A high flux ion permeable polymer resin, its method of preparation and use in thin films

Abstract

The application discloses a high-flux ion permeation polymer resin and belongs to the technical field of high-molecular compound synthesis. The preparation method of the polymer comprises the following specific steps: (1) hydrophobic monomers, functional monomers and hydrophilic monomers are used as raw materials, and a polymer intermediate is obtained after polymerization reaction of the raw materials after adding an initiator; (2) the polymer intermediate is reacted with a lactone, and a high-flux ion permeation polymer resin is obtained. The application adopts the strategy of combining hydrophilic and hydrophobic chain segments with zwitterions, prepares a vinyl type polymer through thermal initiation or redox initiation, controls the proportion of hydrophilic and hydrophobic monomers to regulate the stability of the polymer in a water system, controls the feeding amount of the lactone to regulate the modification rate of the side chain zwitterions, and thus the ion permeation rate can be regulated.

Description

Technical Field

[0001] This invention belongs to the field of polymer compound synthesis technology, specifically relating to a high-flux ion-permeable polymer resin, its preparation method, and its application in thin films. Background Technology

[0002] Bottlebrush polymers (BBPs) are a class of comb-shaped polymers with a unique topological structure. The main chain is connected with a sufficiently high density of side chains, which increases the rigidity of the main chain and allows the side chains to fully extend. Functional BBPs have a wide range of applications in fields such as ultra-soft elastomers, optical crystals, biomimetic lubricants, drug carriers, antifouling coatings, and smart materials.

[0003] There are three main strategies for the synthesis of bio-based polymers (BBPs): "grafting to," "grafting from," and "grafting through." "Grafting through" ensures that each monomer unit on the main chain has side chain modification and a high grafting density. The ring-opening metathesis polymerization of norbornene catalyzed by Grubbs catalyst is the most commonly used reaction type for synthesizing BBPs using the "grafting through" strategy. BBPs with polypeptide side chains have advantages such as rich functionality and good biocompatibility, making them very suitable for use as nanomedicine carriers and biomimetic soft tissues. Synthesizing such BBPs using the "grafting from" method requires selecting a suitable backbone structure as the main chain and then modifying the amino initiation sites. The synthetic steps are complex, and the synthesis process cannot guarantee that each initiation site can initiate the ring-opening polymerization of NCA monomers; the side chain grafting density is uncontrollable. The "grafting to" method also cannot guarantee 100% side chain modification and usually requires a very efficient coupling reaction.

[0004] Therefore, it is urgent for those skilled in the art to provide a new polymer and its synthesis method that can ensure that each monomer unit of the main chain is modified with side chain polyamino acids, while also controlling the side chain density, length and peptide type. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a high-throughput ion-permeable polymer resin, its preparation method, and its application in films. This invention synthesizes a random copolymer with a main chain containing hydrophobic monomers, functional monomers, and hydrophilic monomers via free radical polymerization. By adjusting the monomer-initiator feed ratio, the degree of polymerization is controlled, achieving a number-average molecular weight of over 50,000 for the polymerized product, thus improving the resin's stability in the aqueous phase and meeting application requirements. Simultaneously, through nucleophilic substitution or ring-opening reactions on the pyridine nitrogen atom, ionic groups (sulfonate-SO₄) are modified onto the poly(4-vinylpyridine) monomer unit. 3- phosphate-PO 4- (etc.) to improve ion permeability. The presence of hydrophobic monomer units can ensure the stability of the resin in the aqueous phase, while hydrophilic monomer units help to improve ion permeability. By adjusting the ratio of monomer units and the content of ion group modification, the resin film can achieve high-flux ion permeability.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for preparing a high-flux ion-permeable polymer resin includes the following specific steps:

[0008] (1) Using hydrophobic monomers, functional monomers and hydrophilic monomers as raw materials, an initiator is added and a polymerization reaction is carried out to obtain polymer intermediates;

[0009] (2) After reacting the polymer intermediate with the lactone, a high-flux ion-permeable polymer resin can be obtained.

[0010] Vinyl polymer resins obtained by traditional free radical polymerization have poor biocompatibility and are difficult to biodegrade in vivo. The vinyl polymers modified by the present invention through side chain ionic groups have the advantages of good hydrophilicity, good biocompatibility, and high ion permeability. The present invention improves the biocompatibility of vinyl polymers and enriches the functions of vinyl polymers by modifying zwitterionic groups or hydrophilic groups by using nucleophilic ring-opening or substitution reactions on pyridine nitrogen. Lactones are easily attacked by nucleophilic pyridine nitrogen atoms, thereby undergoing ring-opening reactions and introducing zwitterions into the polymer backbone. These zwitterions can exist stably in vivo or in pure water. The reaction efficiency is close to 100%. By controlling the feed ratio of lactones, the modification rate of side chain ionic groups can be adjusted.

[0011] Preferably, the mass ratio of the hydrophobic monomer, functional monomer, hydrophilic monomer and initiator in step (1) is 2.8-9.5:29.8-98.6:0-3.0:0.06-0.20;

[0012] The polymerization reaction is divided into thermally initiated polymerization and redox initiated polymerization. The conditions for thermally initiated polymerization are: reaction at 60-70℃ for 6-24 hours, and the conditions for redox initiated polymerization are: reaction at room temperature for 6-24 hours.

[0013] Preferably, the hydrophobic monomer in step (1) includes styrene or lauryl methacrylate;

[0014] The functional monomer includes 4-vinylpyridine;

[0015] The hydrophilic monomers include polyethylene glycol monomethyl ether methacrylate or hydroxyethyl acrylate;

[0016] The initiator is an azo thermal initiator or a redox initiator, wherein the azo thermal initiator includes azobisisobutyronitrile or azobisisovalerate, and the redox initiator is a combination of potassium persulfate (KPS) and N,N,N',N'-tetramethylethylenediamine (TEMED), wherein the mass ratio of KPS to TEMED is 0.10-1.35:0.06-0.86.

[0017] Preferably, the polymerization reaction in step (1) further includes a solvent, the solvent being tetrahydrofuran, and the mass ratio of the solvent to the hydrophobic monomer being 31.0-74.1:2.8-9.5.

[0018] The polymerization reaction also includes, after the reaction is completed, the precipitate is subjected to recrystallization, washing and drying to obtain the polymer intermediate.

[0019] Preferably, the mass ratio of the polymer intermediate to the lactone in step (2) is 10:0-1;

[0020] The reaction conditions are: reacting at 60-110℃ for 3-24 hours.

[0021] According to claim 1, the method for preparing a high-flux ion-permeable polymer resin is characterized in that the lactone in step (2) includes sulfonyl lactone or phosphatidyl lactone.

[0022] Preferably, the sulfonyl lactone is 1,3-propanesulfonyl lactone, and the phosphoryl lactone is 2-ethoxy-1,3,2-dioxophosphanecyclopentane-2-oxide.

[0023] Preferably, the reaction in step (2) further includes a solvent, which is tetrahydrofuran or water, the mass ratio of tetrahydrofuran to the polymer intermediate is 5-15:6-20, and the mass ratio of water to the polymer intermediate is 200-1000:6-20;

[0024] The reaction also includes, after the reaction is completed, the precipitate is subjected to recrystallization, washing and drying to obtain the high-flux ion-permeable polymer resin.

[0025] Preferably, the raw materials used in step (1) are filtered through a short aluminum oxide (200-300 mesh) column before feeding to remove the polymerization inhibitors present in the monomers, so as to avoid the influence on the polymerization reaction.

[0026] A high-throughput ion-permeable polymer resin was obtained by the preparation method described above.

[0027] The application of a high-throughput ion-permeable polymer resin prepared by the method described above in the preparation of thin films.

[0028] Preferably, the membrane includes a hemodialysis membrane or an insulin-sensing membrane.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] This invention employs a strategy combining hydrophilic and hydrophobic segments with zwitterions to prepare vinyl-type polymers via thermal or redox initiation. By controlling the ratio of hydrophilic and hydrophobic monomers, the stability of the polymer film in an aqueous system can be regulated. By adjusting the amount of lactone added, the modification rate of zwitterions on the side chains can be adjusted, thereby regulating the ion permeability. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0032] Figure 1 This is a schematic diagram of the polymer resin synthesis route of the present invention;

[0033] Figure 2 The above is the 1H NMR spectrum of the polymer resin in Example 1 of this invention;

[0034] Figure 3 The above is the 1H NMR spectrum of the polymer resin in Example 2 of this invention;

[0035] Figure 4 This is a graph showing the transmittance of different ions in polymer membranes modified with different sulfonates in Example 1 of the present invention. Detailed Implementation

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] Example 1

[0038] like Figure 1 This invention provides a method for preparing a high-flux ion-permeable polymer resin, comprising the following specific steps:

[0039] (1) Mix 9.5 parts by weight of styrene (St), 98.6 parts by weight of 4-vinylpyridine (4VP), 3.0 parts by weight of polyethylene glycol monomethyl ether methacrylate (molecular weight 300) (PEGMA), and 74.1 parts by weight of tetrahydrofuran. Then add 0.21 parts by weight of azobisisobutyronitrile (AIBN). Degas the system with argon gas to remove residual air. Seal the reaction flask and initiate the polymerization reaction at 70°C with a stirring speed of 500 rpm. As the reaction proceeds, the viscosity of the reaction system gradually increases until the stirring of the tetrahydrofuran solution stops, at which point the reaction is stopped. Dissolve and dilute the reaction product in 500 parts by weight of methanol, and then precipitate it in water to obtain a white solid product. Cut the precipitated white solid product into small pieces with scissors, soak in pure water, wash, and vacuum dry to obtain the polymer intermediate PSt. 72 -P4VP 720 -PPEGMA8;

[0040] (2) PSt-P4VP-PPEGMA, 1,3-propanesulfonic acid lactone, and THF were mixed evenly in a mass ratio of 10:1:10 and placed in a single-necked round-bottom flask. The mixture was reacted at 90°C for 12 hours. After the reaction was completed, the mixture was precipitated with diethyl ether and the solvent diethyl ether was removed to obtain a white solid product. The solid product was then dissolved again in methanol and precipitated in pure water. The solid product was soaked in pure water overnight, washed three times, and then vacuum dried at 50°C to remove residual solvent and water, yielding the final product PSt. 72 -P4VP 720 -PPEGMA8-(SO3) 80 The number-average molecular weight of the resin was 65,000 and the dispersibility index was 1.7, as determined by DMF phase gel permeation chromatography.

[0041] (3) According to PST 72 -P4VP 720 -PPEGMA8-(SO3) 80Mix THF and THF at a ratio of 0.01:9 to obtain a polymer concentration of 1 mg / mL. Pour the mixture into a polytetrafluoroethylene rectangular mold. After the solvent has completely evaporated, heat-treat the mixture in a 60°C constant temperature and humidity chamber for 24 hours to remove residual tetrahydrofuran. After cooling to room temperature, peel the membrane off the PTFE plate to obtain an ion-permeable membrane.

[0042] Testing the ion-permeable membrane for different ions (Na+) in aqueous solution + ,K + Ca + Mg + The transmittance of the polymer membrane was measured and compared with the ion transmittance of the polymer membrane without sulfonate modification. The results are shown in [Figure number missing]. Figure 4 In the figure, (a) is a bar chart of the permeability of different ions, and (b) is a bar chart of the ratio of the permeability of different ions. As can be seen from the figure, the ion permeation membrane prepared by the present invention has a good permeability for different ions. Furthermore, the sulfonate-modified ion permeation membrane prepared by the present invention has a better permeability for different ions than the ion permeability of the polymer membrane without sulfonate modification; and Figure 2 The proton NMR spectrum accurately characterizes the chemical structure of the polymer resin. Therefore, the ion-permeable membrane prepared by this invention can meet the application requirements of hemodialysis membranes, glucose sensor films, etc.

[0043] Example 2

[0044] This invention provides a method for preparing a high-flux ion-permeable polymer resin, comprising the following specific steps:

[0045] (1) 7.1 parts by weight of lauryl methacrylate (LMA), 29.8 parts by weight of 4-vinylpyridine (4VP), 1.0 part by weight of polyethylene glycol monomethyl ether methacrylate (molecular weight 300) (PEGMA), and 32.0 parts by weight of tetrahydrofuran (THF) were mixed. Then, 0.06 parts by weight of azobisisobutyronitrile were added. The system was degassed with argon gas to remove residual air. The reaction flask was sealed and the polymerization reaction was initiated at 60°C with a stirring speed of 500 rpm. As the reaction proceeded, the viscosity of the reaction system gradually increased until the stirring of the tetrahydrofuran solution stopped, at which point the reaction was stopped. The reaction product was dissolved and diluted with 500 parts by weight of methanol, and then precipitated in water to obtain a white solid product. The precipitated white solid product was cut into small pieces with scissors, soaked in pure water, washed, and vacuum dried to obtain the polymer intermediate PLMA. 72 -P4VP 720 -PPEGMA8;

[0046] (2) PLMA-P4VP-PPEGMA, 1,3-propanesulfonic acid lactone, and THF were mixed evenly in a mass ratio of 10:0.1:10 and placed in a single-necked round-bottom flask. The mixture was reacted at 90°C for 12 hours. After the reaction was completed, the mixture was precipitated with diethyl ether to remove the solvent, resulting in a white solid product. This solid product was then dissolved again in methanol and precipitated in pure water. The solid product was soaked in pure water overnight, washed three times, and then vacuum dried at 50°C to remove residual solvent and water, yielding the final product PLMA. 72 -P4VP 720 -PPEGMA8-(SO3) 80 The number-average molecular weight of the resin was 84,000 and the dispersibility index was 1.9, as determined by DMF phase gel permeation chromatography.

[0047] Figure 3 The accurate characterization of the chemical structure of the polymer resin in this embodiment by the proton nuclear magnetic resonance spectrum indicates that the synthesis was successful.

[0048] Example 3

[0049] This invention provides a method for preparing a high-flux ion-permeable polymer resin, comprising the following specific steps:

[0050] (1) Mix 4.3 parts by mass of styrene (St), 43.9 parts by mass of 4-vinylpyridine (4VP), 0.6 parts by mass of hydroxyethyl acrylate (HEA), and 500 parts by mass of water. Then add 0.15 parts by mass of potassium persulfate and mix evenly by high-speed stirring (1000 rpm) to emulsify the monomer in water. Degas the system with argon gas to remove residual air. Immediately add 0.06 parts by mass of N,N,N',N'-tetramethylethylenediamine and seal the reaction flask. Initiate the polymerization reaction at room temperature. The reaction product gradually precipitates out until the amount of precipitate no longer increases, and then stop the reaction. Rinse the above polymer product with water, wash the solid product with a large amount of deionized water, cut the white solid product into small pieces with scissors, soak, wash, and vacuum dry in pure water to obtain the polymer intermediate PSt-P4VP-PHEA.

[0051] (2) The mixture of PSt-P4VP-PHEA, 1,3-propanesulfonic acid lactone, and THF was prepared in a mass ratio of 10:0.1:10 and placed in a single-necked round-bottom flask. The mixture was reacted at 90°C for 24 hours. After the reaction was completed, the mixture was precipitated with diethyl ether and the solvent diethyl ether was removed to obtain a white solid product. The solid product was then dissolved in methanol and precipitated in pure water. The solid product was soaked in pure water overnight, washed three times, and then vacuum dried at 50°C to remove residual solvent and water, yielding the final product PSt. 72 -P4VP 720 -PHEA8-(SO3) 80According to DMF phase gel permeation chromatography, the number average molecular weight of the resin is 36,000 and the dispersibility index is 2.0.

[0052] Example 4

[0053] (1) 2.9 parts by weight of styrene (St), 30.0 parts by weight of 4-vinylpyridine (4VP), 0.9 parts by weight of polyethylene glycol monomethyl ether methacrylate (molecular weight 300) (PEGMA), and 30.1 parts by weight of tetrahydrofuran were mixed. Then, 0.12 parts by weight of azobisisobutyronitrile were added. The system was degassed with argon gas to remove residual air. The reaction flask was sealed and the polymerization reaction was initiated at 70°C with a stirring speed of 500 rpm. As the reaction proceeded, the viscosity of the reaction system gradually increased until the stirring of the tetrahydrofuran solution stopped, at which point the reaction was stopped. The reaction product was dissolved and diluted with 300 parts by weight of methanol, and then precipitated in water to obtain a white solid product. The precipitated white solid product was cut into small pieces with scissors, soaked in pure water, washed, and vacuum dried to obtain the polymer intermediate PSt. 36 -P4VP 360 -PPEGMA4;

[0054] (2) PSt-P4VP-PPEGMA, 2-ethoxy-1,3,2-dioxophosphazenecyclopentane-2-oxide, and THF were mixed evenly in a mass ratio of 10:1:10 and placed in a single-necked round-bottom flask. The mixture was reacted at 90°C for 12 hours. After the reaction was completed, the mixture was precipitated with diethyl ether and the solvent diethyl ether was removed to obtain a white solid product. The solid product was then dissolved again in methanol and precipitated in pure water. The solid product was soaked in pure water overnight, washed three times, and then vacuum dried at 50°C to remove residual solvent and water, yielding the final product PSt. 72 -P4VP 720 -PPEGMA8-(PO4) 80 According to DMF phase gel permeation chromatography, the number average molecular weight of the resin is 158,900 and the dispersibility index is 1.5.

[0055] The various embodiments are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. Similar or identical parts between the various embodiments can be referred to each other.

[0056] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. The application of a high-flux ion-permeable polymer resin in the preparation of thin films, characterized in that, The film has high ion permeability; The preparation method of the high-flux ion-permeable polymer resin includes the following specific steps: (1) Using hydrophobic monomers, functional monomers and hydrophilic monomers as raw materials, a polymerization reaction is carried out after adding an initiator to obtain a polymer intermediate; the mass ratio of the hydrophobic monomer, functional monomer, hydrophilic monomer and initiator is 2.8-9.5:29.8-98.6:0.6-3.0:0.06-0.20; the hydrophobic monomer includes styrene or lauryl methacrylate; the functional monomer includes 4-vinylpyridine; the hydrophilic monomer includes polyethylene glycol monomethyl ether methacrylate or hydroxyethyl acrylate; (2) A high-flux ion-permeable polymer resin can be obtained by reacting the polymer intermediate and the lactone; the mass ratio of the polymer intermediate to the lactone is 10:0.1-1, and the lactone includes sulfonyl lactone or phospholipid lactone.

2. The application according to claim 1, characterized in that, The polymerization reaction in step (1) is divided into thermally initiated polymerization and redox initiated polymerization. The conditions for thermally initiated polymerization are: reaction at 60-70℃ for 6-24h, and the conditions for redox initiated polymerization are: reaction at room temperature for 6-24h.

3. The application according to claim 1, characterized in that, The initiator mentioned in step (1) is an azo thermal initiator or a redox initiator, wherein the azo thermal initiator includes azobisisobutyronitrile or azobisisovalerate, and the redox initiator is a combination of potassium persulfate (KPS) and N,N,N',N'-tetramethylethylenediamine (TEMED), and the mass ratio of KPS to TEMED is 0.10-1.35:0.06-0.

86.

4. The application according to claim 1, characterized in that, The polymerization reaction in step (1) also includes a solvent, wherein the solvent is tetrahydrofuran, and the mass ratio of the solvent to the hydrophobic monomer is 31.0-74.1:2.8-9.5; The polymerization reaction also includes, after the reaction is completed, the precipitate is subjected to recrystallization, washing and drying to obtain the polymer intermediate.

5. The application according to claim 1, characterized in that, The reaction conditions described in step (2) are: react at 60-110℃ for 3-24 hours.

6. The application according to claim 1, characterized in that, The reaction in step (2) also includes a solvent, which is tetrahydrofuran or water, with a mass ratio of tetrahydrofuran to polymer intermediate of 5-15:6-20, and a mass ratio of water to polymer intermediate of 200-1000:6-20. The reaction also includes, after the reaction is completed, the precipitate is subjected to recrystallization, washing and drying to obtain the high-flux ion-permeable polymer resin.

7. The application according to claim 1, characterized in that, The membrane includes a hemodialysis membrane or an insulin sensing membrane.

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