KR102600684B1 - Functional polyethylene masterbatch including inorganic-based nano barrier and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a functional polyethylene masterbatch containing an inorganic-based nano-barrier, and in particular, to a nano-structured polyethylene masterbatch with an inorganic material as the core and a hydrocarbon-based polymer as the shell. The idea is to disperse the barrier (Nano Barrier) into polyethylene base resin and manufacture it in the form of pellets.
As a result, when applying the masterbatch manufactured according to the present invention to a sheet-type product, durability is increased and gas permeability is reduced, thereby inhibiting the diffusion of air molecules passing through the cross section of the sheet, thereby preventing corrosion of stainless steel plates, etc. It can be minimized and the weight of the masterbatch can be adjusted when applied to a sheet-type product, so it is easy to control the mixing ratio of the nano barrier and polyethylene base resin, and the shelf life can be extended and stored through the masterbatch in the form of a pellet. And it is very easy to use, maximizing usability.

Description

Functional polyethylene masterbatch including inorganic-based nano barrier and manufacturing method thereof}

The present invention relates to a polyethylene masterbatch and a method for manufacturing the same. In particular, the invention relates to a polyethylene masterbatch and a method for manufacturing the same. In particular, by adding an inorganic nano-barrier to a polyethylene base resin, durability is increased when manufacturing a sheet-shaped material, and gas permeability is reduced to allow gas to pass through the sheet. It relates to a functional polyethylene masterbatch containing an inorganic-based nano-barrier that can minimize corrosion of steel sheets due to gases and a method of manufacturing the same.

A storage tank that stores liquid or gas inside is maintained in a static state, and corrosion occurs on the part inside the storage tank that faces the liquid or gas, reducing the lifespan of the storage tank and causing damage.

For example, in the case of storage tanks that store water, not only storability and structural stability but also hygiene is required, so there is an increasing trend to change existing plastic storage tanks using concrete or polymers to stainless steel materials that are resistant to corrosion. However, in the case of stainless steel, there are disadvantages in that rust may occur at the weld area and corrosion due to chlorine gas may occur, and for this purpose, if epoxy series is used as a lining, environmental pollutants may be eluted due to film separation and corrosion. there is a problem.

On the other hand, when polyethylene is bonded to a stainless steel plate as a sheet-shaped lining and used in a water storage tank, it has excellent compression and impact strength, and because it is a double panel type, the auxiliary waterproofing effect of stainless steel can be maintained even if the polyethylene sheet is damaged. This exists.

However, polyethylene has strong corrosion resistance to chlorine and fluorine gases and has hygienic advantages as it rarely generates harmful substances. However, due to the nature of storage tanks where high pressure is applied for a long period of time, durability is reduced and gas permeability increases, causing damage and corrosion. There is a problem that arises.

Therefore, the purpose of the present invention is to manufacture a masterbatch in the form of a pellet by adding an inorganic nano-barrier to a polyethylene base resin, thereby increasing durability and reducing gas permeability when applied to the production of a sheet-type product in the next step. The aim is to provide a functional polyethylene masterbatch containing an inorganic-based nano-barrier that can minimize corrosion of steel sheets and a manufacturing method thereof.

In addition, another object of the present invention is to easily control the mixing ratio of the nano barrier and polyethylene base resin when applied to a sheet-type product through a masterbatch, and to provide an inorganic material that can minimize the impact on the inherent physical properties of the polyethylene sheet. The purpose is to provide a functional polyethylene masterbatch containing a base nano-barrier and a method for manufacturing the same.

In addition, another object of the present invention is to provide a functional polyethylene masterbatch containing an inorganic-based nano-barrier that can extend the shelf life through a masterbatch in the form of a pellet and maximize usability by being very easy to store and use, and a method for manufacturing the same. It is to provide.

The above object is, according to an embodiment of the present invention, a nano barrier of a core-shell structure with an inorganic material as the core and a hydrocarbon polymer as the shell is formed on a polyethylene base. This is achieved by using a functional polyethylene masterbatch containing an inorganic-based nano-barrier dispersed in resin and manufactured in the form of pellets.

Here, the core is made of an inorganic material selected from the silica (Si), aluminum (Al), and iron (Fe) series or a group containing them, and the polyethylene base resin is high density polyethylene (HDPE), low density polyethylene (LDPE). , it is prepared from either linear low density polyethylene (LLDPE) or ultra low density polyethylene (ULDPE), and the hydraulic diameter of the nano barrier can be in the range of 350 ± 50 nm.

Here, the nano-barrier may be provided in the range of 0.5 ± 0.05 wt% or 1.0 ± 0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin.

Here, it further includes a dispersant added in an amount of 1,000 ppm or less of the total weight of the nano barrier and the polyethylene base resin, and the dispersant is a steric acid series, zinc stearate, calcium stearate, and magnesium. It may be selected from the group consisting of any one of stearates (magnesium strearast) or a mixture thereof.

Meanwhile, the above object, according to another embodiment of the present invention, includes (1) manufacturing an inorganic-based nano-barrier powder; (2) mixing the nano-barrier powder, polyethylene base resin, and dispersant into an extruder; and (3) extruding the molten mixture to obtain a masterbatch in the form of a pellet.

Here, in step (1), (1-1) a hydrocarbon-based polymer is used as the shell, and an inorganic material selected from silica (Si), aluminum (Al), and iron (Fe) series or a group containing these is used as the core. (core), and the hydrodynamic diameter of the manufactured nano-barrier may be in the range of 350 ± 50 nm.

In step (2), the nano-barrier powder is mixed in an amount of either 0.5 ± 0.05 wt% or 1.0 ± 0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin, and the dispersant is mixed at 1,000 ppm or less. may be added.

Here, when the nano-barrier powder is prepared at 0.5 ± 0.05 wt%, step (2) is (2-1a) a mixture of the nano-barrier, the polyethylene base resin, and the dispersant at the melting point of the polyethylene base resin. A step of gradually increasing the melt temperature over a plurality of steps from the above to 190 ± 2.5° C., wherein step (3) further includes the step of extruding (3-1a) the mixture, The extrusion temperature when the mixture is extruded outward from the extrusion port at the tip of the extruder can be set to 192 ± 1.5°C.

In the above example, the step (3-1a) is 130 ± 2.5 ℃ (step 1), 140 ± 2.5 ℃ (step 2), 150 ± 2.5 ℃ (step 3), 160 ± 2.5 ℃ (step 4), It is provided to gradually increase the melt temperature of the mixture in 9 steps: 170 ± 2.5 ℃ (step 5-6), 180 ± 2.5 ℃ (step 7-8), and 190 ± 2.5 ℃ (step 9), and the extruder is prepared with a twin screw extruder (modular intermeshing co-rotating twin-screw extruder), the L/D ratio (length/diameter ratio) is provided at 40:1, and the melt speed is provided in the range of 380 to 400 rpm.

On the other hand, when the nano-barrier powder is prepared at 1.0 ± 0.05 wt%, step (2) is (2-1b) a mixture of the nano-barrier, the polyethylene base resin, and the dispersant at the melting point of the polyethylene base resin. A step of gradually increasing the melt temperature over a plurality of steps from the above to 180 ± 2.5° C., wherein step (3) further includes the step of extruding (3-1b) the mixture, The extrusion temperature when the mixture is extruded out from the extrusion port at the tip of the extruder can be set to 183 ± 1.5°C.

In the above example, the step (3-1b) is 130 ± 2.5 ℃ (step 1), 140 ± 2.5 ℃ (step 2), 150 ± 2.5 ℃ (steps 3 and 4), 160 ± 3.5 ℃ (step 5, It is provided to gradually increase the melting temperature of the mixture in 9 steps: 6 steps), 170 ± 3.5 ℃ (steps 7 and 8), and 180 ± 2.5 ℃ (step 9), and the extruder is a twin screw extruder (modular) It is prepared with an intermeshing co-rotating twin-screw extruder, the L/D ratio (length/diameter ratio) is 40:1, and the melting speed is in the range of 380 to 400 rpm.

Meanwhile, in each of the above-described embodiments, step (3) may further include (3-2) quenching the extruded mixture in the range of 15 ± 2.5°C.

In addition, in each of the above-described embodiments, step (3) may further include (3-2) cutting the mixture extruded through the extrusion port at a cutting speed of 800 ± 12 rpm.

Therefore, according to the functional polyethylene masterbatch containing an inorganic-based nano-barrier according to the present invention and its manufacturing method, when applied to a sheet-type product using the masterbatch manufactured according to the present invention, durability is increased and gas permeability is reduced. This can minimize corrosion of stainless steel plates, etc. by inhibiting the diffusion of air molecules passing through the cross section of the sheet.

In addition, according to the functional polyethylene masterbatch containing an inorganic-based nano-barrier and its manufacturing method according to the present invention, the weight of the masterbatch can be adjusted when applied to a sheet-type product, so the mixing ratio of the nano-barrier and polyethylene base resin can be controlled. It is easy to use, and the impact on the inherent physical properties of polyethylene sheets can be minimized.

In addition, according to the functional polyethylene masterbatch containing an inorganic-based nano-barrier and its manufacturing method according to the present invention, the shelf life can be extended through the masterbatch in the form of a pellet, and storage and use are very easy to maximize usability.

1 is a flow chart of a method for producing a functional polyethylene masterbatch containing an inorganic-based nano-barrier according to an embodiment of the present invention;
Figure 2 is an enlarged photograph of the appearance and scanning electron microscope of a nano-barrier in powder form manufactured according to an embodiment of the present invention;
Figure 3 is a melt temperature control condition table for each content for masterbatch production according to an embodiment of the present invention;
Figure 4 is a photograph of the masterbatch prepared according to an embodiment of the present invention and the polyethylene base resin for producing it;
Figure 5 is a graph showing the results of a physical property test of a functional polyethylene masterbatch containing an inorganic-based nano-barrier manufactured according to an embodiment of the present invention.

The advantages and features of the present invention and methods for achieving the same will become clear by referring to the embodiments described in detail below along with the accompanying drawings. However, the embodiments described below are provided to enable a clear and complete understanding of the technical idea of the present invention, and the present invention is not limited to the presented embodiments and may be embodied in various other forms.

The terms used herein are only used to describe specific embodiments and are not intended to limit the invention. For example, as used herein, singular terms include plural terms unless the context clearly dictates otherwise. In addition, in this specification, terms such as 'include' or 'have' are intended to designate the presence of features, numbers, steps, operations, components, parts, or a combination thereof described in the specification, but are intended to indicate the presence of one or more other Since it is not intended to exclude the presence or possibility of addition of features, numbers, steps, operations, components, parts, or combinations thereof, it should be construed as not excluding them unless an exception to such exclusion is specified. Like reference numerals refer to like elements throughout the specification. Meanwhile, all terms (including technical and scientific terms) used, unless otherwise defined, basically have the same meaning as generally understood by those skilled in the art in the field to which the present invention pertains. However, each term described below is defined in consideration of the function in the embodiment of the present invention, and may vary depending on the intention or custom of the user or operator, so a clear definition of the term is based on the content throughout the specification. It must be interpreted first.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

Referring to Figure 1, the method for producing a functional polyethylene masterbatch containing an inorganic-based nano-barrier (10) according to an embodiment of the present invention includes the steps of (1) manufacturing an inorganic-based nano-barrier (10) powder (S1) ) and (2) mixing the nano-barrier powder, polyethylene base resin and dispersant into an extruder (S2), and (3) extruding the molten mixture to obtain a masterbatch in the form of a pellet. Includes (S3).

The step (1) is a step of manufacturing an inorganic-based nano barrier 10, using a hydrocarbon-based polymer as a shell, and silica (Si), aluminum (Al), and iron (Fe) series or containing these. It may include a step (1-1) of polymerizing an inorganic material selected from the group as a core.

For example, step (1-1) includes mixing styrene monomer, which is the basis of polystyrene, and the inorganic material in an aqueous phase, and heating to a temperature range of 70 ± 10°C after mixing to form a water-soluble initiator. A step of polymerization by adding a cross-linking agent, a step of stirring the mixed solution at a rotation speed of 600 ± 50 rpm to form a core-shell structure after polymerization, and a formation time of 18 ± 2 hours to allow the polymerization process to proceed. It can be prepared in stages.

The core-shell type nano-barrier 10 manufactured by the above method can be recovered in the form of a bright white powder, as shown in (a) of FIG. 2. This powder-type nano barrier 10 has the advantage of being able to be stored for a long period of time at room temperature, and when mixed with the polyethylene base resin 30, the desired weight can be easily measured and mixed at room temperature.

Here, the hydrodynamic diameter of the nano barrier 10 may be set in the range of 350 ± 50 nm. The reason why the size of the nano barrier 10 is measured as a hydraulic diameter is because the nano barrier 10 in a powder state can be dispersed in an aqueous phase and then measured using dynamic light scattering. Figure 2(b) shows that the nano-barrier 10 prepared in step (1-1) was measured using a transmission electron microscope and had a nearly spherical shape. The reason why the size of the nano barrier 10 visible in the transmission electron microscope in FIG. 2(b) appears smaller than the hydraulic diameter is because it is in a dried powder state, and in this state, the error is about 20% compared to the hydraulic diameter. It can happen. Here, limiting the hydraulic diameter of the nano-barrier 10 to the above range means that if it is larger than the above range, the transparency is severely reduced while the effect on improving tear strength is insignificant, and if it is smaller than the above range, the effect of the particles is reduced. Because the size is small and cannot effectively prevent the penetration of liquid or gas, it is difficult to improve the tear strength, so the applicant of the present application derived the optimal range through repeated experiments.

In step (2), the nano-barrier powder, polyethylene base resin, and dispersant are added to an extruder and mixed (S2).

Polyethylene base resin 30 is included in polyolefin resin and depending on the crystal structure, it can be classified into high-density (HDPE, low-density polyethylene), low-density (LDPE), or linear low-density (LLDPE). polyethylene) or ultra low-density polyethylene (ULDPE).

Here, when the nano-barrier 10 is melt-mixed with the polyethylene base resin 30, it may contain a dispersant to facilitate dispersion. The dispersant may be selected from the group consisting of any one or a mixture of stearic acid series, zinc stearate, calcium stearate, and magnesium stearate. The dispersant may further include a dispersant added in an amount of 1,000 ppm or less of the total weight of the nano barrier and the polyethylene base resin. Meanwhile, of course, other chemicals that connect the nano barrier 10 and the polyethylene base resin 30 may be used in addition to the dispersant.

Here, in step (2), the nano-barrier powder may be mixed in any one of 0.5 ± 0.05 wt% or 1.0 ± 0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin.

First of all, as the content of the nano-barrier (10) increases, the brittleness of the sheet-type product increases, making it vulnerable to external shocks. Conversely, if the content of the nano-barrier (10) decreases, the brittleness of the sheet-type product improves. Since it is difficult to expect the effect of improving durability and lowering gas permeability, it is necessary to select the content of the nano barrier 10 in a range that can exert the effect of improving durability and lowering gas permeability while limiting the increase in brittleness. In addition, if the nano-barrier (20) powder is added directly at the sheet-shaped product forming stage without manufacturing the masterbatch (20), not only is it difficult to control the content of the nano-barrier (10), but the dispersion rate is significantly lowered, resulting in durability. There is also a problem that the effect of improving or lowering gas permeability cannot be expected.

Accordingly, as a result of the applicant's repeated experiments, the content of the nano barrier 10 can limit the increase in brittleness in the range of 0.5 ± 0.05 wt% to 1.0 ± 0.05 wt%, while improving durability and lowering gas permeability. Two optimal examples were selected in which it is easy to control the content of the nano barrier 10 when applied to products of this type. However, the present invention is not limited to the above two embodiments as long as the above-mentioned object can be achieved, and it is possible to manufacture the masterbatch 20 with three or more various nano barrier 10 contents as needed. Of course.

Referring to FIG. 3, the mixing temperature during melt mixing of the nano barrier 10 and the polyethylene base resin 30 will be described.

Polyethylene generally has a melting point in the range of 115 to 135°C and a density in the range of 0.88 to 0.96 g/cm3. Polyethylene is classified according to the degree of crystallinity. High-density polyethylene has a density of 0.93 to 0.96 g/cm3 and a melting point of 120 to 140 ℃. Low-density polyethylene has a density of 0.91 to 0.94 g/cm3 and a melting point of 105 to 115 ℃. It has a range. For this reason, when the nano-sized inorganic-based nano barrier 10 is added during the extrusion process, control of the melting point becomes a very important factor. That is, as the weight of the nano-barrier 10 increases, the weight of the polyethylene base resin 30 relatively decreases, so even if there is a small change, the melting point of the polyethylene base resin 30 must be appropriately adjusted to prevent the molten polymer from forming inside the molten polymer. The nano barrier 10 is uniformly dispersed, making it easy to produce a highly concentrated masterbatch 20. For example, when the nano barrier 10 is mixed at a content of 1.0 ± 0.05 wt%, the masterbatch 20 is produced at a relatively lower temperature than when the nano barrier 10 is mixed at a content of 0.5 ± 0.05 wt%.

As an example, when the content of the nano-barrier powder is 0.5 ± 0.05 wt%, step (2) is performed by mixing a mixture of the nano-barrier, the polyethylene base resin, and the dispersant by melting the polyethylene base resin. It may include a step (step (2-1a)) of gradually increasing the melting temperature over a plurality of steps from above to 190 ± 2.5°C.

For example, in this embodiment, referring to FIG. 3, the nano barrier 10 and the polyethylene base resin 30 begin melt mixing in the range of 130 ± 2.5° C. in the starting stage (stage 1), and then proceed to subsequent stages. As you repeat, 140 ± 2.5℃ (step 2), 150 ± 2.5℃ (step 3), 160 ± 2.5℃ (step 4), 170 ± 2.5℃ (step 5-6), 180 ± 2.5℃ (step 7-8) ), the temperature can be gradually increased over 9 steps to 190± 2.5℃ (9 steps). The gradual melt mixing through several steps as described above is intended to maximize the dispersion of the nano barrier 10 within the polyethylene base resin 30, and various temperatures and stages are used between the start and end temperatures as needed. Of course, it can be configured as .

Here, the extruder is provided as a modular intermeshing co-rotating twin-screw extruder, the L/D ratio (length/diameter ratio) is provided at 40:1, and the melt speed is in the range of 380 to 400 rpm. It is prepared with Additionally, the melting temperature maintained at each stage may be set by time, or the melting rate may be set as described above.

The above-described melting conditions set the optimal melting conditions for maximizing the improvement of the dispersion of the nano-barrier 10 in a melted state of the polyethylene base resin 30 according to the structure of the compressor. Here, the configuration of the extruder And depending on the mixture, the number of melting steps and melting conditions can be set in various ways.

Meanwhile, step (3) further includes the step of extruding (3-1) the mixture. Here, the extrusion temperature when the mixture is extruded can be set to 192 ± 1.5°C.

The extrusion temperature is the temperature when the molten mixture passes through the extrusion hole and is discharged to the outside. A sudden change in temperature at the extrusion hole prevents smooth mixing of the nano barrier 10 and the polyethylene base resin 30, causing dispersion. It can lower the degree. On the other hand, if the extrusion temperature is too high, the mixed liquid passing through the extrusion hole becomes saggy and cannot be cut into pellets. Therefore, the applicant of the present application set the temperature range in which cutting can be performed smoothly without affecting the degree of dispersion, based on data obtained through repeated experiments. Since the above description regarding the extrusion temperature setting is equally applied to other embodiments described later, redundant description thereof will be omitted.

Meanwhile, step (3) may further include the step of rapidly cooling the extruded mixture (3-2) in the range of 15 ± 2.5°C. This step is a quenching step, in which the mixture extruded at high temperature is rapidly cooled to room temperature to facilitate pelletization.

Afterwards, cutting is performed in the pelletizing step, and the cutting speed can be set in various ways, for example, 800 ± 12 rpm. Here, the cutting speed can be appropriately changed depending on the above-described extrusion temperature and the composition of the mixture. Meanwhile, the cut functional polyurethane masterbatch 20 may have, for example, a cylindrical shape, in which case the length is 3.0 ± 0.5 mm and the cross-section is oval, with a radial length of 3.0 ± 0.15 mm and a minor axis of 2.5 ± 2.5 mm. It can be prepared in the range of 0.15 mm.

Accordingly, unlike the polyethylene base resin 30 shown in (a) of FIG. 4, the functional polyethylene masterbatch 20 recovered through the above-described manufacturing method, as shown in (b) of FIG. 4, was subjected to an extrusion molding process. After cutting, the sides are recovered in the form of yellowish pellets.

On the other hand, when the nano-barrier powder is prepared at 1.0 ± 0.05 wt%, step (2) is (2-1b) a mixture of the nano-barrier, the polyethylene base resin, and the dispersant, dissolved in the polyethylene base resin. It may include the step of gradually increasing the melt temperature over several steps from a temperature above 180 ± 2.5°C.

As an example, referring to FIG. 3, as in this embodiment, the nano barrier 10 and the polyethylene base resin 30 begin to melt and mix in the range of 130 ± 2.5° C. in the starting stage (stage 1), and in subsequent stages As you repeat, 140 ± 2.5℃ (step 2), 150 ± 2.5℃ (step 3 and 4), 160 ± 3.5℃ (step 5 and 6), 170 ± 3.5℃ (step 7 and 8), 180 ± 2.5℃ (9 steps) The temperature can be gradually increased in 9 steps. As in the above-described embodiment, as long as the nano barrier 10 can maximize dispersion within the polyethylene base resin 30, it can be configured at various temperatures and stages as needed between the start temperature and end temperature. Of course.

In this case, step (3) further includes the step of extruding (3-1b) the mixture, and the extrusion temperature when the mixture is extruded can be set to 183 ± 1.5°C. Hereinafter, descriptions that overlap with those in the above-described embodiment will be omitted.

Accordingly, as described above, the masterbatch 20 manufactured through the composition ratio of the inorganic-based nano barrier 10 and the polyethylene base resin 30 can be used to produce a sheet (for example, a lining sheet). In this case, it has the effect of increasing durability and reducing gas permeability.

Figure 5 shows the results of an experiment for cases in which the nano barrier 10 was added to the polyethylene base resin 30 and cases in which the nano barrier 10 was not added. Referring to FIG. 5, the mixing effect of the nano barrier 10 and the polyethylene base resin 30 can be confirmed by the shear thinning phenomenon. Specifically, it can be confirmed through a decrease in the entanglement density between the nano barrier (10) and the polyethylene base resin (30) in the high frequency region (~10 rad/s) and an increase in the complex viscosity. do. That is, as the content of the nano-barrier 10 increases, the degree of dispersion inside the polyethylene base resin 30 increases, so the attractive force on the surface of the nano-barrier 10 increases, thereby increasing the complex viscosity value.

Meanwhile, after addition of the nano barrier 10, the elastic modulus (G', storage modulus) of the polyethylene base resin 30 crosses the viscosity modulus (G", loss modulus) in the high frequency region. It can be seen that the value is higher when the nano barrier 10 is added (NB in the legend of Figure 5) than when it is not added. This means that the physical properties of the polyethylene base resin 30 are liquid-like. It transitions from a solid-like state to increase durability and reduce gas permeability.

Gas permeability refers to gas molecules dissolving on the surface of the polymer material they come in contact with, allowing the gas molecules to penetrate into the polymer material and pass through the cross section of the polymer material based on diffusion. This is determined by the structure and crystallinity of the polymer material and the relationship between the gas molecules and the gas molecules. This is because it is greatly influenced by mutual manpower.

Meanwhile, referring to Figure 5, in the low frequency range, the loss modulus value of the polyethylene base resin 30 is superior, but in the high frequency range (> 10 rad/s), crossover occurs and the storage modulus value becomes superior. You can check it.

The functional polyethylene masterbatch 20 including an inorganic-based nano barrier according to an embodiment of the present invention is a core-shell consisting of an inorganic material as the core and a hydrocarbon-based polymer as the shell. It is manufactured in the form of pellets by dispersing the -shell structure nano barrier into polyethylene base resin.

The core may be made of an inorganic material selected from the group consisting of silica (Si), aluminum (Al), and iron (Fe).

The polyethylene base resin is prepared from any one of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or ultra low density polyethylene (ULDPE), and the hydraulic diameter of the nano barrier is 350 ± It can be provided in the range of 50 nm.

The nano-barrier may be provided in the range of 0.5±0.05 wt% or 1.0±0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin.

The dispersant may further include a dispersant added in an amount of 1,000 ppm or less of the total weight of the nano barrier and the polyethylene base resin. The dispersant may be, for example, selected from the group consisting of any one or a mixture of stearic acid series, zinc stearate, calcium stearate, and magnesium stearate.

Although the present invention has been described above with limited examples and drawings, the present invention is not limited thereto, and the technical idea and scope of the patent claims can be understood by those skilled in the art in the technical field to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equality. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the equivalent scope should be construed as being included in the present invention.

10: Nano Barrier
20: Masterbatch
30: polyethylene base resin

Claims (13)

Pellets are made by mixing and extruding a nano barrier with a core-shell structure made of an inorganic material as a core and a hydrocarbon polymer as the shell, a dispersant, and polyethylene base resin. Manufactured in the form of
The hydraulic diameter of the nano barrier is set in the range of 350 ± 50 nm,
The nano-barrier is prepared in the range of 0.5 ± 0.05 wt% or 1.0 ± 0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin,
When the content of the nano-barrier is 0.5 ± 0.05 wt%, the melt temperature of the mixture of the nano-barrier, the polyethylene base resin, and the dispersant is gradually increased over a plurality of steps, and the final melt temperature is 190 ± 2.5 ° C. The extrusion temperature when the mixture is extruded out of the extruder is set to 192 ± 1.5°C,
When the content of the nano barrier is 1.0 ± 0.05 wt%, the final melt temperature is set to 180 ± 2.5 ℃, and the extrusion temperature when the mixture is extruded out of the extruder is set to 183 ± 1.5 ℃, inorganic material-based Functional polyethylene masterbatch containing nano-barrier. In paragraph 1:
The core is made of an inorganic material selected from the silica (Si), aluminum (Al) and iron (Fe) series or a group containing these,
The polyethylene base resin is prepared from any one of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or ultra low density polyethylene (ULDPE), and the hydraulic diameter of the nano barrier is 350 ± Functional polyethylene masterbatch containing inorganic-based nano-barrier prepared in the 50 nm range. In paragraph 1:
The dispersant is added in an amount of 1,000 ppm or less of the total weight of the nano barrier and the polyethylene base resin,
The dispersant includes an inorganic-based nano-barrier selected from the group consisting of any one or a mixture of stearic acid series, zinc stearate, calcium stearate, and magnesium stearate. Functional polyethylene masterbatch. (1) manufacturing an inorganic-based nano-barrier powder;
(2) mixing the nano-barrier powder, polyethylene base resin, and dispersant into an extruder; and
(3) extruding the molten mixture to obtain a masterbatch in the form of a pellet;
The step (1) is,
(1-1) A step of polymerizing a hydrocarbon-based polymer as a shell and an inorganic material selected from silica (Si), aluminum (Al), and iron (Fe) series or a group containing these as the core. and the hydraulic diameter of the manufactured nano-barrier is set in the range of 350 ± 50 nm,
In step (2),
The nano-barrier powder is mixed in an amount of 0.5 ± 0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin,
(2-1a) gradually increasing the melting temperature of the mixture of the nano-barrier, the polyethylene base resin, and the dispersant over a plurality of steps from the melting point of the polyethylene base resin to 190 ± 2.5 ° C. ,
In step (3),
(3-1a) further comprising the step of extruding the mixture,
A method for producing a functional polyethylene masterbatch containing an inorganic-based nano-barrier, wherein the extrusion temperature when the mixture is extruded outward from the extrusion port at the tip of the extruder is set to 192 ± 1.5 ° C. In paragraph 4,
The step (3-1a) is 130 ± 2.5 ℃ (step 1), 140 ± 2.5 ℃ (step 2), 150 ± 2.5 ℃ (step 3), 160 ± 2.5 ℃ (step 4), 170 ± 2.5 ℃ (step 4) It is provided to gradually increase the melting temperature of the mixture in 9 steps: 5-6 steps), 180 ± 2.5 ℃ (7-8 steps), 190 ± 2.5 ℃ (9 steps),
The extruder is provided as a modular intermeshing co-rotating twin-screw extruder, the L/D ratio (length/diameter ratio) is set to 40:1, and the melt speed is set in the range of 380 to 400 rpm. Method for producing functional polyethylene masterbatch containing inorganic-based nano-barrier. (1) manufacturing an inorganic-based nano-barrier powder;
(2) mixing the nano-barrier powder, polyethylene base resin, and dispersant into an extruder; and
(3) extruding the molten mixture to obtain a masterbatch in the form of a pellet;
The step (1) is,
(1-1) A step of polymerizing a hydrocarbon-based polymer as a shell and an inorganic material selected from silica (Si), aluminum (Al), and iron (Fe) series or a group containing these as the core. and the hydraulic diameter of the manufactured nano-barrier is set in the range of 350 ± 50 nm,
In step (2),
The nano-barrier powder is mixed in an amount of 1.0 ± 0.05 wt% of the total weight of the nano-barrier and the polyethylene base resin.
(2-1b) gradually increasing the melting temperature of the mixture of the nano-barrier, the polyethylene base resin, and the dispersant over a plurality of steps from the melting point of the polyethylene base resin to 180 ± 2.5 ° C. ,
In step (3),
(3-1b) further comprising the step of extruding the mixture,
A method for producing a functional polyethylene masterbatch containing an inorganic-based nano-barrier, wherein the extrusion temperature when the mixture is extruded out from the extrusion port at the tip of the extruder is set to 183 ± 1.5 ° C. In paragraph 6:
The step (3-1b) is 130 ± 2.5°C (step 1), 140 ± 2.5°C (step 2), 150 ± 2.5°C (steps 3 and 4), 160 ± 3.5°C (steps 5 and 6), 170°C It is provided to gradually increase the melting temperature of the mixture in 9 steps of ± 3.5℃ (steps 7 and 8) and 180 ± 2.5℃ (step 9),
The extruder is provided as a modular intermeshing co-rotating twin-screw extruder, the L/D ratio (length/diameter ratio) is set to 40:1, and the melt speed is set in the range of 380 to 400 rpm. Method for producing functional polyethylene masterbatch containing inorganic-based nano-barrier. In paragraph 4 or 6:
In step (3),
(3-2) quenching the extruded mixture in the range of 15±2.5°C;
(3-3) cutting the mixture extruded through the extrusion port at a cutting speed of 800 ± 12 rpm. A method for producing a functional polyethylene masterbatch comprising an inorganic-based nano-barrier. In paragraph 4 or 6:
The dispersant is added in an amount of 1,000 ppm or less of the total weight of the nano barrier and the polyethylene base resin. delete delete delete delete

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