Polymer composite material composition including a compatibilizer composition to which a multifunctional crosslinking agent has been added

Abstract

The present invention relates to a polymer composite material composition comprising a compatibilizer composition to which a polyfunctional crosslinking agent is added, wherein the compatibilizer composition comprises a polyfunctional crosslinking agent to contribute to the improvement of the physical properties of the compatibilizer composition and further improve the compatibility and mechanical properties of the polymer composite material composition.

Description

Technology Field

[0001] The present invention relates to a polymer composite material comprising a compatibilizer composition, wherein the compatibilizer composition has a polyfunctional crosslinking agent added thereto. Background Technology

[0002] Plastic, one of the greatest inventions of the 20th century, possesses various excellent functions such as durability, processability, and chemical resistance in addition to the advantages of being lightweight and relatively inexpensive. However, due to population growth, the development of various industries, and the rapid increase in the fast food industry, a massive amount of disposable plastic packaging waste has been generated, causing various forms of environmental pollution. Consequently, as the need for environmental conservation is widely recognized globally, research is continuing on biodegradable polymers that are environmentally friendly by decomposing quickly, while also improving mechanical properties such as flexibility and strength, productivity, and processability to extend the lifespan of the product itself, reduce the amount of waste, or enhance recyclability.

[0003] Biodegradable polymers refer to polymers that self-decompose in response to various environmental factors, such as moisture, microorganisms, and temperature, either within the body or in the external environment, and are subsequently excreted or absorbed from the human body, or absorbed as organic matter into soil. Types include natural polymers such as starch extracted from grains, chitin obtained from the shells of crabs or shrimp, and cellulose obtained from grains or wood; synthetic polymers such as polycaprolactone (PCL), polylactic acid (PLA), and polybutylenesuccinate (PBS); and microbially produced polymers such as polyhydroxyalkanoates (PHA).

[0004] In particular, Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-co-4HB)), which is one of the biodegradable polymers and is called polyhydroxyalkanoate (PHA), is a common microorganism-based polymer that is manufactured by microorganisms and degraded by microorganisms. It possesses 100% biodegradability by microorganisms and enzymes in the ocean or on land, and unlike conventional polymer materials made from petroleum resources, it is a carbon-reducing material that generates less carbon dioxide during manufacturing. However, because its mechanical properties are relatively low, research on biodegradable eco-friendly composite materials that mix PHA with various polymers is actively underway to compensate for this.

[0005] Meanwhile, Polyamide 11 (PA11) is a non-biodegradable amide-based polymer and a semi-crystalline polymer derived from castor oil, a plant component, used as a carbon-reducing material. It possesses excellent biocompatibility and, compared to short-chain polyamides, exhibits superior mechanical properties such as chemical resistance, impact resistance, abrasion resistance, weather resistance, and dimensional stability. Furthermore, due to its wide range of applications, combining it with biodegradable polymers enables the development of composite materials that simultaneously satisfy eco-friendliness and versatility.

[0006] In order to mix biodegradable polymers and oil-based polymers to leverage the advantages of each polymer and manufacture them into materials such as fibers and films, the polymer mixture must have high compatibility with one another to possess good mechanical and physical properties. However, there are disadvantages, such as polymers not dissolving or dispersing in water due to hydrophobic properties, phase separation occurring due to differences in molecular structure, or low compatibility between polymers, which makes it difficult to manufacture the composition. To overcome these disadvantages and ensure that the polymer composite resins used as fiber and film materials possess good mechanical and physical properties and excellent processing performance, it is necessary to develop reactive compatibilizers that exhibit a co-continuous morphology at the interfaces of different polymers, as well as processing technologies capable of economically producing biodegradable polymer and oil-based polymer composite resins. Prior art literature

[0008] Republic of Korea Published Patent Application No. 2022-0166847 (December 19, 2022) The problem to be solved

[0009] In order to solve the above-mentioned problems, the present invention is devised as a result of the research on “manufacturing of biodegradable composite materials and improvement of physical properties using microorganism-based biopolymer PHA,” and aims to provide a polymer composite material composition that simultaneously satisfies eco-friendliness and versatility while possessing excellent mechanical properties.

[0010] However, the above purpose is exemplary, and the technical concept of the present invention is not limited thereto. means of solving the problem

[0011] One embodiment of the present invention for achieving the purpose relates to a polymer composite material composition characterized by comprising a compatibilizer composition comprising an acid anhydride-grafted microbial-based polymer and a polyfunctional crosslinking agent, and having a melting index (Mi) of 5.0 to 8.1 g / 10 min.

[0012] In one embodiment of the above, the microorganism-based polymer may be a polyhydroxyalkanoate (PHA).

[0013] In one embodiment above, the acid anhydride may be grafted onto the polyester main chain of the microorganism-based polymer.

[0014] In one embodiment above, the acid anhydride may be one or more selected from maleic anhydride, fumaric anhydride, acetylenedicarboxylic anhydride, glutaconic anhydride, 2-decenedioic anhydride, traumatic anhydride, muconic anhydride, glutinic anhydride, citraconic anhydride, mesaconic anhydride, and itaconic anhydride.

[0015] In one embodiment of the above, the polyfunctional crosslinking agent may be one or more selected from trimethylolpropane trimethacrylate (TMPTMA) and divinylbenzene (DVB).

[0016] In one embodiment above, the polyfunctional crosslinking agent may be included in an amount of more than 2 to less than 4 parts by weight per 100 parts by weight of the microorganism-based polymer.

[0017] In the above embodiment, the polymer may be one or more selected from oil-based polymers and biodegradable polymers.

[0018] In one embodiment above, the oil-based polymer may be polyamide 11 (PA11).

[0019] In one embodiment of the above, the biodegradable polymer may be a polyhydroxyalkanoate (PHA).

[0020] In one embodiment above, the compatibilizer composition may be included in an amount of 3 to 10 parts by weight per 100 parts by weight of the polymer. Effects of the invention

[0021] The present invention can improve processability by imparting excellent compatibility to a polymer composite material composition by adding a compatibilizer composition containing a polyfunctional crosslinking agent to a polymer mixture, thereby providing a polymer composite material composition that simultaneously satisfies eco-friendliness and versatility and possesses excellent mechanical properties. Brief explanation of the drawing

[0022] Figure 1 shows the results of dynamic instrument analysis according to one embodiment of the present invention. Figure 2 shows a graph of the glass transition temperature according to one embodiment of the present invention. Figure 3 shows the FT-IR analysis results according to one embodiment of the present invention. Figure 4 shows the measurement results of the melt index according to one embodiment of the present invention. Figure 5 shows the measurement results of tensile strength according to one embodiment of the present invention. Figure 6 shows the measurement results of the elongation rate according to one embodiment of the present invention. Figure 7 shows the measurement results of impact strength according to one embodiment of the present invention. Figure 8 shows the measurement results of the flexural modulus according to one embodiment of the present invention. FIGS. 9 to 12 show scanning electron microscope images according to one embodiment of the present invention. Specific details for implementing the invention

[0023] A polymer composite material composition comprising a compatibilizer composition containing a polyfunctional crosslinking agent according to the present invention will be described in detail below. The drawings presented below are provided as examples to ensure that the concept of the present invention is sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the concept of the present invention. Unless otherwise defined, technical and scientific terms used herein shall have the meaning commonly understood by those skilled in the art to which this invention pertains, and descriptions of known functions and configurations that could unnecessarily obscure the essence of the present invention in the following description and attached drawings are omitted.

[0024] One aspect of the present invention relates to providing a polymer composite material composition that can improve processability by imparting excellent compatibility to the polymer composite material composition by adding a compatibilizer composition containing a polyfunctional crosslinking agent, thereby simultaneously satisfying eco-friendliness and versatility and having excellent mechanical properties.

[0025] Hereinafter, a polymer composite material composition according to an example of the present invention will be described in detail.

[0026] First, a compatibilizing agent composition containing a polyfunctional crosslinking agent according to one example of the present invention will be described.

[0027] A compatibilizer composition containing a multifunctional crosslinking agent according to one example of the present invention is characterized by being prepared from a microorganism-based biodegradable polymer, wherein the microorganism-based polymer may be a polyhydroxyalkanoate (PHA). Polyhydroxyalkanoate (hereinafter PHA) is a thermoplastic linear polyester natural polymer that accumulates within microbial cells, is harmless to the human body, and possesses excellent biodegradability even under marine conditions. Specifically, polyhydroxyalkanoate (PHA) has the structure of Chemical Formula 1 below.

[0028] [Chemical Formula 1]

[0029]

[0030] The above PHA is a resource-recycling material that is 100% biodegradable by microorganisms and enzymes in the ocean or on land, making it compostable, and unlike conventional polymer materials made from petroleum resources, it does not emit toxic gases when incinerated and does not increase the concentration of carbon dioxide in the atmosphere.

[0031] A biodegradable polymer compatibilizer composition according to one example of the present invention may comprise an acid anhydride grafted to the polyester main chain of the microorganism-based polymer. The above acid anhydride may be one or more selected from maleic anhydride (MA), fumaric anhydride, acetylenedicarboxylic anhydride, glutaconic anhydride, 2-decenedioic anhydride, traumatic anhydride, muconic anhydride, glutinic anhydride, citraconic anhydride, mesaconic anhydride, and itaconic anhydride. However, when considering the miscibility with the components constituting the mixture, mechanical strength, or hygroscopicity when mixing the biodegradable polymer later, it is preferable to use maleic anhydride (MA) of Chemical Formula 2 below.

[0032] [Chemical Formula 2]

[0034]

[0036] The above acid anhydride may be included in an amount of more than 2 to less than 4 parts by weight per 100 parts by weight of the microorganism-based polymer, but if added in an amount of 2 parts by weight or less, the grafting efficiency does not meet expectations, and if added in an amount of 4 parts by weight or more, there is a disadvantage that the physical properties are degraded due to unreacted crosslinking agent.

[0037] A radical initiator may be added for grafting the above acid anhydride and the microorganism-based polymer. Considering the graft reaction efficiency, the above radical initiator is preferably a peroxide-based radical initiator, such as di-(tert-butylperoxyisopropyl)benzene, di-(2,4-dichlorobenzoyl)-peroxide, dibenzoyl peroxide, di(t-butyl peroxybenzoate), dicumyl peroxide, di-t-butylperoxide, and 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane. It may be one or more selected from t-butylcumylperoxide and 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane. Specifically, di-(tert-butylperoxyisopropyl)benzene of Chemical Formula 3 below may be used, and the di-(tert-butylperoxyisopropyl)benzene is hereinafter referred to as PK-14.

[0038] [Chemical Formula 3]

[0039]

[0041] The above radical initiator may be included in an amount of 0.05 to 0.15 parts by weight per 100 parts by weight of the microorganism-based polymer.

[0042] The above acid anhydride-grafted microorganism-based polymer may be PHA-g-MA prepared by grafting the above PHA and maleic anhydride, specifically reacting as shown in the following reaction scheme 1.

[0043] [Reaction Equation 1]

[0044]

[0045] Specifically, after the PHA-radical is formed by the radical initiator in Reaction Scheme 1, the addition reaction of Reaction Scheme 2 below may be entailed.

[0046] [Reaction Equation 2]

[0047]

[0048] When a radical initiator is used as in Reaction Scheme 2 above, the polymer becomes smaller and the molecular weight decreases due to an addition reaction in which β-cleavage occurs between the polymer chains of the primary generated PHA-radical, which may result in a decrease in mechanical properties. Accordingly, the present invention includes a multifunctional crosslinking agent to suppress the β-cleavage, thereby preventing the decrease in molecular weight and the deterioration of PHA-g-MA properties caused by the addition reaction.

[0049] The above-mentioned polyfunctional crosslinking agent includes trimethylolpropane trimethacrylate (TMPTMA), trimethylolethane triacrylate (TMETA), trimethylolpropane triacrylate (TMPTA), trimethylolethane trimethacrylate (TMETMA), divinylbenzene (DVB), pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentacrylate, diethyleneglycol dimethacrylate, and It may be one or more selected from bis(2-methacryloxyethyl)phosphate. More preferably, one or more selected from trimethylolpropane trimethacrylate (TMPTMA) shown in Chemical Formula 4 below or divinylbenzene (DVB) shown in Chemical Formula 5 below may be used.

[0050] [Chemical Formula 4]

[0052]

[0054] [Chemical Formula 5]

[0056]

[0057] The above trimethylolpropane trimethacrylate (TMPTMA) is a polyfunctional crosslinking agent that has two or more structurally active bonding sites within the compound, making it easy for the polymer to crosslink.

[0058] The above-mentioned divinylbenzene (DVB) is also a polyfunctional crosslinking agent that has two vinyl groups structurally, making crosslinking possible.

[0059] The double bond of the aforementioned DVB is a vinyl group and tends to generate free radical intermediates, whereas the methacrylate double bond of TMPTMA can participate not only in radical intermediates but also in isomer exchange reactions. Since these isomer exchange reactions affect the crosslinking reaction rate, they cause the reactivity of TMPTMA to be lower than that of DVB. In other words, compared to TMPTMA, which must access specific pathways to interact with other compounds due to its internal stereochemical configuration, DVB exhibits better reactivity because it is relatively less constrained by spatial structure.

[0060] The above-mentioned multifunctional crosslinking agent may be included in an amount of more than 2 parts by weight and less than 4 parts by weight per 100 parts by weight of the microorganism-based polymer. If the content of the multifunctional crosslinking agent is 2 parts by weight or less, it is difficult to inhibit the chain cleavage of radicals in the microorganism-based polymer, and there is a disadvantage of a low crosslinking ratio with the crosslinking agent. If it is 4 parts by weight or more, the crosslinking rate is high, fluidity decreases rapidly, and processability is poor; furthermore, residual crosslinking agent remains after the crosslinking reaction and may later stick to the hands, so it is preferable to use it within the above range.

[0061] The reaction in which the PHA radical, cleaved radical, and polymer are crosslinked by TMPTMA in the above reaction scheme 2 is as shown in the following reaction scheme 3.

[0062] [Reaction Equation 3]

[0063]

[0064] The reaction in which the PHA radical, the cleaved radical, and the polymer are crosslinked by DVB in the above reaction scheme 2 is as shown in the following reaction scheme 4.

[0065] [Reaction Equation 4]

[0066]

[0067] In the process of reaction scheme 2 above, the PHA radical is decomposed by β-cleavage, which may cause the molecular weight of the polymer to decrease and the melt index to increase. However, when the polyfunctional crosslinking agent is added, as shown in reaction schemes 3 and 4, the PHA radical, the cleaved radical, and the polymer form bonds with the polyfunctional crosslinking agent, resulting in a higher molecular weight and thus a lower melt index, and furthermore, the physical properties of PHA-g-MA can be improved.

[0068] As shown in Figure 4, when the melt index was measured using the compatibilizer composition containing the above TMPTMA and DVB in a polymer composite composition, the melt index of the polymer composite composition increased as the content of the compatibilizer composition increased when TMPTMA was used, and when DVB was used, the melt index decreased and the grafting yield could be high. A decrease in the melt index means that more imide bonds were formed between the compatibilizer composition and the polymer, resulting in an increase in molecular weight. Since a melt index that is too high has the disadvantage of lowering physical properties due to a low molecular weight or making it difficult to process due to high fluidity of the polymer composite, and a melt index that is too low has the difficulty of reducing processability, the melt index of the polymer composite composition is most appropriate in the range of 5.0 to 8.1 g / 10 min.

[0069] Meanwhile, the above-mentioned compatibilizer composition can be prepared in detail by preparing a mixture containing a microorganism-based polymer, an acid anhydride, a radical initiator, and a multifunctional crosslinking agent, and then reactively extruding the mixture using a twin-screw extruder to produce it in the form of pellets, but is not limited thereto and can be prepared according to processes conventionally used in the industry.

[0070] In addition, in the step of inducing chemical bonding between the microbial-based polymer and the acid anhydride according to the present invention, the graft reaction temperature can preferably be selected in the range of 150 to 205°C when considering reaction efficiency.

[0071] Next, a polymer composite material composition comprising a compatibilizer composition to which the above-prepared polyfunctional crosslinking agent is added is described. The inclusion of the compatibilizer composition to which the above-prepared polyfunctional crosslinking agent is added to the polymer composite material composition provides excellent compatibility and has the advantage of improving processability and moldability by increasing the melt index compared to when only the polymer is composited.

[0072] The polymer of the above polymer composite material composition is one or more selected from oil-based polymers and biodegradable polymers, and the oil-based polymer is characterized as being polyamide 11 (PA11) as shown in Chemical Formula 6 below.

[0073] [Chemical Formula 6]

[0074]

[0076] The above PA11 is a polymer having a main chain structure of an aliphatic amide, and aliphatic polyamides are generally known by the trade name nylon. The above PA11 is a thermoplastic polyamide, an aliphatic polyamide that can be obtained by condensation polymerization of 11-aminoundecaidic acid obtained from castor oil. It is environmentally friendly in that it uses monomers obtained from castor oil, possesses various properties such as thermoplasticity and semi-crystallineness, has excellent impact resistance and hydrolysis resistance, and also has the advantage of being resistant to many chemicals. Due to these advantages, it is used in various fields such as automobiles, electronic devices, and sporting goods, and recent developments of new materials based on this are forming a new high-value-added market to replace existing engineering plastics made from petroleum resources.

[0077] The above-mentioned biodegradable polymer is characterized as being a polyhydroxyalkanoate (PHA). Since the above-mentioned PHA is as described above in the compatibilizer composition, a redundant description is omitted.

[0078] The polymer in the above polymer composite material composition may be an oil-based polymer and a biodegradable polymer mixed in a weight ratio of 70:30 to 60:40, and specifically, may include a polymer mixed in a weight ratio of 70:30. Since the PA11 has the characteristic of having a high processing temperature, and as the mixing amount of PHA increases, an auto-oxidation reaction at high temperatures may occur, it is preferable to mix within the above range.

[0079] The compatibilizer composition of the present invention can form an imide bond between the PA11 and the PHA. Specifically, as shown in Chemical Formula 7 below, an imide bond is formed between the PA11 and the MA group present in the compatibilizer composition, thereby improving the insufficient interfacial adhesion between the two materials, the PA11 and the PHA, and strengthening the physical properties of the polymer composite material through an increase in molecular weight.

[0080] [Chemical Formula 7]

[0081]

[0082] The above polymer composite material composition can be manufactured into a polymer composite material by mixing the polymer and the compatibilizer composition and performing a reaction extrusion process, but is not limited thereto, and can be manufactured into a polymer composite material by a process conventionally practiced in the industry.

[0083] Hereinafter, a polymer composite material composition comprising a compatibilizer composition containing a polyfunctional crosslinking agent according to the present invention will be described in more detail through examples. However, the following examples are merely for reference to explain the present invention in detail, and the present invention is not limited thereto and can be implemented in various forms.

[0084] Furthermore, unless otherwise defined, all technical and scientific terms have the same meaning as generally understood by one of the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention. Additionally, units of additives not specifically stated in the specification may be in weight percent.

[0086] [Reagents and Materials]

[0087] 1) Microbial-based polymer: CJ Bio's PHA, Poly(3HB-co-4HB) was used. (T m : 85℃, T g :-15℃, MI: 19.29 g / 10 min(190℃ / 2.16 kg) @ NOVA, Density: 1.23 g / cm 3 )

[0088] 2) Acid Anhydride: Maleic Anhydride (MA) (M188) from Aldrich was used. (Density: 1.48 g / cm³ 3 , mp: 52.6℃)

[0089] 3) Radical initiator: Akzonovel’s Perkadox 14 (PK-14) was used. (Half-life: 90 s (170°C), 15 s (190°C), Crosslinking temperature: 175°C)

[0090] 4) Polyfunctional crosslinking agent: Trimethylolpropane trimethacrylate (TMPTMA, manufactured by Aldrich, Density: 1.06 g / ml at 25℃, MW: 338.40 g / mol, bp:-14℃) and divinylbenzene (DVB, manufactured by Samchun) were used.

[0092] [Preparation of Compatibilizer Compositions Examples 1 to 4]

[0093] The above reagents and materials were mixed as shown in Table 1 below, and a reaction extrusion process was carried out using a twin screw extruder (model name: Bautek BA-19, L / D=40, diameter: 19Φ, co-rotating type). The temperature of the extruder was set to 150 to 170 ℃, and the screw rotation speed was fixed at 150 rpm. The materials for reaction extrusion were reaction-extruded while passing through the conveying zone, kneading zone, and reverse zone of the extruder screw, and after cooling in a water bath zone, the PHA-g-MA samples of Preparation Examples 1 to 4 were produced in the form of pellets through a pelletizer.

[0095] PHA-g-MA PHA (g) PK-14 (weight part) MA (parts by weight) TMPTMA (parts by weight) DVB (parts by weight) Preparation Example 1 M3T3 100 0.1 3 3 - Preparation Example 2 M3D1 100 0.1 3 - 1 Manufacturing Example 3M3D2 100 0.1 3 - 2 Preparation Example 4M3D3 100 0.1 3 - 3

[0097] [Preparation of Polymer Composite Material Composition According to Compatibilizer Composition Content]

[0098] The above Preparation Examples 1 to 4 and PA11 (Rilsan® BMNO grade product of Arkema, Density: 1.03 g / cm3, MI: 7 g / 10 min, T m: 189℃) and PHA (Poly(3HB-co-4HB) of CJ BIO) were mixed according to the composition shown in Table 2 below, and a reactive extrusion process was carried out using a twin screw extruder (model name: BA-19 of Bautek, L / D=40, diameter: 19Φ, co-rotating type). The temperature of the extruder was set to 170 to 190 ℃, and the screw rotation speed was fixed at 200 rpm. The polymer composite material compositions of Comparative Example 1 and Examples 1 to 16 were prepared in pellet form using a pelletizer after passing through the conveying zone, kneading zone, and reverse zone of the extruder screw and cooling in a water bath zone.

[0099] PA11 (weight%) PHA (weight%) Content of compatibilizer composition (parts by weight relative to PA11 / PHA mixture) Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Comparative Example 1 (PA70PHA30) 70 30 - - - - Example 1 (PA70PHA30C3-T3) 70 30 3 - - - Example 2 (PA70PHA30C3-D1) 70 30 - 3 - - Example 3 (PA70PHA30C3-D2) 70 30 - - 3 - Example 4 (PA70PHA30C3-D3) 70 30 - - - 3 Example 5 (PA70PHA30C5-T3) 70 30 5 - - - Example 6 (PA70PHA30C5-D1) 70 30 5 Example 7 (PA70PHA30C5-D2) 70 30 - - 5 - Example 8 (PA70PHA30C5-D3) 70 30 - - - 5 Example 9 (PA70PHA30C10-T3) 70 30 10 - - - Example 10 (PA70PHA30C10-D1) 70 30 - 10 - - Example 11 (PA70PHA30C10-D2) 70 30 - - 10 - Example 12 (PA70PHA30C10-D3) 70 30 - - - 10 Example 13 (PA70C30-T3) 70 30 30 - - - Example 14 (PA70C30-D1) 70 30 - 30 - - Example 15 (PA70C30-D2) 70 30 - - 30 - Example 16 (PA70C30-D3) 70 30 - - - 30

[0100] [Characteristic Evaluation Method]

[0101] 1) Dynamic Mechanical Analysis (DMA): To evaluate compatibility, DMA analysis was performed at -90 to -80°C and 2°C / min to measure the storage modulus, and the results are shown in Figure 1.

[0102] 2) Glass transition temperature (T g ) analyze: To determine the glass transition temperature of PA70PH30C0 when PA11 and PHA could be mixed, the glass transition temperature was calculated using the Fox equation in Equation 1 below. Using the Fox equation, the T of the single polymer produced from individual monomers g Based on the value, the glass transition temperature of the polymer composite composition when mixed can be estimated.

[0103] [Equation 1]

[0104] (Fox equation)

[0105] (Here, T g1The glass transition temperature of PA11, T g2 is the glass transition temperature of PHA, w1 is the weight fraction of PA11, and w2 is the weight fraction of PHA.

[0106] The glass transition temperature (T) calculated from Equation 1 above g ) is shown in Figure 2.

[0107] 3) FT-IR Analysis: FT-IR analysis was performed to confirm whether the above PA11, PHA, and PHA-g-MA reacted, and the results are shown in Figure 3.

[0108] 4) Measurement of Melt Index (MI): The melt indices of Comparative Example 1 and Examples 1 to 16 were measured according to the content of the above-mentioned compatibilizer composition. A Tinius Olsen MP 600 was used, and the measurement method was applied in accordance with ASTM 1238 standards, with measurement conditions of 150°C and 2.16 kg. The evaluation results of the melt indices are shown in Fig. 4.

[0109] 3) Tensile strength: Tensile strength was measured according to ASTM D638 standards, and the results are shown in Figure 5.

[0110] 4) Elongation: The elongation was measured according to the ASTM D638 standard, and the results are shown in Figure 6.

[0111] 5) Impact strength (Izod Impact strength): Impact strength was measured according to the ASTM D256 standard, and the results are shown in Figure 7.

[0112] 6) Flexural Modulus: Impact strength was measured according to ASTM D790 standards, and the results are shown in Figure 8.

[0113] 7) Scanning electron microscopy (SEM): To confirm the compatibility between the above PA11 and PHA, the fracture surface was analyzed using a scanning electron microscope, and the results are shown in Figures 9 to 12.

[0115] [Characteristics Evaluation]

[0116] Referring to Fig. 1, the storage modulus measured by Dynamic Mechanical Analysis (DMA, -90 to -80°C, 2°C / min) at 0 to 35°C is 4 to 7 MPa when TMPTMA is used, and 4 to 6 MPa when DVB is used. At 0 to 35°C, the decrease in storage modulus decreased as the compatibilizer composition using TMPTMA or DVB as a crosslinking agent was added. In this case, the fact that the decrease was further reduced when DVB was used as a crosslinking agent means that the compatibilizer composition with added DVB has higher compatibility.

[0117] Referring to Figure 2, when compatibility is evaluated by comparing it to the glass transition temperature of the compatibilizable composition, 33°C, it means that compatibility is high when the glass transition temperature is formed close to 33°C. Therefore, in Figure 2, when TMPTMA or DVB is used, it can be seen that compatibility increases as the glass transition temperature moves closer to 33°C as the content of the compatibilizer composition increases, and it can be seen that when 3 to 5 parts by weight of the compatibilizer composition are used, compatibility is higher when the multifunctional crosslinking agent is DVB.

[0118] Referring to Fig. 3, in the PA11 / PHA polymer composite composition to which the compatibilizer composition was introduced, the Imide IC=O peak is 1730 cm⁻¹. -1 It was discovered in, and the Imide II C=O peak is at 1380 cm⁻¹ -1 This was observed. This is because a chemical imide bond is formed between the MA group of PHA-g-MA, which is a compatibilizer composition, and the amide group of PA11. Therefore, it can be seen that the introduction of the compatibilizer composition forms an imide bond with PA11, increasing the molecular weight and significantly improving the compatibility and mechanical properties of the PA11 / PHA polymer composite material composition.

[0119] Referring to Figure 4, when the compatibilizer composition of Preparation Example 1, prepared using 3 parts by weight of TMPTMA as a polyfunctional crosslinking agent, was added to the polymer composite composition, the melt index increased as the content of the compatibilizer composition increased, and when 3 parts by weight of DVB was used, the melt index decreased as the content of the compatibilizer composition increased. This implies that when DVB is used, the structural constraint is relatively lower, allowing for a more active reaction and better grafting of MA into the compatibilizer composition. Therefore, it can be determined that the MA in the compatibilizer composition using DVB forms more imide bonds with PA11, and the molecular weight of the polymer composite composition increases, which is reflected in the melt index.

[0120] Referring to Fig. 5, compared to Comparative Example 1, in which only PA11 and PHA were mixed without a compatibilizer composition, when 3 parts by weight of the compatibilizer composition were added, the tensile strength was the same as that of Comparative Example 1 regardless of the multifunctional crosslinking agent, but as the content of the compatibilizer composition increased, the tensile strength increased, and when 10 parts by weight of the compatibilizer composition were added, the tensile strength was 25 to 26 MPa.

[0121] Referring to Fig. 6, compared to Comparative Example 1, in which only PA11 and PHA were mixed without a compatibilizer composition, the elongation was improved from 107% to 150% or more as 3 parts by weight of the compatibilizer composition was added, and the elongation was excellent at 152 to 210% in the range of 3 to 10 parts by weight of the compatibilizer composition content.

[0122] Referring to Fig. 7, compared to Comparative Example 1, in which only PA11 and PHA were mixed without a compatibilizer composition, the impact strength was improved from 608 J / m to 645 J / m or higher when 3 parts by weight of the compatibilizer composition was added, and the impact strength was excellent at 645 to 774 J / m in the range of 3 to 10 parts by weight of the compatibilizer composition content.

[0123] Referring to FIG. 8, compared to Comparative Example 1, in which only PA11 and PHA were mixed without the compatibilizer composition, the flexural modulus is 6750 kg / cm² when 3 parts by weight of the compatibilizer composition is added. 2 At 7360 kg / cm² 2 Improved as described above, with an impact strength of 7360 to 8400 kg / cm² in a content of 3 to 10 parts by weight of the compatibilizer composition. 2 It was excellent.

[0124] Referring to FIGS. 9 to 12, compared to Comparative Example 1, in which only PA11 and PHA were mixed without a compatibilizer composition, it can be observed that the pores improve as the content of the compatibilizer increases, regardless of the type of multifunctional crosslinking agent, and the distinction between the matrix and the domains becomes ambiguous. In particular, looking at FIGS. 10 to 12, the surface of FIG. 11, in which 2 parts by weight of the compatibilizer composition using DVB were added, becomes finer than FIG. 10, in which 1 part by weight of the compatibilizer composition using DVB was added, and FIG. 12, in which 3 parts by weight were added, has an even finer surface than FIG. 10 and FIG. 11. This confirms that the compatibility improvement effect is most excellent when 10 parts by weight of the compatibilizer composition using DVB as a multifunctional crosslinking agent is used.

[0125] Based on the above results, it was confirmed that when a compatibilizer composition containing a multifunctional crosslinking agent according to the present invention is added to a polymer composite material composition, the mechanical properties of the polymer composite material can be improved as the content increases. In particular, when 3 to 10 parts by weight of Preparation Example 1, which contains 3 parts by weight of TMPTMA as the multifunctional crosslinking agent, was used as the compatibilizer composition (Examples 1, 5, and 9), the melt index satisfied the range of 5.0 to 8.1 g / 10 min, and the excellent mechanical properties of the polymer composite material composition were also confirmed.

[0126] When Preparation Example 4, containing 3 parts by weight of DVB as the polyfunctional crosslinking agent, was used in an amount of 3 to 10 parts by weight as a compatibilizer composition (Examples 4, 8, and 12), the content of the compatibilizer composition was added in an amount of 3 to 10 parts by weight, satisfying the range of 5.0 to 8.1 g / 10 min, and excellent mechanical properties were confirmed. In particular, Example 12 had a melt index of 5.0 g / 10 min and the best mechanical properties, and furthermore, a fine surface could be observed when observing the fracture surface.

[0127] Although the present invention has been described above through specific details and limited embodiments, this is provided merely to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

[0128] Accordingly, the scope of the present invention is not limited to the described embodiments, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to fall within the scope of the concept of the present invention.

Claims

Claim 1 A compatibilizer composition comprising an acid anhydride-grafted microbial-based polymer and a multifunctional crosslinking agent, wherein the microbial-based polymer is polyhydroxyalkanoate (PHA), and the multifunctional crosslinking agent is one or more selected from trimethylolpropane trimethacrylate (TMPTMA) and divinylbenzene (DVB), and is included in an amount of more than 2 to less than 4 parts by weight per 100 parts by weight of the microbial-based polymer, and the compatibilizer composition is included in an amount of 3 to 10 parts by weight per 100 parts by weight of the polymer of the polymer composite material composition, wherein the polymer of the polymer composite material composition is a mixture of polyamide 11 (PA11) and polyhydroxyalkanoate (PHA) in a weight ratio of 70:30, and has a melting index (Mi) of 5.0 to A polymer composite material composition characterized by having 8.1 g / 10 min. Claim 2 delete Claim 3 A polymer composite material composition according to claim 1, characterized in that the acid anhydride is grafted onto the polyester main chain of the microorganism-based polymer. Claim 4 A polymer composite material composition according to claim 1, characterized in that the acid anhydride is one or more selected from maleic anhydride, fumaric anhydride, acetylenedicarboxylic anhydride, glutaconic anhydride, 2-decenedioic anhydride, traumatic anhydride, muconic anhydride, glutinic anhydride, citraconic anhydride, mesaconic anhydride, and itaconic anhydride. Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 delete Claim 10 delete

Images