Novel polymer, membrane composition comprising same, and pes membrane

Abstract

The present invention relates to a novel polymer having amphiphilicity by the introduction of ethyl lauroyl arginate into a sulfonated polyethersulfone-based polymer, a membrane composition comprising the novel polymer, and a PES membrane manufactured using the membrane composition.

Description

Novel polymer, membrane composition comprising same, and PES membrane

[0001] The present invention relates to a novel polymer, a novel polymer having amphiphilicity by introducing ethyl lauroyl arginate into a sulfonated polyethersulfone polymer, a membrane composition comprising the novel polymer, and a PES membrane manufactured using the membrane composition.

[0002] Membranes act as a selective barrier, allowing the passage of certain components and retaining others, and are used for purification, sterilization, filtration, and discharge purposes.

[0003] Membranes are widely used in pharmaceutical production and downstream processes in the pharmaceutical industry, and in the medical industry, membranes are used for drug filtration, hemodialysis, drug delivery, intravenous injection, and sterilization.

[0004] The most common chemicals used in medical membranes include polysulfone (PSU), polyethersulfone (PES), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polypropylene (PP), and modified acrylics, while the most common technologies used in medical membranes include ultrafiltration (UF), microfiltration (MF), and nanofiltration (NF).

[0005] In addition, existing PES (Polyethersulfone)-based membranes have low hydrophilicity, causing problems with protein adsorption. Therefore, in order to improve hydrophilicity, a sulfonated PES material was developed through research on 'Polymer resin for biopharmaceutical purification or diagnostic membrane containing nitro group and its manufacturing method (Korean Patent No. 10-2084359).'

[0006] In addition, ethyl lauroyl alginate causes leakage in the bacterial cell wall, which results in the loss of nucleic acids, DNA, proteins, etc. necessary for survival, as well as intracellular K, which is essential for maintaining bacterial membrane potential. + It is a substance that kills bacteria by causing them to release , and is mainly used as a packaging material for food.

[0007] [Prior Art Literature]

[0008] [Patent Document]

[0009] Republic of Korea Patent Publication No. 10-2018-0087312

[0010] The present invention is to provide a membrane including polyethersulfone and ethyl lauroyl alginate, which improves the water permeability of existing membranes to biological substances and has an antibacterial effect.

[0011] To achieve the above object, a novel polymer according to one embodiment of the present invention includes a first repeating unit in which ethyl lauroyl arginate and sulfonated polyethersulfone interact.

[0012] The above first repeating unit may be represented by the following chemical formula A.

[0013] [Chemical Formula A]

[0014]

[0015] The above first repeating unit may be represented by the following chemical formula A-1.

[0016] [Chemical Formula A-1]

[0017]

[0018] The novel polymer may include a second repeating unit represented by the following chemical formula B.

[0019] [Chemical Formula B]

[0020]

[0021] The above novel polymer may be represented by the following chemical formula 1.

[0022] [Chemical Formula 1]

[0023]

[0024] In the above chemical formula 1, n and m are integers greater than or equal to 0.

[0025]

[0026] In addition, a membrane composition according to another embodiment of the present invention includes the novel polymer and may further include polyethersulfone.

[0027]

[0028] In addition, a polyethersulfone (PES) membrane according to another embodiment of the present invention includes an amphiphilic polymer into which ethyl lauroyl arginate is introduced.

[0029] The above amphiphilic polymer comprises a first repeating unit in which ethyl lauroyl arginate and sulfonated polyethersulfone interact with each other.

[0030]

[0031] The present invention has the effect of providing a novel polymer having amphipathic properties through the interaction of hydrophobic ethyl lauroyl alginate and hydrophilic sPES (sulfonated polyethersulfone).

[0032] In addition, by providing the novel polymer, it is possible to provide a membrane that is superior in preventing membrane fouling of existing PES materials and has improved water permeability to biological substances.

[0033] Figure 1 illustrates the results of SLS (Static Light Scattering) measurement of a novel polymer according to one embodiment of the present invention.

[0034] Figure 2 illustrates the NMR measurement results of a novel polymer according to one embodiment of the present invention.

[0035] Figure 3 illustrates the results of measuring the flow rate of a membrane according to one embodiment of the present invention.

[0036] Figure 4 illustrates the results of measuring the removal rate of a membrane according to one embodiment of the present invention.

[0037] To achieve the above object, a novel polymer according to one embodiment of the present invention includes a first repeating unit in which ethyl lauroyl arginate and sulfonated polyethersulfone interact.

[0038] The above first repeating unit may be represented by the following chemical formula A.

[0039] [Chemical Formula A]

[0040]

[0041] The above first repeating unit may be represented by the following chemical formula A-1.

[0042] [Chemical Formula A-1]

[0043]

[0044] The novel polymer may include a second repeating unit represented by the following chemical formula B.

[0045] [Chemical Formula B]

[0046]

[0047] The above novel polymer may be represented by the following chemical formula 1.

[0048] [Chemical Formula 1]

[0049]

[0050] In the above chemical formula 1, n and m are integers greater than or equal to 0.

[0051]

[0052] In addition, a membrane composition according to another embodiment of the present invention includes the novel polymer and may further include polyethersulfone.

[0053]

[0054] In addition, a polyethersulfone (PES) membrane according to another embodiment of the present invention includes an amphiphilic polymer into which ethyl lauroyl arginate is introduced.

[0055] The above amphiphilic polymer comprises a first repeating unit in which ethyl lauroyl arginate and sulfonated polyethersulfone interact with each other.

[0056] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0057]

[0058] A novel polymer according to one embodiment of the present invention is based on a sulfonated polyethersulfone into which hydrophobic ethyl lauroyl arginate is introduced.

[0059] The novel polymer comprises a first repeating unit in which ethyl lauroyl arginate and a sulfonated polyethersulfone interact with each other.

[0060] The above first repeating unit may be represented by the following chemical formula A.

[0061] [Chemical Formula A]

[0062]

[0063] More specifically, the first repeating unit may be represented by the following chemical formula A-1.

[0064] [Chemical Formula A-1]

[0065]

[0066] The novel polymer may include a second repeating unit represented by the following chemical formula B.

[0067] [Chemical Formula B]

[0068]

[0069] The above novel polymer may be represented by the following chemical formula 1.

[0070] [Chemical Formula 1]

[0071]

[0072] In the above chemical formula 1, n and m are integers greater than or equal to 0, and in the above chemical formula 1, m may be 250 to 270, and n may be 15 to 75. The above m and n are mole numbers.

[0073]

[0074] A membrane composition according to another embodiment of the present invention comprises a novel polymer according to one embodiment of the present invention.

[0075] The above membrane composition may further include polyethersulfone, and may include the novel polymer and polyethersulfone.

[0076] The above membrane composition may further comprise a pore-forming agent. The pore-forming agent may be polyvinylpyrrolidone (PVP) and / or poly ethylene glycol (PEG).

[0077] The PVP may be 0.1 to 2 wt% based on 100 wt% of the total weight of the membrane composition, and the PEG may be 10 to 40 wt% based on 100 wt% of the total weight of the membrane composition. The PEG may be PEG 200.

[0078]

[0079] The above membrane composition may further include a pore control agent. The pore control agent may control the pore size of the membrane by controlling the solvent extraction rate during the pore formation process. The pore control agent may be LiCl or CaCl2. The pore control agent may be present in an amount of 0.1 to 2 wt% relative to 100 wt% of the total weight of the membrane composition.

[0080]

[0081] The above membrane composition further comprises a solvent, and the solvent may be dimethyl sulfoxide (DMSO). The solvent may be present in an amount of 50.9 to 53.4 wt% relative to 100 wt% of the total weight of the membrane composition.

[0082]

[0083] In addition, a polyethersulfone (PES) membrane according to another embodiment of the present invention includes an amphiphilic polymer into which ethyl lauroyl arginate is introduced.

[0084] The above amphiphilic polymer comprises a first repeating unit in which ethyl lauroyl arginate and sulfonated polyethersulfone interact with each other.

[0085] The above first repeating unit may be represented by the following chemical formula A.

[0086] [Chemical Formula A]

[0087]

[0088] More specifically, the first repeating unit may be represented by the following chemical formula A-1.

[0089] [Chemical Formula A-1]

[0090]

[0091] The above amphiphilic polymer may include a second repeating unit represented by the following chemical formula B.

[0092] [Chemical Formula B]

[0093]

[0094] The above amphiphilic polymer may be represented by the following chemical formula 1.

[0095] [Chemical Formula 1]

[0096]

[0097] In the above chemical formula 1, n and m are integers greater than or equal to 0, and in the above chemical formula 1, m may be 250 to 270, and n may be 15 to 75. The above m and n are mole numbers.

[0098]

[0099] The above polyethersulfone (PES) membrane may be manufactured using the above membrane composition.

[0100]

[0101] The present invention is further described in detail through the following examples. The following examples are illustrative and do not limit the scope of the present invention. These examples are merely examples of synthesis, and the amounts and ratios of the components may vary depending on the synthesis ratio and amount.

[0102]

[0103] Manufacturing example. Synthesis of a novel polymer

[0104] To synthesize a novel polymer, sLAE (sulfonated Polyethersulfone-ethyl lauroyl arginate), the following procedure was followed.

[0105] First, 0.86 mol of DCDPS (4,4'-Dichlorodiphenyl sulfone), 0.64 mol of BPA (Bisphenol A), 0.21 mol of sHQ (sulfonated hydroquinone), 0.21 mol of LAE (Ethyl lauroyl arginate HCl), and 2.22 g of K2CO3 are mixed in 1 L of a mixture solvent with a volume ratio of NMP (N-Methyl-2-pyrrolidone): toluene = 2:1, and then heated with stirring at 160 °C for 48 hours (hr) under nitrogen conditions. Afterwards, stir at 190 °C for 4 hours (hr) and then cool naturally. The resulting product was washed with deionized water, separated with DCM (dichrolomethane), and dried to obtain a new polymer represented by the following chemical formula 1 as the final product. In the following experimental examples, the new polymer was defined as sLAE (sulfonated Polyethersulfone-ethyl lauroyl arginate).

[0106] [Chemical Formula 1]

[0107]

[0108] In the chemical formula 1 of the above manufacturing example, m is 296 and n is 37. The above m and n are mole numbers.

[0109]

[0110] Measurement example. Molecular weight measurement

[0111] The molar mass of sLAE represented by chemical formula 1 synthesized in the above manufacturing example was measured through SLS (Static Light Scattering), and the measurement result graph is shown in Fig. 1. Referring to Fig. 1, the molar mass (M) of sLAE represented by chemical formula 1 synthesized in the above manufacturing example W ) was measured to be 190,000 g / mol.

[0112]

[0113] Measurement example. NMR analysis

[0114] NMR analysis was performed on sLAE represented by chemical formula 1 synthesized in the above manufacturing example, and NMR was H 1 -NMR was used and the results of analyzing the peak positions for each element are shown in Fig. 2. Referring to Fig. 2, the integrals of each peak were calculated as a+c=69.68, b+f=32.66, d+e=38.76 based on g=1, and the integral of the "*" peak with 3 Hs was calculated as 3.28. Based on this, sLAE represented by the chemical formula 1 in the example is calculated at a ratio of m:n of 8:1.

[0115]

[0116] Example. Method for manufacturing a PES (Polyethersulfone) membrane

[0117] A membrane composition having a composition ratio of sLAE (synthesized in the manufacturing example), PES (Polyethersulfone), PVP (Polyvinylpyirolidone), PEG (Poly Ethylene Glycol) 200, CaCl2, and DMSO (Dimethyl sulfoxide) was prepared according to the composition ratio in Table 1 below.

[0118] A membrane manufacturing solution was prepared by mixing sLAE, PVP, PEG 200, CaCl2, and DMSO with the composition shown in Table 1.

[0119] After casting the above membrane manufacturing solution to a thickness of 400 μm on a PET film (thickness 100 to 800 μm), NIPS (nonsolvent induced phase separation) was treated in a constant-temperature water bath of deionized water (DI water) for 10 minutes (min), and then the membrane precursor was manufactured through a secondary NIPS (nonsolvent induced phase separation) treatment by immersing in a constant-temperature water bath composed of 5 wt% glycerol (Gly) and 95 wt% deionized water for 10 minutes (min), and then drying in a drying device at a temperature of 53°C for 25 minutes (min), thereby manufacturing a membrane.

[0120] Classification sLAE (wt%) PES (wt%) PVP (wt%) PEG 200 (wt%) CaCl2 (wt%) DMSO (wt%) Example 10.5 20.00.125.01.05 3.4 Example 21.0 20.00.125.01.05 2.9 Example 31.5 20.00.125.01.05 2.4 Example 42.0 20.00.125.01.05 1.9 Example 53.0 20.00.125.01.05 0.9

[0121]

[0122] Comparative example. Manufacturing method of PES (Polyethersulfone) membrane

[0123] A membrane composition having the composition ratio shown in Table 2 below was prepared. A membrane manufacturing solution was prepared by mixing PVP, PEG 200, CaCl2, and DMSO with the composition shown in Table 2.

[0124] The prepared manufacturing solution was used to manufacture a membrane in the same manner as in the above example.

[0125] Classification PES (wt%) PVP (wt%) PEG 200 (wt%) CaCl2 (wt%) DMSO (wt%) Comparative Example 20.00.125.01.053.9

[0126]

[0127] Measurement example. Physical property measurement

[0128] The pure water (DI water) flux of each membrane manufactured in the above example was measured 4 or 5 times and the results are summarized in Table 3.

[0129] Additionally, the thickness of each membrane manufactured in the above example was measured 10 times, the average was calculated, and the results are summarized in Table 3 below.

[0130] In addition, the MWCO (Molecular weight cutoff) was measured for each membrane manufactured in the above example, and the measurement was performed 4 or 5 times, and the results are summarized in Table 3 below. From the measured data, the pore size and porosity were summarized in Table 3 below using Equations 1 and 2 below.

[0131]

[0132] [Formula 1]

[0133]

[0134] In the above equation 1, “ε” is porosity, “W w ", "Wd" are the membrane weights in wet and dry states, respectively, and "ρ w " is the density of water, and "V" is the volume of the membrane in a wet state.

[0135] [Formula 2]

[0136]

[0137] In the above equation 2, “ε” is the porosity, “η” is the viscosity of water, and “Q” is the volumetric flow rate of water (m 3 / s), “A” is membrane effective area (m 2 ), "ΔP" is the applied pressure (pascal, 1 bar = 100000 pa), "L" is the membrane thickness (m). In Table 3, LMH is L / m 2 ·hr.

[0138] Flux [ml / min / cm] 2]Thickness[㎛]Rejection[%]Poer size[㎛]PorosityExample 10.318228.283.950.05060.61430.400237.684.050.06070.57830.26823987.960.04730.61520.342231.395.10.05290.61280.277231.494.730.04880.5951Example 20.440234.296.240.07870.42610.268239.592.870.04770.61260.286239.889.020.04890.61830.276234.787.90.05110.56290.223237.788.230.04430.5963Example 30.493239.686.930.07500.5030.285245.192.710.05330.5590.323279.394.120.05700.6070.202246.892.060.04280.600Example 40.512240.990.770.07940.4790.549238.990.240.08550.4500.494236.391.40.06910.5580.403238.487.430.06040.5870.387234.589.520.560.0605Example 50.705235.690.490.08010.5790.510237.588.120.06630.6030.450233.390.270.06480.5660.479231.388.90.06610.571

[0139]

[0140] Referring to Table 3, it can be seen that as the sLAE ratio increases, the pore size increases and the porosity decreases up to 2.0 wt%. Meanwhile, the removal rate increases up to 1.5 wt%, and the flow rate continuously increases. Therefore, it can be seen that the performance of the membrane can be controlled through the sLAE ratio.

[0141]

[0142] For each of the membranes manufactured in the comparative examples and examples, the pure water flowrate and the flow rate of 0.25 wt% PEG200k (“PEG200 flow rate”) are summarized in Fig. 3. In Fig. 3, the x-axis represents the content of sLAE, where “0” represents the membrane manufactured in the comparative examples, “0.5” represents the membrane manufactured in the example 1, “1” represents the membrane manufactured in the example 2, “1.5” represents the membrane manufactured in the example 3, “2” represents the membrane manufactured in the example 4, and “3” represents the membrane manufactured in the example 5. In Fig. 3, the measurement was performed using an amicon stirred cell under a pressure of 1 bar. The "pure water flowrate" was performed without stirring, and the "PEG 200 flowrate" was performed with stirring at 180 rpm. At this time, the filtered liquid was connected to a scale and the weight change was measured over time to calculate the value.

[0143] For each of the membranes manufactured in the comparative examples and examples, 0.25 wt% PEG200k was passed through them, and the removal rate was measured as the ratio of the height of the peak of PEG200k of the liquid that passed through them to 0.25 wt% using UV-vis, and the results are shown in Fig. 4. In Fig. 4, the x-axis represents the content of sLAE, where “0” is the membrane manufactured in the comparative example, “0.5” is the membrane manufactured in the example 1, “1” is the membrane manufactured in the example 2, “1.5” is the membrane manufactured in the example 3, “2” is the membrane manufactured in the example 4, and “3” is the membrane manufactured in the example 5. As an example, in Fig. 4, if 0.25 wt% of PEG200k has a peak height of 2 in UV-Vis and the peak value at the same position of the passed liquid is 0.5, it can be seen that it has a removal rate of (2-0.5) / 2*100 = 75%.

[0144]

[0145] Referring to Fig. 4, it can be confirmed that the membrane manufactured in the above example has a high removal rate for PEG200.

[0146]

[0147] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

Claims

1. A first repeating unit comprising ethyl lauroyl arginate and sulfonated polyethersulfone interacting with each other. New polymer.

2. In paragraph 1, The above first repeating unit is represented by the following chemical formula A: New polymer. [Chemical Formula A] 3. In paragraph 2, The above first repeating unit is represented by the following chemical formula A-1, New polymer. [Chemical Formula A-1] 4. In paragraph 1, A second repeating unit represented by the following chemical formula B is included. New polymer. [Chemical Formula B] 5. In paragraph 1, The above novel polymer is represented by the following chemical formula 1: New polymer. [Chemical Formula 1] In the above chemical formula 1, n and m are integers greater than or equal to 0.

6. A membrane composition comprising a polymer according to any one of claims 1 to 5.

7. In paragraph 6, A membrane composition further comprising polyethersulfone.

8. A polyethersulfone (PES) membrane containing an amphiphilic polymer into which ethyl lauroyl arginate is introduced.

9. In paragraph 8, The above amphiphilic polymer comprises a first repeating unit in which ethyl lauroyl arginate and sulfonated polyethersulfone interact with each other. Polyethersulfone (PES) membrane.

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