KR20220144945A - Flow modifier comprising linear polymer and polymer composition with enhanced flowability by comprising the same - Google Patents

Abstract

The present invention relates to a fluidic modifier comprising a linear polymer and to a polymer composition with enhanced flowability by comprising the same, and specifically, to the fluidic modifier comprising the linear polymer, which improves the flowability of the polymer resin to greatly reduce torque applied to a processing machine of the polymer resin to improve the dispersibility of reinforcing fibers in a polymer composite material in which reinforcing fibers are mixed, and has excellent uniformity and thermal stability and can prevent corrosion of processing equipment, and to the polymer composition with enhanced flowability by comprising the same.

Description

A flow modifier comprising a linear polymer and a polymer composition comprising the same with improved flowability

The present invention relates to a rheology modifier comprising a linear polymer and a polymer composition having improved fluidity including the same. Specifically, the present invention can greatly reduce the torque applied to the processing machine of the polymer resin by improving the flowability of the polymer resin, and at the same time can improve the dispersibility of the reinforcing fibers in the polymer composite material mixed with the reinforcing fibers, and the uniformity And it relates to a fluidity modifier comprising a linear polymer, which has excellent thermal stability and can prevent corrosion of processing equipment, and a polymer composition with improved fluidity including the same.

Recently, as governments around the world strengthen regulations on fuel efficiency and exhaust gas, automobile manufacturers 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 can maximize the weight reduction effect by not only reducing the weight of the parts, but also enabling optimal design and parts integration.

Here, fiber-reinforced plastic or fiber-reinforced composite material is a generic term for a composite material reinforced with glass fiber, carbon fiber, aramid fiber, etc. with plastic as a matrix. It is widely used where necessary. 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.

In particular, polyamide-based composite material is a material with excellent rigidity, toughness, and chemical resistance, and has excellent light weight, impact resistance, coefficient of thermal expansion, and economic feasibility. Since the reduction is possible up to 30% or more, it is difficult to present a solution using advanced materials in the automobile market that requires weight reduction, design flexibility, and ease of molding when applied not only for exterior of automobiles, but also for interior parts including housings. It is possible.

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. 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 higher, 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 .

Here, in order to realize the high function of the polyamide-based composite material, compounding technology with various reinforcing materials is essential, and when high content glass fiber is added, the fluidity is not good, and when the physical properties are satisfied, the processability is poor. It is difficult to mold through the process or 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 melt as well as selection of processing equipment should be used to improve processability. do.

However, the flow control agent of the conventional polyamide-based polymer resin is insufficient to improve the flowability, and in particular, when applied to a polymer composite material in which reinforcing fibers are mixed, there is a limit in improving the dispersibility of the reinforcing fibers, uniformity and heat There was a problem of poor stability and causing corrosion of processing equipment.

Therefore, it is possible to significantly reduce the torque applied to the processing equipment of the polymer resin by improving the flowability of the polymer resin, and at the same time, it is possible to improve the dispersibility of the reinforcing fibers in the polymer composite material mixed with the reinforcing fibers, and the uniformity and thermal stability are improved. There is an urgent need for a new flow control agent that is excellent and can prevent corrosion of processing equipment.

The present invention is a fluidity containing a linear polymer that can improve the flowability of a polymer resin to greatly reduce the torque applied to the processing machine of the polymer resin, and at the same time improve the dispersibility of the reinforcing fibers in a polymer composite material mixed with reinforcing fibers An object of the present invention is to provide a polymer composition with improved fluidity including a modifier and the same.

Another object of the present invention is to provide a fluidity modifier including a linear polymer having excellent uniformity and thermal stability and preventing corrosion of processing equipment, and a polymer composition having improved fluidity including the same.

In order to solve the above problems, the present invention,

A rheology modifier comprising a linear polymer, wherein the linear polymer is prepared by converting an unreacted residual organic acid group into an alkyl ester group after an amide formation reaction between a divalent organic carboxylic acid or carboxylic acid chloride and a linear alkyl diamine compound. provides

Here, it provides a rheology modifier, characterized in that it has a structure of the following formula (1).

[Formula 1]

In Formula 1,

R is a divalent unsaturated hydrocarbon having 1 to 10 carbon atoms,

R' is a divalent unsaturated hydrocarbon having 1 to 15 carbon atoms,

R ₁ is an alkyl group having 1 or 2 carbon atoms,

n is 5 to 50;

In addition, the divalent organic carboxylic acid or carboxylic acid chloride provides a flow modifier, characterized in that it has a structure of the following formula (2).

[Formula 2]

In Formula 2,

R is a divalent unsaturated hydrocarbon having 1 to 10 carbon atoms,

X is -OH or -Cl.

And, the linear alkyl diamine compound provides a rheology modifier, characterized in that it has a structure of the following formula (3).

[Formula 3]

In Formula 3,

R' is a divalent unsaturated hydrocarbon having 1 to 15 carbon atoms.

Furthermore, the divalent organic carboxylic acid or carboxylic acid chloride provides a rheology modifier, characterized in that it has the structures of Chemical Formulas 4 to 6 below.

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6,

X is -OH or -Cl.

In addition, the linear alkyl diamine compound provides a rheology modifier, characterized in that it has a structure of the following formulas 7 to 9 selectively.

[Formula 7]

[Formula 8]

[Formula 9]

Further, it provides a flow modifier, characterized in that the intrinsic viscosity of the linear polymer is 0.01 to 0.60 dL / g.

On the other hand, it provides a method for preparing a rheology modifier containing the linear polymer by the following Reaction Scheme 1.

[Scheme 1]

In addition, polymer resin; And it provides a polymer composition comprising the rheology modifier.

Here, based on 100 parts by weight of the polymer resin, the content of the flow modifier is 0.1 to 5 parts by weight, it provides a polymer composition.

The fluidity modifier containing the linear polymer according to the present invention improves the flowability of the polymer resin through a specific molecular structure to greatly reduce the torque applied to the processing machine of the polymer resin, and at the same time, the reinforcing fiber in the polymer composite material mixed with the reinforcing fiber It shows an excellent effect of improving the dispersibility of

In addition, the rheology modifier containing the linear polymer according to the present invention exhibits excellent uniformity and thermal stability by converting residual organic acid groups into alkyl ester groups in a specific molecular structure, and an excellent effect of preventing corrosion of processing equipment.

1 shows FT-IR spectra of rheology modifiers prepared according to Examples 1 to 4 of the present invention.
2 shows the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) results of the rheology modifiers prepared according to Examples 1 to 4 of the present invention.
3 is a result of measuring the viscosity of a polymer composition prepared by adding 0 phr, 0.1 phr, and 0.3 phr to polyamide 66 (PA66) of the rheology modifiers prepared according to Examples 1 to 4 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In the rheology modifier comprising the linear polymer according to the present invention, the linear polymer is adipoyl chloride, sebacoyl chloride, isophthaloy chloride, terephthaloyl chloride, etc. amide formation with divalent organic carboxylic acids or carboxylic acid chlorides of linear alkyl diamine compounds such as diaminohexane, diaminooctane, diaminododecane, oxydianiline, methylenebis(cyclohexylamine), etc. It can be prepared by converting the unreacted residual organic acid group into an alkyl ester group after the reaction.

For example, the linear polymer may have a structure of Formula 1 below.

[Formula 1]

In Formula 1,

R is a divalent unsaturated hydrocarbon having 1 to 10 carbon atoms,

R' is a divalent unsaturated hydrocarbon having 1 to 15 carbon atoms,

R ₁ is an alkyl group having 1 or 2 carbon atoms,

n is 5 to 50;

In particular, R may be an aliphatic or aromatic hydrocarbon, and R' may be an aliphatic, cycloaliphatic or aromatic hydrocarbon.

Specifically, the divalent organic carboxylic acid or carboxylic acid chloride may have a structure of Formula 2 below, and the linear alkyl diamine compound may have a structure of Formula 3 below.

[Formula 2]

In Formula 2,

X is -OH or -Cl.

[Formula 3]

In Formula 3,

R' is a divalent unsaturated hydrocarbon having 1 to 15 carbon atoms.

In particular, the divalent organic carboxylic acid or carboxylic acid chloride of Formula 2 may have structures of Formulas 4 to 6 below.

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6,

X is -OH or -Cl.

In addition, the linear alkyl diamine compound of Formula 3 may have structures of Formulas 7 to 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

For reference, the linear polymer of Formula 1 may be prepared through the reaction shown in Scheme 1 below.

[Scheme 1]

The linear polymer may have a molecular weight of 0.01 to 0.60 dL/g based on intrinsic viscosity. Here, when the intrinsic viscosity of the linear polymer is less than 0.01 dL/g, the viscosity is too low to improve the flowability of the added polymer resin, but may reduce physical properties such as mechanical properties, while the intrinsic viscosity is 0.60 dL/g In the case of more than g, the viscosity may be too high and the improvement in flowability of the added polymer resin may be insignificant.

Accordingly, the flow modifier containing the linear polymer according to the present invention has excellent miscibility or compatibility with the added polymer resin, particularly the polyamide-based resin, compared to the conventional flow control agent, and the polyamide-based resin By improving the flowability of the polymer resin, the torque applied to the processing equipment of the polymer resin is greatly reduced, and when the reinforcing fiber is added to the mixed polymer composite material, the dispersibility of the reinforcing fiber can be improved, such as high content glass fiber or carbon fiber, etc. It can be usefully applied in compounding, extrusion, and injection molding of engineering plastics with reinforcing fibers of

Specifically, the fluidity modifier containing the linear polymer according to the present invention exhibits an effect of lowering the viscosity toward the high-speed shear region during processing of the polymer composition, which improves the fluidity of the polymer composition under actual extrusion and injection conditions to be applied to molding equipment. It increases the lifespan of molding equipment by reducing the load, and it is effective in significantly lowering the overall production cost by lowering the production power or output energy. can be applied in the field.

In addition, since the linear polymer according to the present invention improves the uniformity and thermal stability by replacing the unreacted residual organic acid group with an alkylester group, and at the same time increases the pH, the unreacted residual organic acid group reacts with distilled water to form an organic acid, thereby continuously increasing acidity. It can effectively solve the problem of corrosion of processing equipment.

On the other hand, the flow modifier comprising the linear polymer according to the present invention may be added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the added polymer resin. Here, if the content of the flow modifier is less than 0.1 parts by weight, the effect of improving the flowability of the polymer resin may be insignificant, whereas if it is more than 5 parts by weight, physical properties such as mechanical strength of a molded article formed from the polymer composition may be reduced.

Here, the polymer resin to which the rheology modifier is added, particularly the polyamide-based resin, may be a homopolymer or a copolymer. In addition, the polyamide-based resin may include one or more linear or branched polyamides. The linear polyamide may be prepared from the reaction of a dicarboxylic acid with a diamine, wherein the branched polyamide may contain more than two acid groups or amine groups in the monomer, and thus branching points may occur with amines and carboxyl groups. It can be prepared from the reaction of acids.

The polyamide-based resin may be a polyamide obtained through reaction with a lactam-derived polycaprolactam, polycaprylolactam, polylaurolactam, dicarboxylic acid and the like having a ring member having 7 to 13 carbon atoms with diamine.

The dicarboxylic acids that can be used are alkanedicarboxylic acids or aromatic dicarboxylic acids having 6 to 12 carbon atoms, in particular 6 to 10 carbon atoms, preferably adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, iso phthalic acid and the like, preferred diamines are alkanediamines having 6 to 12 carbon atoms, especially 6 to 8 carbon atoms, also m-xylylenediamine, di(4-aminophenyl)methane, di(4-aminocyclohexyl)methane, 2,2 -di(4-aminophenyl)propane, 2,2-di(4-aminocyclohexyl)propane, 1,5-diamino-2-methylpentane, and the like.

Particularly preferred polyamides are polyhexamethyleneadipamide, polyhexamethylenesebacamide, polycaprolactam, in particular nylon-6/66 copolyamide 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.

Furthermore, when the polymer composition includes reinforcing fibers such as glass fibers and carbon fibers in the polymer resin, the content of the reinforcing fibers is 10 to 80% by weight, preferably 50, based on the total weight of the polymer composition. to 80% by weight.

Conventionally, when the reinforcing fiber is included in a high content of 50% by weight or more, there have been problems such as a decrease in productivity and a decrease in physical properties due to the breakage of the reinforcing fiber. Physical properties such as improvement and mechanical strength can be improved.

The polymer composition with improved fluidity by adding the fluidity modifier comprising the linear polymer according to the present invention can be prepared through melt-kneading in which the fluidity modifier and the polymer resin are mixed and heated, wherein the temperature at which the melt-kneading is performed is the polymer. It is not limited as long as the resin can be melted, and for example, it may be carried out at a temperature of 200 to 500 °C.

<Example>

1. Preparation example of linear polyamide

1) Synthesis of linear polyamide (ACHA) of Example 1

In a 500 ml beaker, 6.3 g (HA, 30 mmol) of 4,4'-diaminodicyclohexylmethane (4,4'-Methylenebis(cyclohexylamine)) was dissolved in 200 ml of acetone as a solvent, and then distilled water was added to 75 ml and prepare the HA solution. Prepare AC solution by dissolving 4.4 ml (AC, 30 mmol) of adipoyl chloride (AC, 30 mmol) with 100 ml of acetone in a 250 ml beaker. Place the HA solution in a water bath (Low Form Dewar Flask, 850ml) and fill with ice to adjust the temperature to 0°C, and then add the AC solution to the HA solution. After reacting for 2 hours using a tip sonicator, store at room temperature for 24 hours. The product was filtered and mixed with 300 ml of methanol in a 1L capacity beaker, stirred, and then 700 ml of acetone was added to precipitate the product for 1 hour, followed by filtering. Thereafter, the product was vacuum dried at 80° C. for 24 hours to obtain a clean product (ACHA).

2) Synthesis of linear polyamide (ACDA) of Example 2

In a 500 ml capacity beaker, 6.0 g (Oxy, 30 mmol) of 4,4'-Oxydianiline was dissolved in 200 ml of acetone as a solvent, and then 75 ml of distilled water was added to prepare an Oxy solution. . Prepare AC solution by dissolving 4.4 ml (AC, 30 mmol) of adipoyl chloride (AC, 30 mmol) with 100 ml of acetone in a 250 ml beaker. Place the Oxy solution in a water bath (Low Form Dewar Flask, 850ml), fill with ice, adjust the temperature to 0°C, and add AC solution to the Oxy solution. After reacting for 2 hours using a tip sonicator, store at room temperature for 24 hours. The product was filtered and mixed with 300 ml of methanol in a 1L capacity beaker, stirred, and then 700 ml of acetone was added to precipitate the product for 1 hour, followed by filtering. Thereafter, the product was vacuum dried at 80° C. for 24 hours to obtain a clean product (ACDA).

3) Synthesis of linear polyamide (ICDA) of Example 3

In a 500 ml capacity beaker, 4.3 g (OMDA, 30 mmol) of 1,8-diaminooctane (OMDA, 30 mmol) was dissolved in 200 ml of acetone as a solvent, and then 75 ml of distilled water was added to prepare an OMDA solution. Prepare an IC solution by dissolving 6.1 g (IC, 30 mmol) of isophthaloyl chloride in a 250 ml beaker with 100 ml of acetone. Place the OMDA solution in a water bath (Low Form Dewar Flask, 850ml), fill with ice, adjust the temperature to 0°C, and add the IC solution to the OMDA solution. After reacting for 2 hours using a tip sonicator, store at room temperature for 24 hours. The product was filtered and mixed with 300 ml of methanol in a 1L capacity beaker, stirred, and then 700 ml of acetone was added to precipitate the product for 1 hour, followed by filtering. Thereafter, the product was vacuum dried at 80° C. for 24 hours to obtain a clean product (ICDA).

4) Synthesis of linear polyamide (TCDA) of Example 4

In a 500 ml capacity beaker, 4.3 g (OMDA, 30 mmol) of 1,8-diaminooctane (OMDA, 30 mmol) was dissolved in 200 ml of acetone as a solvent, and then 75 ml of distilled water was added to prepare an OMDA solution. Prepare a TC solution by dissolving 6.1 g (TC, 30 mmol) of terephthaloyl chloride (TC, 30 mmol) in 100 ml of acetone in a 250 ml beaker. Place the OMDA solution in a water bath (Low Form Dewar Flask, 850ml), fill with ice, adjust the temperature to 0°C, and add the TC solution to the OMDA solution. After reacting for 2 hours using a tip sonicator, store at room temperature for 24 hours. The product was filtered and mixed with 300 ml of methanol in a 1L capacity beaker, stirred, and then 700 ml of acetone was added to precipitate the product for 1 hour, followed by filtering. Thereafter, the product was vacuum dried at 80° C. for 24 hours to obtain a clean product (TCDA).

1 shows FT-IR spectra of linear polyamides, which are rheology modifiers, prepared according to Examples ¹ to 4 of the present invention ^. Linear polyamides as four rheology modifiers by identifying stretching bands of oxy groups, stretching of alkyl at 2850 to 3000 cm ^-1 , NH bending of amides at 1550 to 1640 cm ^-1 , and CO stretching bands at 1400 to 1600 cm ^-1 . production was confirmed.

That is, it can be seen that the linear polyamide included in the rheology modifier according to the present invention is converted into a methoxy group by reacting all of the organic acid chloride remaining unreacted upon washing with methanol.

Figure 2 shows the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) results of the rheology modifiers prepared according to Examples 1 to 4 of the present invention, Example 1 is 195.26 ℃, Example 2 is 137.59 ℃ , Example 3 was found to show a glass transition temperature (Tg) at 95.96 ℃, Example 4 198.05 ℃, Example 1 is 250.27 ℃, Example 2 is 274.60 ℃, Example 3 is 285.25 ℃, Example 3 Example 4 was found to show a polymer decomposition temperature (Td 5%) at 280.62 ℃.

2. Preparation of specimens of polymer composition

1) Preparation of specimens of Examples 1 to 4

100 parts by weight of polyamide-based resin (Woosung Chemical, PA66) and 0.1/0.3 parts by weight of each of the linear polyamides of Examples 1 to 4, which are fluidity modifiers, using a 15 cc micro compounder (DSM Xplore) in the form of a twin screw After kneading for 3 minutes at a temperature of 280°C and a screw rotation speed of 80 rpm, it was injected in a mold set at 80°C to prepare a disc specimen for checking fluidity.

2) Preparation of specimens of comparative examples

A specimen was prepared in the same manner as in the specimen except that the rheology modifier was not used in the embodiment.

3. Physical property evaluation

1) Viscosity reduction rate analysis

In each of Examples and Comparative Examples, the polymer composition was measured using a rotational viscometer (TA instruments, ARES-G2) in the process of preparing the specimen. Specifically, the disc-shaped (Disc) specimens prepared in Examples and Comparative Examples were measured at 270° C., which is a PA66 processing temperature, and the results are as shown in FIG. 3 .

As shown in FIG. 3 , the polyamide-based polymer composition of the embodiment including the rheology modifier according to the present invention has improved flowability by increasing the viscosity reduction rate compared to the polyamide-based polymer composition of the comparative example that does not include the rheology modifier according to the present invention. In particular, it was confirmed that the viscosity decrease rate increased as the content of the rheology modifier increased and toward the high-speed shear region.

Claims (10)

A rheology modifier comprising a linear polymer, comprising:
The linear polymer is prepared by converting an unreacted residual organic acid group into an alkyl ester group after an amide formation reaction between a divalent organic carboxylic acid or carboxylic acid chloride and a linear alkyl diamine compound. The method of claim 1,
A rheology modifier, characterized in that it has the structure of Formula 1 below.
[Formula 1]

In Formula 1,
R is a divalent unsaturated hydrocarbon having 1 to 10 carbon atoms,
R' is a divalent unsaturated hydrocarbon having 1 to 15 carbon atoms,
R ₁ is an alkyl group having 1 or 2 carbon atoms,
n is 5 to 50. 3. The method of claim 2,
The divalent organic carboxylic acid or carboxylic acid chloride is characterized in that it has a structure of the following formula (2), flow modifier.
[Formula 2]

In Formula 2,
R is a divalent unsaturated hydrocarbon having 1 to 10 carbon atoms,
X is -OH or -Cl. 3. The method of claim 2,
The linear alkyl diamine compound is characterized in that it has a structure of the following formula (3), rheology modifier.
[Formula 3]

In Formula 3,
R' is a divalent unsaturated hydrocarbon having 1 to 15 carbon atoms. 4. The method of claim 3,
The divalent organic carboxylic acid or carboxylic acid chloride is a rheology modifier, characterized in that it has a structure of the following formulas 4 to 6 selectively.
[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6,
X is -OH or -Cl. 5. The method of claim 4,
The linear alkyl diamine compound is characterized in that it has the structures of formulas 7 to 9 below, the flow modifier.
[Formula 7]

[Formula 8]

[Formula 9]

7. The method according to any one of claims 1 to 6,
The flow modifier, characterized in that the intrinsic viscosity of the linear polymer is 0.01 to 0.60 dL / g. A method for preparing a rheology modifier comprising the linear polymer of claim 2 by Scheme 1 below.
[Scheme 1]

polymer resin; and
A polymer composition comprising the rheology modifier of any one of claims 1 to 6. 10. The method of claim 9,
Based on 100 parts by weight of the polymer resin, the content of the rheology modifier is 0.1 to 5 parts by weight, the polymer composition.

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