbranched polyamide as the flow control agent is a linear alkyl diamine compound, a linear alkyl amine compound and a trivalent or higher organic carboxylic acid or carboxylic acid It can be prepared by amide formation with carboxylic acid chloride. Preferably, it may be a diamine having an alkyl group having 1 to 15 carbon atoms, an amine having an alkyl group having 2 to 4 carbon atoms, or trimesic acid or trimesic acid chloride having 3 carboxyl groups. More preferably, the linear alkyl diamine compound may be diaminohexane, diaminooctane, or diaminododecane, and the linear alkyl amine compound is ethylamine, propylamine ( propylamine).

In the polyamide-based polymer composition having improved fluidity according to the present invention, the hyperbranched polyamide, which is the flow control agent, may be prepared by the reaction represented by Scheme A below.

<Scheme A>

However, in Scheme A, R is one of an alkylene group having 1 to 15 carbon atoms, R' is one of an alkyl group having 2 to 4 carbon atoms, and R″ is an alkyl group having 1 to 6 carbon atoms.

More specifically, R″-OH is any one of methanol, ethanol, propanol, butanol, pentanol, or hexanol.

In addition, the present invention is a polyamide-based resin flow regulator by the amide formation reaction between the linear diamine compound represented by the following formula (A), the linear amine compound represented by the formula (B), and a polyhydric organic acid or organic acid chloride represented by the following formula (C) Hyper-branched polyamide manufacturing step of preparing branched polyamide; A modified hyperbranched polyamide manufacturing step of converting the residual organic acid group of the hyperbranched polyamide into an alkylester group; a melt-kneading step of mixing and heating the modified hyperbranched polyamide with a polyamide-based resin to prepare a melt-kneaded product; And it provides a method for producing a polyamide-based composition having improved fluidity, characterized in that it comprises a molding manufacturing step of molding the melt-kneaded product.

<Formula A>

However, in Formula A, R is one of an alkylene group having 1 to 15 carbon atoms,

<Formula B>

However, in Formula B, R 'is one of the alkyl group having 2 to 4 carbon atoms,

<Formula C>

However, in Formula C, X is -OH or -Cl.

In the method for producing a polyamide-based polymer composition having improved fluidity according to the present invention, the polyamide-based resin is a polyamide derived from lactam, a polyamide obtained through a reaction between a dicarboxylic acid and a diamine, and a copolymerized polyamide. It may be one or more polyamides selected from the group consisting of.

In the method for producing a polyamide-based polymer composition having improved flowability according to the present invention, the hyperbranched polyamide as the flow control agent is a linear alkyl diamine compound, a linear alkyl amine compound, a trivalent or higher organic carboxylic acid, or It can be prepared by amide formation with carboxylic acid chloride. Preferably, it may be a diamine having an alkyl group having 1 to 15 carbon atoms, an amine having an alkyl group having 2 to 4 carbon atoms, or trimesic acid or trimesic acid chloride having 3 carboxyl groups. More preferably, the linear alkyl diamine compound may be diaminohexane, diaminooctane, or diaminododecane, and the linear alkyl amine compound is ethylamine, propylamine ( propylamine).

In the method for producing a polyamide-based polymer composition having improved fluidity according to the present invention, the hyperbranched polyamide, which is the flow control agent, may be prepared by the reaction represented by Scheme A below.

<Scheme A>

However, in Scheme A, R is one of an alkylene group having 1 to 15 carbon atoms, R' is one of an alkylene group having 2 to 4 carbon atoms, and R″ is an alkyl group having 1 to 6 carbon atoms.

More specifically, R″-OH is any one of methanol, ethanol, propanol, butanol, pentanol, or hexanol.

In the method for producing a polyamide-based polymer composition having improved fluidity according to the present invention, the melt-kneading step may be performed at a temperature of 200 to 500° C. The molding method can be used.

The molding manufacturing step may be extrusion molding or injection molding the melt-kneaded material. First, the extrusion molding is preferably performed at a temperature of 200 ℃ to 350 ℃. If the extrusion molding is performed at a temperature of less than 200 ° C, it is difficult to mix evenly, and when the extrusion molding is performed at a temperature exceeding 350 ° C, the mechanical properties of the polyamide-based composite material to be manufactured decrease, or the process at a high temperature As a result, there is a problem of lowering economic efficiency. Meanwhile, in the method for manufacturing a polyamide-based composite material according to the present invention, injection molding may be performed by a known method using an apparatus such as an injection molding machine.

Furthermore, the melt-kneading step is not limited as long as it is a temperature capable of melting the polyamide-based resin, and may be performed at a temperature of 200°C to 500°C.

In addition, when manufacturing a composite material using the polyamide-based polymer composition having improved fluidity according to the present invention, any one of glass fiber and carbon fiber may be used as the reinforcing fiber, and for effective mixing, the reinforcing fiber is shorter than the long fiber. Fiber is preferable, and glass fiber is more preferable in consideration of economic feasibility.

In addition, in the production of the composite material, the reinforcing fiber is preferably a mixture of 20 wt% to 90 wt% of the polyamide-based resin composition and 10 wt% to 80 wt% of the reinforcing fiber, and 20 wt% to 50 wt% of the polyamide-based resin ; and 50 wt% to 80 wt% of glass fibers; more preferably comprising.

The polyamide-based resin composition with improved fluidity according to the present invention can be used as a composition for manufacturing a glass fiber-reinforced composite material having a high content of 50% by weight or more of glass fibers.

Conventionally, when a high content of glass fibers is included as described above, there are limitations in productivity and physical properties improvement due to breakage of glass fibers, but the polymer composition according to the present invention controls the flow of hyperbranched polymers derived from alkyl diaminobenzoate monomer By using zero, not only excellent fluidity but also excellent mechanical strength can be exhibited.

Hereinafter, the present invention will be described in detail by the following Preparation Examples and Examples. However, the following Preparation Examples and Examples are merely illustrative of the present invention, and the scope of the invention is not limited by the Examples and Experimental Examples.

Hyperbranched polyamides HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ according to the present invention are prepared by the reaction represented by Scheme A below.

<Scheme A>

More specifically, in Scheme A, R is an octylene group, R' is a propyl group, and R″ is either a methyl or an ethyl group.

<Preparation Example 1> Synthesis of hyperbranched polyamide HBPA_H2O

Prepare a magnetic stirrer, a metering pump, a mechanical stirrer, a 250 ml capacity beaker, and a 500 ml capacity beaker. Put 26.54g (TMC, 100mmol) of 1,3,5-benzenetricarbonyl chloride (1,3,5-Benzenetricarbonyl chloride, aka trismetic acid chloride) in 100 ml of dimethyl chloride (DCM) in a 500 ml beaker and dissolve 1,8-diaminooctane (1,8-Diaminooctane) 14.43 g (OMDA, 100 mmol) and propylamine 5.91 g (PrA, 100 mmol) in 125 ml of distilled water in a 250 ml beaker , Prepare an aqueous solution by dissolving 10 g of sodium hydroxide. After reacting by injecting an aqueous solution in an amount of 11 ml/min to the organic layer with a metering pump, the synthesized polymer was obtained at a speed of 15 RPM using a mechanical stirrer. The product was washed three times with distilled water, and then ground with a mixer and stirred with distilled water for 1 hour. Thereafter, the product was filtered and vacuum dried at 100° C. for 24 hours to obtain a clean product.

<Preparation Example 2> Hyperbranched polyamide HBPA_OCH ₃ synthesis of

Prepare a magnetic stirrer, a metering pump, a mechanical stirrer, a 250 ml capacity beaker, and a 500 ml capacity beaker. Put 26.54g (TMC, 100mmol) of 1,3,5-benzenetricarbonyl chloride (1,3,5-Benzenetricarbonyl chloride, aka trismetic acid chloride) in 100 ml of dimethyl chloride (DCM) in a 500 ml beaker and dissolve 1,8-diaminooctane (1,8-Diaminooctane) 14.43 g (OMDA, 100 mmol) and propylamine 5.91 g (PrA, 100 mmol) in 125 ml of distilled water in a 250 ml beaker , Prepare an aqueous solution by dissolving 10 g of sodium hydroxide. After reacting by injecting an aqueous solution in an amount of 11 ml/min to the organic layer with a metering pump, the synthesized polymer was obtained at a speed of 15 RPM using a mechanical stirrer. The product was washed three times with methanol, and then ground with a mixer and half-stirred with methanol for 1 hour. Thereafter, the product was filtered and vacuum dried at 100° C. for 24 hours to obtain a clean product.

<Preparation Example 3> Hyperbranched polyamide HBPA_OCH ₂ CH ₃ synthesis of

Prepare a magnetic stirrer, a metering pump, a mechanical stirrer, a 250 ml capacity beaker, and a 500 ml capacity beaker. Put 26.54g (TMC, 100mmol) of 1,3,5-benzenetricarbonyl chloride (1,3,5-Benzenetricarbonyl chloride, aka trismetic acid chloride) in 100 ml of dimethyl chloride (DCM) in a 500 ml beaker and dissolve 1,8-diaminooctane (1,8-Diaminooctane) 14.43 g (OMDA, 100 mmol) and propylamine 5.91 g (PrA, 100 mmol) in 125 ml of distilled water in a 250 ml beaker , Prepare an aqueous solution by dissolving 10 g of sodium hydroxide. After reacting by injecting an aqueous solution in an amount of 11 ml/min to the organic layer with a metering pump, the synthesized polymer was obtained at a speed of 15 RPM using a mechanical stirrer. The product was washed with ethanol three times, and then ground with a mixer and stirred with ethanol for 1 hour. Thereafter, the product was filtered and vacuum dried at 100° C. for 24 hours to obtain a clean product.

<Preparation Example 4> Preparation of hyperbranched polyamide: non-equivalent reaction

Prepare a magnetic stirrer, a metering pump, a mechanical stirrer, a 250 ml capacity beaker, and a 500 ml capacity beaker. Put 26.54g (TMC, 100mmol) of 1,3,5-benzenetricarbonyl chloride (1,3,5-Benzenetricarbonyl chloride, aka trismetic acid chloride) in 100 ml of dimethyl chloride (DCM) in a 500 ml beaker and dissolve to prepare an organic layer, and 17.31 g (OMDA, 120 mmol) of 1,8-diaminooctane (1,8-Diaminooctane) and 7.09 g (PrA, 120 mmol) of 1,8-diaminooctane in 125 ml of distilled water in a 250 ml beaker , an aqueous solution was prepared by dissolving 10 g of sodium hydroxide. However, a phenomenon of layer separation occurred during the reaction, and as this layer separation occurred, interfacial polymerization could not proceed uniformly, making it impossible to synthesize the hyperbranched polyamide to be prepared.

That is, in Preparation Examples 1 to 3 of the present invention, the equivalent of the linear diamine compound, the linear amine compound, and the polyvalent organic acid or organic acid chloride used in the preparation of the hyperbranched polyamide, that is, each compound is substantially the same in mole (mol) When administered to the reaction, equivalents of the organic acid or organic acid chloride group in the reaction system and the amine group of the linear diamine compound and the linear amine compound are added to each other to achieve the reaction, whereas in Preparation Example 4, the reaction is linear compared to the reactor of the polyvalent organic acid or organic acid chloride It was found that when the amine groups of the diamine compound and the linear amine compound were added in 1.2 times each, the hyperbranched polyamide to be prepared could not be synthesized due to the non-uniform reaction and layer separation.

Table 1 summarizes the pH changed as the flow control agent prepared according to an embodiment of the present invention was washed three times using distilled water, methanol, and ethanol.

reaction solvent pH After 1 washing After washing 2 times After washing 3 times Preparation Example 1 Distilled water 3.612 3.162 3.051 Preparation 2 Methanol 8.769 8.697 8.591 Preparation 3 Ethanol 5.001 5.908 5.981 Preparation 4 no synthesis

In the present invention, when washing with distilled water, the unreacted chloride group of HBPA_H2O reacts with distilled water to form carboxylic acid, so that HBPA_H2O is continuously acidic. It can be seen that. However, when methanol or ethanol is used, it can be confirmed that all unreacted chloride groups react and are converted to a methoxy group or an ethoxy group, thereby increasing the pH.

Figure 1 shows the FT-IR spectrum of hyperbranched polyamide HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ , which is a flow control agent prepared according to an embodiment of the present invention, NH stretching of the amide group at 3300 to 3500 cm ^-1 ; Aromatic CH stretching from 3000 to 3100 cm ^-1 , stretching of alkyls from 2850 to 3000 cm ^-1 , C=O stretching of amides from 1640 to 1690 cm ^-1 , NH bending of amides from 1550 to 1640 cm ^-1 , 1400 to 1600 By confirming the aromatic C=C stretching band at cm ⁻¹ , the production of hyperbranched polyamides, which are three types of flow control agents, was confirmed.

In addition, in the case of HBPA_H2O, it can be seen that there is an acyl halide stretching band at 1800 to 1900 cm ^-1 and there is a chloride group remaining unreacted, and in the case of HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ 3000 to 3100 cm ^- In ¹ , you can see a stretching band of an ethoxy group or a methoxy group.

That is, when the hyperbranched polyamide, a flow control agent prepared according to the present invention, was washed with methanol and ethanol, the organic acid chloride remaining unreacted reacted as shown in Scheme B and Scheme C below to react with a methoxy group (Methoxy group) group) or an ethoxy group.

<Scheme B>

<Scheme C>

Figure 2 shows the differential scanning calorimetry (DSC) results of hyperbranched polyamides HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ which are flow control agents prepared according to an embodiment of the present invention, HBPA_H2O is 148.63 ℃, HBPA_OCH ₃ is 171.97 ℃, HBPA_OCH ₂ CH ₃ It was found to show a glass transition temperature (Tg) at 162.57 ℃.

Figure 3 shows the thermogravimetric analysis (TGA) results of hyperbranched polyamides HBPA_H2O, HBPA_OCH ₃ , HBPA_OCH ₂ CH ₃ , which are flow control agents prepared according to an embodiment of the present invention. HBPA_H2O 1.00 is 248.28 ℃, HBPA_OCH ₃ 1.00 is At 371.66℃, HBPA_OCH ₂ CH ₃ 1.00, the polymer decomposition temperature (Td 5%) was found at 376.36℃, that is, the prepared hyperbranched polyamide was higher when washed with an alcohol solvent than when washed with distilled water. It can be seen that thermal stability is exhibited.

4 is data confirming the reproducibility of hyperbranched polyamide HBPA_OCH ₃ , which is a flow control agent prepared according to an embodiment of the present invention. It can be seen that a relatively uniform sample with higher thermal stability was prepared.

<Comparative Example 1> Preparation of specimen of polymer composition

100% by weight of polyamide-based resin (Woosung Chemical, PA6) was kneaded for 3 minutes at a temperature of 260 ℃ and a screw rotation speed of 80 rpm using a 15 cc micro compounder (DSM Xplore) in the form of a twin screw, and then heated to 80 ℃. By injection from a set mold, a spiral specimen for fluidity check and a disc specimen for viscosity analysis were produced.

<Comparative Example 2> Preparation of specimen of polymer composition

100% by weight of polyamide-based resin (Woosung Chemical, PA66) was kneaded for 3 minutes at a temperature of 280 ℃ and a screw rotation speed of 80 rpm using a 15 cc micro compounder (DSM Xplore) in the form of a twin screw, and then heated to 80 ℃. By injection from a set mold, a spiral specimen for fluidity check and a disc specimen for viscosity analysis were produced.

<Example 1> Preparation of specimens of polymer composition with addition of flow control agent

A specimen was prepared in the same manner as in Comparative Example 1, except that HBPA_OCH ₃ 1.00 1phr (parts by weight relative to 100 parts by weight of the total polymer composition) was used as the flow control agent in Comparative Example 1.

<Example 2> Preparation of rheology control agent-added polymer composition specimen

A specimen was prepared in the same manner as in Comparative Example 1, except that HBPA_OCH ₃ 1.00 3 phr (parts by weight relative to 100 parts by weight of the total polymer composition) was used as the flow control agent in Comparative Example 1.

<Example 3> Preparation of polymer composition specimen with addition of flow control agent

A specimen was prepared in the same manner as in Comparative Example 2, except that HBPA_OCH ₃ 1.00 1phr (parts by weight relative to 100 parts by weight of the total polymer composition) was used as a flow control agent in Comparative Example 2.

<Example 4> Preparation of polymer composition specimen with addition of flow control agent

A specimen was prepared in the same manner as in Comparative Example 2, except that HBPA_OCH ₃ 1.00 3 phr (parts by weight relative to 100 parts by weight of the total polymer composition) was used as the flow control agent in Comparative Example 2.

<Experimental Example 1> Viscosity reduction rate analysis

In order to measure the viscosity reduction rate of the polymer composition according to the present invention, an experiment was conducted as follows.

The polymer compositions prepared in Comparative Examples 1 to 2 and Examples 1 to 4 were measured using a rotational viscometer (TA instruments, ARES-G2). Specifically, the disc-shaped (Disc) specimens prepared in Comparative Example 1 and Examples 1 to 2 were measured at a PA6 processing temperature of 260° C., and the disc-shaped (Disc) specimens prepared in Comparative Example 2 and Examples 3 to 4 were measured. ) The specimen was measured at 270°C, which is the processing temperature of PA66. The results are shown in FIG. 8 and are summarized in Table 2 below.

polyamide resin
(parts by weight) flow regulator
type Flow control agent content
(phr) average viscosity
(Pa.s) decrease rate
(%) Comparative Example 1 PA6 (100) - - 141.47 - Comparative Example 2 PA66 (100) - - 93.64 - Example 1 PA6 (100) HBPA_OCH ₃ One 119.07 15.83 Example 2 PA6 (100) HBPA_OCH ₃ 3 110.06 22.20 Example 3 PA66 (100) HBPA_OCH ₃ One 76.53 18.27 Example 4 PA66 (100) HBPA_OCH ₃ 3 71.30 23.85

5 shows the viscosity of a polyamide-based polymer composition according to an embodiment of the present invention. As can be seen from FIG. 5 , it can be confirmed that the viscosity decreases when the polymer composition according to an embodiment of the present invention is used, and it can be confirmed that the viscosity decrease rate further increases as the content increases. In addition, it can be seen that the viscosity decreases toward the high-speed shear region.

<Experimental Example 2> Flowability evaluation by measuring the length of a spiral specimen

By measuring the length of the spiral specimens prepared in Comparative Examples 1 to 2 and Examples 1 to 4, the flowability effect of the flow control agent including the hyperbranched polyamide was evaluated. An image of the prepared specimen is shown in FIG. 6, and injection conditions and results are summarized in Table 3 below.

6 is a spiral (Spiral) specimen prepared in order to confirm the flowability of the polymer composition prepared by adding 0 phr, 1 phr, and 3 phr of HBPA_OCH ₃ prepared according to an embodiment of the present invention to PA6 and PA66, respectively. look. The better the fluidity, the longer the specimen length, and it can be seen that the specimen lengthens as the content increases.

polyamide resin
(parts by weight) flow regulator
type Flow control agent content
(phr) injection pressure
(bar) flowability
(cm) rate of increase
(%) Comparative Example 1 PA6 (100) - - 16 33.4 - Comparative Example 2 PA66 (100) - - 12 30.4 - Example 1 PA6 (100) HBPA_OCH ₃ One 16 35.0 4.79 Example 2 PA6 (100) HBPA_OCH ₃ 3 16 36.8 10.18 Example 3 PA66 (100) HBPA_OCH ₃ One 12 32.4 6.58 Example 4 PA66 (100) HBPA_OCH ₃ 3 12 36.1 18.75

As shown in Table 3, it can be seen that the polyamide-based polymer composition including the flow control agent according to the present invention has an effect on improving the flowability. Comparing Comparative Example 1 and Example 2, the flowability of the polyamide-based (PA6) polymer composition containing the flow control agent in Example 2 was about 10% higher than that of the polymer composition without the flow control agent in Comparative Example 1 It can be seen that the increase, and comparing Comparative Example 2 and Example 4, it can be seen that the flowability of the polyamide-based (PA66) polymer composition increased by about 18%.

This can have a great effect in reducing the load on the equipment by improving the fluidity under the actual extrusion and injection conditions, thereby increasing the lifespan of the equipment, and lowering the production power or output energy to lower the overall production cost.

Accordingly, the polymer composition according to the present invention can be usefully applied to compounding, extrusion, and injection molding of polyamide-based engineering plastics containing high content of glass fibers, and also to the addition of the flow control agent according to the present invention. As a result, the flowability during processing is greatly improved, and an even mixing of the reinforcing fiber and the polymer resin is induced.

Claims (9)

After the amide formation reaction between the linear diamine compound represented by the following formula (A), the linear amine compound represented by the formula (B), and the polyvalent organic acid or organic acid chloride represented by the following formula (C) as a flow control agent in the polyamide-based resin, the residual organic acid group is converted to an alkyl ester group A polyamide-based polymer composition having improved fluidity, characterized in that it contains a hyperbranched polyamide:
<Formula A>

However, in Formula A, R is one of an alkylene group having 1 to 15 carbon atoms,
<Formula B>

However, in Formula B, R' is one of an alkyl group having 2 to 4 carbon atoms,
<Formula C>

However, in Formula C, X is -OH or -Cl. The method according to claim 1,
The polyamide-based resin is a polyamide having improved fluidity, characterized in that it is at least one polyamide selected from the group consisting of polyamide derived from lactam, polyamide obtained through the reaction of dicarboxylic acid with diamine, and copolyamide. based polymer composition. The method according to claim 1,
The polyamide-based polymer composition is a polyamide-based polymer composition having improved fluidity, characterized in that it contains 0.1 to 5 parts by weight of the hyperbranched polyamide, which is a flow control agent, based on 100 parts by weight of the polyamide-based resin. The method according to claim 1,
The hyperbranched polyamide, which is the flow control agent, is a polyamide-based polymer composition having improved fluidity, characterized in that it is prepared by the reaction of Scheme A:
<Scheme A>

However, in Scheme A, R is one of an alkylene group having 1 to 15 carbon atoms, R' is one of an alkyl group having 2 to 4 carbon atoms, and R″ is an alkyl group having 1 to 6 carbon atoms. As a polyamide-based resin flow control agent, hyperbranched polyamide is produced by amide formation between a linear diamine compound represented by the following formula (A), a linear amine compound represented by formula (B), and a polyvalent organic acid or organic acid chloride represented by the following formula (C) hyperbranched polyamide manufacturing step;
A modified hyperbranched polyamide manufacturing step of converting the residual organic acid group of the hyperbranched polyamide into an alkylester group;
a melt-kneading step of mixing and heating the modified hyperbranched polyamide with a polyamide-based resin to prepare a melt-kneaded product; and
Method for producing a polyamide-based composition having improved fluidity, characterized in that it comprises a molding manufacturing step of molding the melt-kneaded product:
<Formula A>

However, in Formula A, R is one of an alkylene group having 1 to 15 carbon atoms,
<Formula B>

However, in Formula B, R' is one of the alkyl groups having 2 to 4 carbon atoms,
<Formula C>

However, in Formula C, X is -OH or -Cl. 6. The method of claim 5,
The polyamide-based resin is a polyamide having improved fluidity, characterized in that it is at least one polyamide selected from the group consisting of polyamide derived from lactam, polyamide obtained through the reaction of dicarboxylic acid with diamine, and copolyamide. Method for preparing a system composition. 6. The method of claim 5,
The method for producing a polyamide-based composition having improved fluidity, characterized in that the hyperbranched polyamide, which is the flow control agent, is prepared by the reaction of Scheme A:
<Scheme A>

However, in Scheme A, R is one of an alkylene group having 1 to 15 carbon atoms, R' is one of an alkyl group having 2 to 4 carbon atoms, and R″ is an alkyl group having 1 to 6 carbon atoms. 6. The method of claim 5,
The method for producing a polyamide-based composition having improved fluidity, characterized in that the step of preparing the modified hyperbranched polyamide converts the residual organic acid group of the hyperbranched polyamide to an alkylester group through a reaction with an alcohol-based compound. 6. The method of claim 5
The melt-kneading step is a method for producing a polyamide-based composition having improved fluidity, characterized in that it is performed at a temperature of 200 to 500 ℃.

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