KR20190090995A - Functional capsule for enhancing thermal stability comprising functional materials, filaments and manufacturing methods using the same - Google Patents

Abstract

The present invention relates to a functional material capsule for improving thermal stability of a functional material for melt compounding (melt processing), a filament using the same and a method for preparing the same, and more particularly, to adsorb a functional material to porous nanoparticles. When coated with a metal oxide on the encapsulated capsule, the heat resistance of the encapsulated functional material can be improved, and the functional material can remain sufficiently even after melting and extrusion with a high melting point polymer such as PET. Extruded functional fibers can be prepared.

Description

Functional capsule for enhancing thermal stability comprising functional materials, filaments and manufacturing methods using the same

The present invention relates to a functional material capsule for improving thermal stability of a functional material for polymer compounding, which is melt processing, a filament using the same, and a method of manufacturing the same.

The development of monofilament is being developed into various types of monofilament having a functional material through nylon filament and tapered PBT filament. However, in the production of monofilament, the temperature used for spinning of the monofilament is typically 200 to 300 ° C. It is virtually impossible to add or use a material that is pyrolyzed or changes in physical properties at this temperature.

In addition, even if the functional material for constituting the functional monofilament is a weak heat-resistant material or limited use is possible, it is difficult to have a desired product form due to the color change in the spinning process or the physical property in the warm state, and the type and characteristic of the required functional material However, there is a significant limitation in the concentration used.

In particular, when a polymer having a relatively low melting temperature such as nylon 6 polymer is used around 220 ° C., a functional material-containing functional fiber can be manufactured. However, a general-purpose polymer having a high melting temperature such as polyester (polyethylene terephthalate (PET)) can be used. In the case, it was not possible to produce functional fibers containing functional materials that are susceptible to heat.

Therefore, there is a need for the development of a process for producing a functional monofilament containing a functional material that is weak to heat.

Republic of Korea Patent No. 10-0749762 (2007.08.09)

An object of the present invention is to provide a functional material capsule for improving the thermal stability of the functional material for polymer compounding capable of melt processing (melt processing).

Another object of the present invention is to provide a functional material-containing filament using the functional material capsule and a method of manufacturing the same.

In order to achieve the above object, the present invention is a core capsule made of porous nanoparticles, and a functional material adsorbed on the porous nanoparticles; And a skin layer coated on the surface of the core capsule with a metal oxide.

In another aspect, the present invention provides a functional material-containing filament melt-extruded by mixing the functional material capsule with a polymer.

In addition, the present invention comprises the steps of preparing a functional material capsule by adding porous nanoparticles and a functional material to the metal oxide precursor solution; And it provides a functional material-containing filament manufacturing method comprising the step of melt-extrusion mixing the functional material capsule with a polymer.

In addition, the present invention comprises the steps of preparing a core capsule by adsorbing a functional material to the porous nanoparticles; Preparing a functional material capsule having a skin layer formed by adding the core capsule to a metal oxide precursor solution; And it provides a functional material-containing filament manufacturing method comprising the step of melt-extrusion mixing the functional material capsule with a polymer.

According to the present invention, when the functional material is coated with a metal oxide on the capsule adsorbed on the porous nanoparticles, the heat resistance of the encapsulated functional material is improved, and the functional material remains sufficiently even after being melt-extruded after being combined with a high melting polymer such as PET. The functional material can be melt-extruded with a general purpose polymer having a high melting point to produce a functional fiber.

Figure 1 shows a schematic diagram of the manufacturing process of the TiO ₂ @ (Zeolite / caffeine) capsule.
Figure 2 shows the UV absorbance curve (left) for each concentration of the caffeine aqueous solution, caffeine aqueous solution concentration black (right).
Figure 3 shows the concentration test line (left: low concentration region, right: high concentration region) of the aqueous solution of caffeine added with zeolite according to the present invention.
Figure 4 shows the absorbance results (left: absorbance curve, right: absorbance maximum value) of caffeine adsorbed to the zeolite for each concentration of the caffeine aqueous solution.
5 shows the absorbance results (left: absorbance curve, right: absorbance maximum value) of caffeine adsorbed to zeolite according to adsorption time of aqueous solution of caffeine.
Figure 6 shows the X-ray diffraction curve of the TiO ₂ @ (Zeolite / caffeine) capsule prepared in the present invention.
Figure 7 shows a SEM photograph of the TiO ₂ @ (Zeolite / caffeine) capsule prepared in the present invention.
8 shows the results of SEM-EDS analysis of TiO ₂ @ (Zeolite / caffeine) capsules prepared in the present invention.
Figure 9 shows the TGA results of the TiO ₂ @ (Zeolite / caffeine) capsule prepared in the present invention.
Figure 10 shows a conceptual diagram of a process for producing a melt-spun PET / TiO ₂ @ (Zeolite / caffeine) composite filament using the TiO ₂ @ (Zeolite / caffeine) capsule prepared in the present invention.
Figure 11 shows the absorbance of the caffeine solution extracted from the melt-spun PET / TiO ₂ @ (Zeolite / caffeine) composite filament according to the present invention.
Figure 12 shows the maximum absorbance according to the production method and extrusion temperature of the caffeine solution extracted from the melt-spun PET / TiO ₂ @ (Zeolite / caffeine) composite filament according to the present invention.
Figure 13 shows the concentration converted by using a calibration line according to the production method and extrusion temperature of the caffeine solution extracted from the melt-spun PET / TiO ₂ @ (Zeolite / caffeine) composite filament according to the present invention.
Figure 14 shows the concentration according to the nanoparticle content converted using the calibration line of the caffeine solution extracted from the melt-spun PET / TiO ₂ @ (Zeolite / caffeine) composite filament according to the present invention.
Figure 15 shows the mechanism of each TiO ₂ @ (Zeolite / caffeine) capsule manufacturing process.
16 shows a conceptual diagram of a TiO ₂ @ (Zeolite / caffeine) capsule according to the present invention.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention have made diligent efforts to develop a functional material capable of remaining without losing the functional material even after melt-extrusion spinning with a general-purpose polymer having a high melting point such as polyester terephthalate (PET) and porous nanoparticles. When the capsules adsorbed on the metal oxide were coated with a metal oxide, the heat resistance of the encapsulated functional material was improved to allow melt extrusion after complexing with a high melting point polymer such as PET.

The present invention provides a core capsule comprising a porous nanoparticle and a functional material adsorbed on the porous nanoparticle; And a skin layer coated on the surface of the core capsule with a metal oxide.

The porous nanoparticles may have a specific surface area of 600-800 m ² / g, an average pore volume of 0.7-1.5 cm ³ / g, an average pore diameter of 4-5 nm, and an average diameter of the nanoparticles of 5 to 5 May be 800 nm and may be one selected from the group consisting of zeolite, silica, zinc oxide, graphite, carbon nanotubes and clay. It is not limited to this.

The functional material may be one selected from the group consisting of caffeine, vitamin D, vitamin E, malic acid, citric acid, enzymes, propolis, polyphenols and chitosan. It is not limited to this.

The core capsule according to the present invention can be stably placed even if the maximum amount of adsorption of the functional material on the porous nanoparticles.

The skin layer may improve heat resistance of a functional material that is weak to heat.

The metal oxide is one nanoparticle selected from the group consisting of titanium dioxide (TiO ₂ ), zinc oxide (ZnO), silicon dioxide (SiO ₂ ), silver (Ag), gold (Au) and zircon oxide (ZrO ₂ ). It may be, but is not limited to such.

The core capsules are (3-aminopropyl) trimethoxysilane, methacryloxypropyl trimethoxysilane, hexamethyldisilazane and polystyrene-brush to improve dispersibility of functional material and coating property of skin layer. It can be surface modified with a material selected from the group consisting of (chlorosilane-terminated polystyrene).

The functional material capsule according to the present invention preferably has a maximum functional adsorption concentration of at least 0.1 g / g (functional additive / core capsule material), a particle size dispersion coefficient (ε) of 1.0 or less, and an average particle size of 800 nm or less. Do.

In another aspect, the present invention provides a functional material-containing filament melt-extruded by mixing the functional material capsule with a polymer.

The polymer is a polymer having a melting point of 100 ~ 300 ℃, polyethylene terephthalate (PET), nylon (nylon), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polylactic acid (PLA), polyethylene Although it may be a high melting point polymer selected from the group consisting of (PE) and polypropylene (PP). It is not limited to this.

In addition, the present invention comprises the steps of preparing a functional material capsule by adding porous nanoparticles and a functional material to the metal oxide precursor solution; And it provides a functional material-containing filament manufacturing method comprising the step of melt-extrusion mixing the functional material capsule with a polymer.

In addition, the present invention comprises the steps of preparing a core capsule by adsorbing a functional material to the porous nanoparticles; Preparing a functional material capsule having a skin layer formed by adding the core capsule to a metal oxide precursor solution; And it provides a functional material-containing filament manufacturing method comprising the step of melt-extrusion mixing the functional material capsule with a polymer.

The polymer is a polymer having a melting point of 100 ~ 300 ℃, polyethylene terephthalate (PET), nylon (nylon), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polylactic acid (PLA), polyethylene Although it may be a high melting point polymer selected from the group consisting of (PE) and polypropylene (PP). It is not limited to this.

The masterbatch chip prepared by compounding the capsule containing the functional material according to the present invention with the polymer substrate is preferably at least 10% concentration of the nanoparticles and at least 30% residual ratio of the functional material after melt extrusion.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.

Example 1 TiO ₂ (Skin layer) @ (Zeolite / Caffeine) (Core) Composite nanoparticles manufacture

1. Zeolite / Caffeine Capsule Manufacturing

The materials used in the experiment were beta zeolite [SiO ₂ / Al ₂ O ₃ = 98/2, Cosmo Fine Chemicla] and caffeine [1,3,7 Trimethylpurine 2,6-dione, C ₈ H ₁₀ N ₄ O ₂ , SIGMA-ALDRICH ] Was used.

8 g of caffeine was added to 100 ml of distilled water to dissolve at 60 ° C. for 1 hour to prepare a caffeine solution, and 3 g of dried zeolite was added to the caffeine solution. The solubility of caffeine can be increased with increasing water temperature, but if the solvent temperature is too high, the caffeine is extracted after adsorption on zeolite at high temperature, so the dissolution temperature is set to 60 ℃ and the caffeine concentration is 80 mg / ml.

The zeolite-added caffeine solution was stirred at 60 ° C. for 30 minutes, centrifuged at 3000 rpm for 1 hour using a centrifuge, and dried to prepare a zeolite / caffeine powder (capsule).

The following Table 1 is a condition for preparing capsules by varying the conditions depending on caffeine concentration, treatment time (h), and pH as a condition of maximally adsorbing caffeine to zeolite.

Condition
Sample Caffeine Concentration (mg / ml) Processing time (h) pH Sample 1 20 4 6 Sample 2 40 4 6 Sample 3 60 4 6 Sample 4 80 4 6 Sample 5 80 0.5 6 Sample 6 80 One 6 Sample 7 80 2 6 Sample 8 80 3 6 Sample 9 80 4 6 Sample 10 80 5 6 Sample 11 80 4 3 Sample 12 80 4 10

2. TiO ₂  coating

₄ TiO ₂ precursor of titanium (IV) iso-proxy polyepoxide ([Titanium (Ⅳ) isopropoxide, Ti (OCH (CH 3) 2) to the TiO ₂ coating using the gel method [-sol to the previously prepared zeolite / caffeine Capsules TTIP 97%, SIGMA-ALDRICH]). Distilled water was used for hydrolysis of the precursor TTIP, and isopropyl alcohol (CH (CH ₃ ) ₂ OH [IPA 99.5%, DUSKAN]) was used as a solvent.

1 is a schematic of two coating steps of TiO ₂ . According to the TiO ₂ coating step, the method of coating the capsule powder into the TTIP solution after caffeine adsorption by the conventional method was named 2step. Named it.

1) TiO ₂ @ (zeolite / caffeine)-2 step

After stirring 5 ml of TTIP and 13 ml of solvent IPA at 60 ° C. for 1 hour, 3 g of a zeolite / caffeine capsule prepared in the manner described in 1.1 was added to the TTIP solution and stirred for 30 minutes. 70 ml of distilled water and 30 ml of IPA were mixed and stirred at 60 ° C. for 2 hours. When the layers of the solution thus obtained were separated, the supernatant was discarded and dried at 60 ° C for 12 hours.

2) TiO ₂ @ (zeolite / caffeine)-1 step

3 g of zeolite was added to a solution of 80 mg / ml caffeine, and a solution obtained by stirring at 60 ° C. for 30 minutes and a solution of 5 ml of TTIP and 13 ml of IPA at 60 ° C. for 1 hour was prepared. Then, both zeolite / caffeine solution and TTIP solution were added to a solution of 70 ml of distilled water and 30 ml of IPA, followed by stirring at 60 ° C. for 2 hours. After stirring like this, if the layers of the solution were separated, the supernatant was discarded and dried at 60 ° C. for 12 hours.

Next, as shown in Table 2, the nanoparticles were prepared by varying the pH and treatment time (h) of coating TiO ₂ on the zeolite / caffeine capsule through the manufacturing method of 1step.

Condition
Sample Processing time (h) pH Sample 1 0.5 6 Sample 2 One 6 Sample 3 2 6 Sample 4 3 6 Sample 5 2 3 Sample 6 2 10

Example 2 TiO ₂ (Skin Layer) @ (Zeolite / Caffeine) (Core) Composite Nanoparticle Properties and Structure Measurement

1. Analysis method

The light transmittance of the liquid sample was measured using UV-visible spectroscopy (Cary 5000, Agilent). The measured samples were measured by adding caffeine to each concentration in distilled water to make a calibration curve of caffeine. In addition, 1.5 g of the prepared nanoparticles were placed in 30 ml of ethanol, and the caffeine solution extracted with auto clave was put in a quartz cell, and the light transmittance was measured in the range of 200 to 600 nm.

X-ray diffraction analyzer (XRD bulk) to confirm the crystal structure of the nanoparticles prepared above and whether TiO _{2 is} coated with zeolite / caffeine, TiO ₂ @ (zeolite / caffeine) -2step, TiO ₂ @ (zeolite / caffeine) -1step (powder), PANalytical) was used. The measurement conditions were 40 kV and 100 mA, and the range of 2θ was measured at a rate of 5 ° / min at 10 ° to 80 °.

In order to confirm the structural analysis of the nanoparticles, a sample was attached to a carbon tape, vacuum deposited with platinum using a metal ion coating machine (Ion-Sputter, E-1030), and then scanned in a microscope (SEM, Hitachi) in shape and size. In order to confirm the coating of the inorganic particles TiO ₂ , the elemental components of the particles were identified through an EDS (Energy Dispersive Spectrometer, Hitachi). In the observation of samples using transmission electron microscope (TEM, Hitachi), 0.1g of powder and 10ml of distilled water were dispersed for 1 hour, floated on a grid, dried, and then confirmed the shape and size of the particles in nano size.

Thermogravimetric analysis (TGA, TA Instruments) was measured up to 30 ~ 500 ℃ at 20 ℃ / min rate using 5mg of powder, through which the thermal stability of caffeine present according to the capsule powder manufacturing method.

2. Analysis Results

1) UV Caffeine Black Line

In order to measure the concentration of caffeine using UV absorbance, caffeine solutions were prepared by varying the concentrations, and their absorbance (FIG. 2, left) was measured to prepare a concentration calibration line (FIG. 2, right) of the caffeine solution.

In addition, it was confirmed that the area of low caffeine in the solution of zeolite added caffeine showed linearity (FIG. 3, left), and the absorbance was increased in the area of high caffeine concentration (FIG. 3, right). A calibration line of high concentration region was created.

2) Zeolite adsorption of caffeine solution (caffeine concentration, adsorption time effect)

After preparing a capsule by adsorbing caffeine to zeolite particles, UV absorbance of the solution of caffeine extracted from the caffeine-adsorbed capsule was measured to determine how much caffeine was adsorbed.

Figure 4 shows the absorbance of the caffeine adsorbed to the zeolite particles according to the concentration of caffeine solution, which is related to the amount of caffeine adsorbed, the amount of caffeine adsorbed to the zeolite particles increases as the concentration of the caffeine adsorbed increases It was.

After fixing the concentration of the solution of caffeine to 80mg / ml and looked at the adsorption to the zeolite of caffeine according to the adsorption time, as shown in Figure 5 it was confirmed that the adsorption sufficiently in the adsorption time of about 30 minutes without significant effect.

3) TiO to Zeolite / Caffeine Capsules ₂  Check coating

After adsorbing caffeine on zeolite, TiO ₂ was coated. Whether TiO ₂ was formed on the zeolite surface was analyzed by X-ray diffraction. The comparison of the zeolite and X-ray diffraction curves of TiO ₂ single particles confirmed that TiO ₂ was formed on the surface of the zeolite in the method of 1 step and 2 step as shown in FIG. 6.

As shown in FIG. 7, it was confirmed that TiO ₂ particles were formed on the surface of the zeolite particles as shown in FIG. 7 (FIG. 7). As shown in FIG. 8, Ti, which is a main component of TiO ₂ , was detected through SEM-EDS elemental analysis.

4) Zeolite / Caffeine Capsules, TiO ₂ Caffeine Thermal Stability Analysis of @ (zeolite / caffeine) Capsule

TGA results measured to measure the thermal stability of the caffeine adsorbed to the zeolite as shown in Figure 9 can be seen that the melting point from the melting point near the melting point of 178 ℃ in case of single caffeine is rapidly decomposed at 200 ℃ or more. Except that the water is removed in the vicinity of 100 ℃ it can be confirmed that the thermally stable.

When caffeine was adsorbed on zeolite, pyrolysis was delayed compared to when caffeine was present alone, and the amount of caffeine adsorbed in the 2 step TiO ₂ @ (Zeolite / caffeine) capsule was less than that of 1 step. This is due to the extraction and desorption of some of the caffeine solution present in the Zeolite / caffeine capsule in the step of coating TiO ₂ in a two-step process.

Example 3 Preparation of PET Melt Spinning Monofilament

1. PET melt spinning filament manufacturing

In order to confirm the thermal stability of caffeine, a functional material contained in the nanoparticles prepared above, polypropylene [PP MI 8.5, Korea Emulsification] polymer having a low melting point (165 ° C.) and polyethylene having a high melting point (260 ° C.) polymer To each of terephthalate [PET IV 0.8, Toray Chemical], zeolite / caffeine, TiO ₂ @ (zeolite / caffeine) -2step and TiO ₂ @ (zeolite / caffeine) -1step particles, which were previously prepared nanoparticle powders, were mixed. . The winding speed was 10 rpm in the extruder [Noztek Pro Filament Extruder, Φ1.7 die]. The extrusion temperature was 220 ° C for PP, 285 ° C, 290 ° C, and 295 ° C for PET. , 7% by weight.

2. Caffeine Extraction Test from Melt-Spun Filament

In order to check the content of caffeine contained in the filament prepared through high temperature melt extrusion without pyrolysis, 1.5 g of the extruded filament was cut to about 1 cm and placed in 30 ml of ethanol at 130 ° C. in a hydrothermal autoclave reactor. , 4 hours extraction. The extracted solution was filtered using a syringe filter (200 nm class) to remove impurities and leave only ethanol and caffeine.

Example 4 PET / TiO ₂ Caffeine Content and Physical Properties of @ (Zeolite / caffeine) Composite Monofilament

1.5 g of the PET monofilament mixed with the nanoparticles prepared in Example 1 was cut and a solution of caffeine extracted from 30 ml ethanol was prepared using UV-visible spectroscopy (Cary 5000, Agilent). The caffeine content was measured in the 200 ~ 600nm range into the quartz cell. In order to measure the physical properties of the extruded PET monofilament, differential scanning calorimetry (DSC, Perkin Elmer) was used at a temperature range of 40 to 290 ° C. at a rate of 20 ° C./min.

In order to quantify the caffeine in the capsule present in the filament prepared through the melt extrusion process, the prepared filament was cut into 10 cm length and the UV absorbance was measured after filtering the extracted solution after hot extraction in an autoclave reactor.

As shown in FIG. 11, the caffeine component remained undecomposed even after the melt extruding process through the UV absorbance curve as shown in FIG. 11. As shown in FIG. 12, the absorbance size according to the extrusion temperature showed a tendency to decrease as the extrusion temperature increased. It did not decrease and confirmed that caffeine remained at a high temperature of 295 ° C.

As a result of comparing the concentration of caffeine present in the melt-extruded PET / TiO ₂ @ (Zeolite / caffeine) composite filament from the absorbance calibration line for each concentration of caffeine solution, TiO ₂ @ ( Zeolite / caffeine) capsules showed the highest caffeine residues. The TiO ₂ @ (Zeolite / caffeine) capsule of the 2 step method showed lower value than the Zeolite / caffeine capsule without TiO ₂ coating, which is also consistent with the TGA result.The TiO ₂ @ (Zeolite / caffeine) This is due to the extraction and desorption of some of the caffeine solution present in the Zeolite / caffeine capsule in the TiO ₂ coating process.

As a result of comparing the concentration of caffeine present in the filament according to the nanoparticle content in PET / TiO ₂ @ (Zeolite / caffeine) composite filament, as the content of nanoparticles increases, the concentration of remaining caffeine increases. As the result of the extrusion temperature, the caffeine residual ratio was the largest when manufactured by the 1 step process.

Fig. 15 shows the formation of TiO ₂ @ (Zeolite / caffeine) capsules and the caffeine adsorption mechanism based on these experimental results. In the case of the two step process, the first step was adsorbed on zeolite and dried and then coated on TiO ₂ using TTIP. Part of the caffeine was extracted in the step to decrease the content of caffeine in the capsule, and in the 1 step process is less caffeine desorption compared to the 2 step process is considered to have a high caffeine content.

As mentioned above, although this invention was demonstrated by the limited embodiment and drawing, this invention is not limited by this, The person of ordinary skill in the art to which this invention belongs, Of course, various modifications and variations are possible within the scope of equivalents of the claims to be described.

Claims (12)

A core capsule made of porous nanoparticles and a functional material adsorbed on the porous nanoparticles; And
Functional core capsule, wherein the core capsule surface comprises a skin layer coated with a metal oxide. The method of claim 1, wherein the porous nanoparticles functional material capsule, characterized in that one selected from the group consisting of zeolite, silica, zinc oxide, graphite, carbon nanotubes and clay. The functional substance capsule according to claim 1, wherein the functional substance is one selected from the group consisting of caffeine, vitamin D, vitamin E, malic acid, citric acid, enzymes, propolis, polyphenols, and chitosan. The method of claim 1, wherein the metal oxide is selected from the group consisting of titanium dioxide (TiO ₂ ), zinc oxide (ZnO), silicon dioxide (SiO ₂ ), silver (Ag), gold (Au) and zircon oxide (ZrO ₂ ). Functional material capsule, characterized in that one nanoparticle. The group of claim 1, wherein the core capsule is a group consisting of (3-aminopropyl) trimethoxysilane, methacryloxypropyl trimethoxysilane, hexamethyldisilazane and chlorosilane-terminated polystyrene. Functional material capsule, characterized in that the surface modified with a material selected from. A functional material-containing filament obtained by melt-extruding a functional material capsule according to any one of claims 1 to 5 by mixing with a polymer. The filament of claim 6, wherein the polymer is a polymer having a melting point of 100 to 300 ° C. The method of claim 7, wherein the polymer is polyethylene terephthalate (PET), nylon (nylon), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polylactic acid (PLA), polyethylene (PE) and poly Functional material-containing filament, characterized in that the high melting point polymer selected from the group consisting of propylene (PP). Preparing a functional material capsule by adding porous nanoparticles and a functional material to the metal oxide precursor solution; And
The functional material-containing filament manufacturing method comprising the step of mixing the functional material capsule with a polymer melt extrusion. Preparing a core capsule by adsorbing a functional material on the porous nanoparticles;
Preparing a functional material capsule having a skin layer formed by adding the core capsule to a metal oxide precursor solution; And
The functional material-containing filament manufacturing method comprising the step of mixing the functional material capsule with a polymer melt extrusion. The method of claim 9 or 10, wherein the polymer is a functional material-containing filament manufacturing method, characterized in that the polymer having a melting point of 100 ~ 300 ℃. The method according to claim 9 or 10, wherein the polymer is polyethylene terephthalate (PET), nylon (nylon), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polylactic acid (PLA), polyethylene (PE) And a high melting point polymer selected from the group consisting of polypropylene (PP).

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