Polyamide based polymer compositions comprising cyclic compound and polymer based composite material using the same

Abstract

The present disclosure relates to a polyamide-based polymer composition with superior fluidity and a polyamide-based composite material with superior mechanical strength prepared therefrom. More specifically, it relates to a polyamide-based polymer composition containing 0.1-5 parts by weight of dicyclohexylmethane bisdecanoamide, which is a cyclic compound, as a fluidity control agent based on 100 parts by weight of a mixture consisting of 20-90 wt % of a polyamide-based resin and 10-80 wt % of a reinforcing fiber, a polyamide-based composite material prepared using the same, and a method for preparing the same. The polymer composition according to the present disclosure, wherein dicyclohexylmethane bisdecanoamide is used as a fluidity control agent, provides an effect of reducing friction between a molten resin and a processing machine and greatly reducing torque by effectively dispersing a reinforcing fiber in a polyamide-based resin. Also, the polymer composition according to the present disclosure may be usefully used in compounding, extrusion molding and injection molding of polyamide-based engineering plastics containing reinforcing fibers at high contents. In addition, according to the present disclosure, the addition of the fluidity control agent greatly improves flowability during processing. Therefore, a polyamide-based composite material with superior mechanical strength can be prepared under relatively mild conditions because uniform mixing of the reinforcing fiber and the polymer resin is induced.

Claims

1. A polyamide-based polymer composition comprising a mixture of a polyamide-based resin and a reinforcing fiber and dicyclohexylmethane bisdecanoamide as a fluidity control agent.

2. The polyamide-based polymer composition according to claim 1, wherein the mixture consists of 20-90 wt % of a polyamide-based resin and 10-80 wt % of a reinforcing fiber.

3. The polyamide-based polymer composition according to claim 1, wherein the polyamide-based resin is one or more polyamide selected from a group consisting of a polyamide derived from a lactam, a polyamide obtained from a reaction of a dicarboxylic acid and a diamine and a copolymer polyamide.

4. The polyamide-based polymer composition according to claim 1, wherein the reinforcing fiber is one of a glass fiber and a carbon fiber.

5. The polyamide-based polymer composition according to claim 1, wherein the dicyclohexylmethane bisdecanoamide as a fluidity control agent is comprised in an amount of 0.1-5 parts by weight based on 100 parts by weight of the mixture.

6. A method for preparing a polyamide-based composite material, which comprises: a melt-mixing step of preparing a molten mixture by adding dicyclohexylmethane bisdecanoamide as a fluidity control agent to a mixture of a polyamide-based resin and a reinforcing fiber and then mixing the same while heating; and a molding step of molding the molten mixture.

7. The method for preparing a polyamide-based composite material according to claim 6, wherein the mixture consists of 20-90 wt % of a polyamide-based resin and 10-80 wt % of a reinforcing fiber.

8. The method for preparing a polyamide-based composite material according to claim 6, wherein the melt-mixing step is performed at 200-500 C.

9. The method for preparing a polyamide-based composite material according to claim 6, wherein the molding step is performed by extrusion-molding or injection-molding the molten mixture.

10. A polyamide-based composite material prepared by the method according to claim 6, which comprises a polyamide-based resin, a reinforcing fiber and dicyclohexylmethane bisdecanoamide as a fluidity control agent.

Description

BEST MODE

(1) It will be understood that the terms or words used in the detailed description and claims of the present disclosure should be interpreted as having a meaning that is consistent with their meaning in the context of the technical idea of the invention, based on the principle that an inventor may properly define the meaning of the terms or words to best explain the invention. It should also be understood that the exemplary embodiments described in the present disclosure do not represent all the technical idea of the present disclosure. Accordingly, there may exist various equivalents and modifications that can replace them within the purpose of the present disclosure at the time of the filing of this application.

(2) The term polyamide-based resin used in the present disclosure may refer to a homopolymer or a copolymer. In the present disclosure, one or more linear or branched polyamide may be used as the polyamide. The linear polyamide may be prepared from a dicarboxylic acid and a diamine. The branched polyamide may be prepared from monomers having more than two acid or amine groups. Accordingly, it may be prepared from an amine and a carboxylic acid where a branching point may occur.

(3) For example, the polyamide may be 7- to 13-membered cyclic polycaprolactam, polycaprylolactam or polylaurolactam derived from lactam or a polyamide obtained from a reaction of a dicarboxylic acid and a diamine.

(4) Specifically, the dicarboxylic acid may be an alkanedicarboxylic acid or an aromatic dicarboxylic acid having 6 to 12, particularly 6 to 10, carbon atoms, specifically, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, etc. And, the diamine may be specifically an alkanediamine having 6 to 12, particularly 6 to 8, carbon atoms, 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, etc.

(5) Accordingly, the polyamide may be specifically polyhexamethylene adipamide, polyhexamethylene sebacamide, polycaprolactam or, in particular, nylon 6/6, 6 copolyamide having a caprolactam unit content of 5-95 wt %. In addition, a mixture of a plurality of polyamides with any desired mixing ratio or a polyamide that can be obtained from copolymerization of the two or more monomers described above may be used.

(6) Hereinafter, the polyamide-based polymer composition according to the present disclosure is described in detail.

(7) The polymer composition according to the present disclosure, which contains 0.1-5 parts by weight of dicyclohexylmethane bisdecanoamide, which is a cyclic compound, as a fluidity control agent based on 100 parts by weight of a mixture consisting of 20-90 wt % of a polyamide-based resin and 10-80 wt % of a reinforcing fiber, may exhibit superior fluidity and superior mechanical strength.

(8) A composite material prepared from the polymer composition exhibiting superior fluidity and superior mechanical strength may be usefully used in compounding, extrusion molding and injection molding of polyamide-based engineering plastics containing reinforcing fibers at high contents.

(9) The reinforcing fiber may be one of a glass fiber and a carbon fiber. For effective mixing, the reinforcing fiber may be specifically a short fiber rather than a long fiber. Also, it may be specifically a glass fiber when considering economic efficiency, etc.

(10) Specifically, the polymer composition according to the present disclosure provides an effect of decreasing viscosity toward a high-shear-rate range. This is significantly effective in reducing overall production cost by reducing load applied to a machine by improving fluidity in actual extrusion and injection conditions, thereby prolonging the service life of the machine, and by reducing power consumption, output energy, etc. In addition, the polymer composition according to the present disclosure can be used in various applications because it has superior mechanical strength.

(11) In the polymer composition according to the present disclosure, the fluidity control agent dicyclohexylmethane bisdecanoamide is a compound represented by Chemical Formula 1.

(12) ##STR00001##

(13) The dicyclohexylmethane bisdecanoamide used in the present disclosure as a fluidity control agent may exhibit very superior fluidity as compared to the existing fluidity control agent.

(14) Specifically, the fluidity control agent may be used in an amount of 0.1-5.0 parts by weight based on the mixture of the polyamide-based resin and the reinforcing fiber. When the amount of the fluidity control agent based on the mixture of the polyamide-based resin and the reinforcing fiber is less than 0.1 part by weight, superior fluidity cannot be achieved by adding the fluidity control agent. And, when the amount exceeds 5.0 parts by weight, a composite material prepared from the mixture of the polyamide-based resin and the reinforcing fiber has unsatisfactory mechanical strength.

(15) The mixture of the polyamide-based resin and the reinforcing fiber according to the present disclosure may contain specifically 20-90 wt % of the polyamide-based resin and 10-80 wt % of the glass fiber, more specifically 20-50 wt % of the polyamide-based resin and 50-80 wt % of the glass fiber. The mixture of the polyamide-based resin and the reinforcing fiber according to the present disclosure may be used as a composition for preparing a glass fiber-reinforced composite material with a glass fiber content of 50 wt % or higher.

(16) Hitherto, there have been limitations in improving productivity and physical properties when the glass fiber content is so high, due to the fracture of the glass fiber. However, the polymer composition according to the present disclosure can exhibit not only superior fluidity but also superior mechanical strength because of the use of the dicyclohexylmethane bisdecanoamide as the fluidity control agent.

(17) The present disclosure also provides a method for preparing a polyamide-based composite material, which includes: a melt-mixing step of preparing a molten mixture by adding dicyclohexylmethane bisdecanoamide as a fluidity control agent to a mixture of a polyamide-based resin and a reinforcing fiber and then mixing the same while heating; and a molding step of molding the molten mixture.

(18) Specifically, the mixture may be a mixture of 20-90 wt % of the polyamide-based resin and 10-80 wt % of the reinforcing fiber. More specifically, it may contain 20-50 wt % of the polyamide-based resin and 50-80 wt % of the glass fiber.

(19) The method for preparing a polyamide-based composite material according to the present disclosure is for preparing a glass fiber-reinforced composite material with a glass fiber content of 50 wt % or higher. Hitherto, there have been limitations in improving productivity and physical properties when the glass fiber content is so high, due to the fracture of the glass fiber. However, superior fluidity as well as superior mechanical strength can be achieved by using the dicyclohexylmethane bisdecanoamide as the fluidity control agent.

(20) A composite material prepared from the polymer composition exhibiting superior fluidity and superior mechanical strength may be usefully used in compounding, extrusion molding and injection molding of polyamide-based engineering plastics containing glass fibers at high contents.

(21) Specifically, the dicyclohexylmethane bisdecanoamide as a fluidity control agent may be used in an amount of 0.1-5.0 parts by weight based on the mixture of the polyamide-based resin and the reinforcing fiber. When the fluidity control agent is used in an amount less than 0.1 part by weight based on the mixture of the polyamide-based resin and the reinforcing fiber, superior fluidity cannot be achieved by adding the fluidity control agent. And, when the amount exceeds 5.0 parts by weight, the prepared composite may have unsatisfactory mechanical strength.

(22) The melt-mixing step may be performed at any temperature where the polyamide-based resin can be melted. For example, it may be performed at 200-500 C.

(23) The molding step may be performed by extrusion-molding or injection-molding the molten mixture. Specifically, the extrusion molding may be performed at 200-350 C. When the extrusion molding is performed at a temperature below 200 C., it is difficult to uniformly mix the polyamide-based resin and the glass fiber. And, when it is performed at a temperature above 350 C., the prepared polyamide-based composite material may have unsatisfactory mechanical properties or economic efficiency may decrease due to the processing at high temperature. And, the injection molding in the method for preparing a polyamide-based composite material according to the present disclosure may be performed by a known method using an apparatus such as an injection molding machine.

(24) Hereinafter, the present disclosure will be described in detail through examples and test examples. However, the following examples and test examples are for illustrative purposes only and the scope of the present disclosure is not limited by the examples and test examples.

Preparation of Polyamide-Based Polymer Composition

(25) 50 wt % of a polyamide-based resin (21ZLV, Ascend), 50 wt % of a glass fiber (123D, Owens Corning, length: 3 mm, diameter: 10 m, chopped) and 1 phr (parts by weight based on 100 parts by weight of the total polymer composition) of dicyclohexylmethane bisdecanoamide (MCHA_DA) as a fluidity control agent were mixed uniformly.

(26) Then, a polyamide-based polymer composition was prepared by melting and mixing the mixture using a twin screw-type 15 cc microcompounder (DSM Xplore) under the condition of a temperature of 280 C. and a screw rotation speed of 80 rpm for 4 minutes.

Comparative Example 1

(27) A polymer composition was prepared by melting and mixing 50 wt % of a polyamide-based resin (21ZLV, Ascend) and 50 wt % of a glass fiber (123D, Owens Corning, length: 3 mm, diameter: 10 m, chopped) using a twin screw-type 15 cc microcompounder (DSM Xplore) under the condition of a temperature of 280 C. and a screw rotation speed of 80 rpm for 4 minutes.

Comparative Example 2

(28) 50 wt % of a polyamide-based resin (21ZLV, Ascend), 50 wt % of a glass fiber (123D, Owens Corning, length: 3 mm, diameter: 10 m, chopped) and 1 phr (parts by weight based on 100 parts by weight of the total polymer composition) of diphenylmethane bisdecanoamide (MDA_DA) as a fluidity control agent were mixed uniformly.

(29) Then, a polymer composition was prepared by melting and mixing the mixture using a twin screw-type 15 cc microcompounder (DSM Xplore) under the condition of a temperature of 280 C. and a screw rotation speed of 80 rpm for 4 minutes.

Analysis of Average Torque

(30) The following experiment was carried out in order to measure the average torque of the polymer composition according to the present disclosure.

(31) Average torque was measured after melting and mixing the polymer compositions prepared in Example 1 and Comparative Examples 1-2 using a twin screw-type 15 cc microcompounder (DSM Xplore) under the condition of a temperature of 280 C. and a screw rotation speed of 80 rpm for 4 minutes. The result is shown in Table 1.

(32) TABLE-US-00001 TABLE 1 Polyamide- Glass Fluidity based fiber control Content Average resin (wt %) (wt %) agent (phr) torque (N) Example 1 50 50 MCHA_DA 1 1313 Comparative 50 50 0 1715 Example 1 Comparative 50 50 MDA_DA 1 1297 Example 2

(33) As seen from Table 1, the polymer composition containing dicyclohexylmethane bisdecanoamide as a fluidity control agent according to the present disclosure shows a very superior effect of reducing average torque. To compare Example 1 with Comparative Example 1, it can be seen that the average torque of the polymer composition containing dicyclohexylmethane bisdecanoamide (MCHA_DA) of Example 1 is decreased by about 23% as compared to the polymer composition not containing dicyclohexylmethane bisdecanoamide (MCHA_DA) of Comparative Example 1. To compare Example 1 with Comparative Example 2, it can be seen that the polymer composition containing dicyclohexylmethane bisdecanoamide (MCHA_DA) of Example 1 shows a comparable effect of decreasing average torque as compared to the polymer composition containing diphenylmethane bisdecanoamide (MDA_DA) of Comparative Example 2.

Analysis of Viscosity

(34) The following experiment was carried out in order to measure the viscosity of the polymer composition according to the present disclosure.

(35) The viscosity of the polymer compositions prepared in Example 1 and Comparative Examples 1-2 was measured using a capillary viscometer (Rheograph 25, Gttfert). The result is shown in Table 2.

(36) TABLE-US-00002 TABLE 2 Fluidity control Content Shear rate Shear stress Viscosity agent (phr) (1/s) (Pa) (Pa .Math. s) Example 1 MCHA_ 1 100.0001 12818.3330 128.1832 DA 500.0004 37509.0820 75.0181 1000.0008 62490.7500 62.4907 5000.0039 176480.0000 35.2960 9999.9902 260166.8675 26.0167 Comparative 0 100.0001 332330.0000 168.9915 Example 1 500.0004 53085.8320 106.1716 1000.0008 88700.0000 88.6999 5000.0039 238105.0156 47.6210 9999.9902 332330.0000 33.2330 Comparative MDA_ 1 100.0001 15107.5000 151.0749 Example 2 DA 500.0004 45535.8320 91.0716 1000.0008 73505.0000 73.5049 5000.0039 206219.1719 41.2438 9999.9902 296412.5000 29.6413

(37) As seen from Table 2, the polymer composition containing dicyclohexylmethane bisdecanoamide (MCHA_DA) as a fluidity control agent according to the present disclosure shows an effect of decreasing viscosity toward a high-shear-rate range.

(38) This is significantly effective in reducing overall production cost by reducing load applied to a machine by improving fluidity in actual extrusion and injection conditions, thereby prolonging the service life of the machine, and by reducing power consumption, output energy, etc.

Analysis of Flowability

(39) The following experiment was carried out in order to measure the flowability of the polymer composition according to the present disclosure.

(40) The flowability of the polymer compositions prepared in Example 1 and Comparative Examples 1-2 was measured using a spiral mold under the condition of a mold temperature of 80 C. and an injection pressure of 6 bar. The result is shown in Table 3.

(41) TABLE-US-00003 TABLE 3 Polyamide- Fluidity based resin Glass fiber control Content Flowability (wt %) (wt %) agent (phr) (cm) Example 1 50 50 MCHA_DA 1 44 Comparative 50 50 0 35.6 Example 1 Comparative 50 50 MDA_DA 1 40.7 Example 2

(42) As seen from Table 3, the polymer composition containing dicyclohexylmethane bisdecanoamide (MCHA_DA) as a fluidity control agent according to the present disclosure shows a significantly improved flowability. To compare Example 1 with Comparative Example 1, it can be seen that the flowability of the polymer composition containing dicyclohexylmethane bisdecanoamide of Example 1 is increased by about 23% as compared to the polymer composition not containing dicyclohexylmethane bisdecanoamide of Comparative Example 1. To compare Example 1 with Comparative Example 2, it can be seen that the flowability of the polymer composition containing dicyclohexylmethane bisdecanoamide (MCHA_DA) of Example 1 is increased by about 14% as compared to the polymer composition containing diphenylmethane bisdecanoamide (MDA_DA) of Comparative Example 2.

Measurement of Physical Properties

(43) The following experiment was carried out in order to measure the physical properties of the polymer composition according to the present disclosure.

(44) The physical properties of the polymer compositions prepared in Example 1 and Comparative Examples 1-2 were measured using a universal testing machine (Instron) and an Izod impact tester (Instron). The result is shown in Table 4.

(45) TABLE-US-00004 TABLE 4 Polyamide- Glass Fluidity Flexural Tensile Impact based resin fiber control Content modulus strength strength (wt %) (wt %) agent (phr) (MPa) (MPa) (kJ/m.sup.2) Ex. 1 50 50 MCHA_DA 1 14830 244 20 Comp. Ex. 1 50 50 0 14155 236 19 Comp. Ex. 2 50 50 MDA_DA 1 15025 242 20

(46) As seen from Table 4, the polymer composition containing dicyclohexylmethane bisdecanoamide as a fluidity control agent according to the present disclosure has excellent fluidity for molding and improved mechanical properties as compared to the compositions not containing dicyclohexylmethane bisdecanoamide.

(47) As described above, it can be seen that the polymer composition according to the present disclosure, wherein dicyclohexylmethane bisdecanoamide is used as a fluidity control agent, provides an effect of reducing friction between a molten resin and a processing machine and greatly reducing torque by effectively dispersing a reinforcing fiber in a polyamide-based resin.

(48) Also, the polymer composition according to the present disclosure may be usefully used in compounding, extrusion molding and injection molding of polyamide-based engineering plastics containing reinforcing fibers at high contents. In addition, according to the present disclosure, the addition of the fluidity control agent greatly improves flowability during processing. Therefore, a polyamide-based composite material with superior mechanical strength can be prepared under relatively mild conditions because uniform mixing of the reinforcing fiber and the polymer resin is induced.