High-flux ion-permeable polymer resin, preparation method thereof and application of high-flux ion-permeable polymer resin in thin film

Abstract

The invention discloses high-flux ion-permeable polymer resin, and belongs to the technical field of high-molecular compound synthesis, a preparation method of a polymer comprises the following specific steps: (1) taking a hydrophobic monomer, a functional monomer and a hydrophilic monomer as raw materials, adding an initiator, and carrying out polymerization reaction to obtain a polymer intermediate; and (2) reacting the polymer intermediate with lactone to obtain the high-flux ion-permeable polymer resin. By adopting a strategy of combining hydrophilic and hydrophobic chain segments and zwitterions, a vinyl polymer is prepared through thermal initiation or redox initiation, the film-forming stability of the polymer in a water system is regulated and controlled by controlling the proportion of hydrophilic and hydrophobic monomers, and the modification rate of side-chain zwitterions is regulated and controlled by regulating and controlling the feeding amount of lactone, so that the film-forming stability of the polymer in the water system is improved. Therefore, the ion transmittance can be adjusted.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer compound synthesis, and in particular relates to a high-flux ion permeation polymer resin and a preparation method thereof and application in a film. Background Art

[0002] Bottlebrush polymer (BBP) is a type of comb-shaped polymer with a unique topological structure. The main chain is connected to a sufficiently high density of side chains, which increases the rigidity of the main chain and fully extends the side chains. Functional BBP has a wide range of application value in ultra-soft elastomers, optical crystals, biomimetic lubrication, drug carriers, antifouling coatings and smart materials.

[0003] There are three main strategies for the synthesis of BBP: "grafting to", "grafting from" and "grafting through". Among them, "grafting through" can ensure that each monomer unit on the main chain has side chain modification and 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 the advantages of rich functions and good biocompatibility. Such BBPs are very suitable for use as nano-drug carriers, biomimetic soft tissues, etc.; the synthesis of such BBPs using the "grafting from" method requires the selection of a suitable skeleton structure as the main chain, and then the modification of the amino initiation site. The synthesis steps are complicated, and the synthesis process cannot guarantee that each initiation site can initiate the ring-opening polymerization of the NCA monomer, and the side chain grafting density is uncontrollable; the "grafting to" method cannot guarantee 100% side chain modification, and usually requires a very efficient coupling reaction.

[0004] To this end, it is an urgent problem for those skilled in the art to provide a new polymer and a method for synthesizing the same, which can ensure that each monomer unit of the main chain is modified with a side chain polyamino acid while also controlling the side chain density, length and polypeptide type. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a high-flux ion permeation polymer resin and a preparation method thereof and an application in a film. The present invention synthesizes a random copolymer whose main chain contains a hydrophobic monomer, a functional monomer and a hydrophilic monomer through a free radical polymerization reaction, adjusts the feeding ratio of the monomer and the initiator, adjusts the polymerization degree of the polymerization reaction, and makes the number average molecular weight of the polymerization product reach more than 50,000, thereby improving the stability of the resin in the aqueous phase and meeting the use requirements; at the same time, through a nucleophilic substitution reaction or a ring-opening reaction on the pyridine nitrogen atom, an ionic group (sulfonate-SO 3- , phosphate-PO 4- The presence of hydrophobic monomer units can ensure the stability of the resin in the aqueous phase, while the hydrophilic monomer units help to improve the permeability of ions. By adjusting the ratio of monomer units and the content of ionic group modification, the resin film can achieve high-flux ion permeability.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

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

[0008] (1) using a hydrophobic monomer, a functional monomer and a hydrophilic monomer as raw materials, adding an initiator and conducting a polymerization reaction to obtain a polymer intermediate;

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

[0010] The vinyl polymer resin obtained by traditional free radical polymerization has poor biocompatibility in vivo and is difficult to biodegrade. The vinyl polymer modified by the side chain ionic group of the present invention has the advantages of good hydrophilicity, good biocompatibility and high ion permeability. The present invention can improve the biocompatibility of the vinyl polymer and enrich the function of the vinyl polymer by modifying the zwitterionic group or the hydrophilic group by nucleophilic ring opening or substitution reaction on the pyridine nitrogen; and the lactone is easily attacked by the nucleophilic nitrogen atom of the pyridine, thereby generating a ring opening reaction and introducing zwitterions on the main chain of the polymer. The zwitterions can stably exist in vivo or in a pure water environment; the reaction efficiency is close to 100%, and the modification rate of the side chain ionic group can be adjusted by controlling the feed ratio of the lactone.

[0011] Preferably, the mass ratio of the hydrophobic monomer, the functional monomer, the hydrophilic monomer and the 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, wherein the conditions for the thermally initiated polymerization are: reacting at 60-70° C. for 6-24 hours, and the conditions for the redox initiated polymerization are: reacting at room temperature for 6-24 hours.

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

[0014] The functional monomer includes 4-vinylpyridine;

[0015] The hydrophilic monomer includes 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 azobisisovaleronitrile, and the redox initiator is a combination of potassium persulfate KPS and N,N,N',N'-tetramethylethylenediamine TEMED, and the mass ratio of the KPS to the TEMED is 0.10-1.35:0.06-0.86.

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

[0018] The polymerization reaction further comprises re-precipitating, washing and drying the precipitate after the reaction is completed 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° C. for 3-24 hours.

[0021] The method for preparing a high-flux ion permeation polymer resin according to claim 1, characterized in that the lactone in step (2) comprises sultone or phosphorus lactone.

[0022] Preferably, the sultone is 1,3-propane sultone, and the phosphorus lactone is 2-ethoxy-1,3,2-dioxaphospholane-2-oxide.

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

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

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

[0026] A high flux ion permeation polymer resin is obtained by the preparation method as described above.

[0027] The application of a high flux ion permeable polymer resin obtained by the preparation method as described above in the preparation of a film.

[0028] Preferably, the film includes a hemodialysis membrane or an insulin sensor membrane.

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

[0030] The present invention adopts a strategy of combining hydrophilic and hydrophobic segments with zwitterions, prepares a vinyl polymer through thermal initiation or redox initiation, controls the ratio of hydrophilic and hydrophobic monomers, regulates the stability of polymer film formation in a water system, and regulates the modification rate of side chain zwitterions by regulating the feed amount of lactone, thereby regulating the ion permeability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0032] Figure 1 Schematic diagram of the synthetic route of the polymer resin of the present invention;

[0033] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the polymer resin of Example 1 of the present invention;

[0034] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the polymer resin of Example 2 of the present invention;

[0035] Figure 4 This is a graph showing the transmittance of different ions of different sulfonate-modified polymer membranes in Example 1 of the present invention. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Example 1

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

[0039] (1) 9.5 parts by mass of styrene (St), 98.6 parts by mass of 4-vinylpyridine (4VP), 3.0 parts by mass of polyethylene glycol monomethyl ether methacrylate (molecular weight 300) (PEGMA), and 74.1 parts by mass of tetrahydrofuran were mixed, and then 0.21 parts by mass of azobisisobutyronitrile was added, and the residual air in the system was removed by degassing with argon gas. The reaction bottle was sealed, and a 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, and the reaction was stopped; 500 parts by mass of methanol was added to the reaction product to dissolve and dilute it, and then a white solid product was precipitated in water. The precipitated white solid product was cut into small pieces with scissors, immersed in pure water, washed, and vacuum dried to obtain a polymer intermediate PSt 72 -P4VP 720 -PPEGMA8;

[0040] (2) PSt-P4VP-PPEGMA, 1,3-propane sultone and THF were mixed evenly in a mass ratio of 10:1:10, placed in a single-mouth round-bottom flask, and reacted at 90°C for 12 hours; after the reaction was completed, ether was used for precipitation and the solvent ether was removed to obtain a white solid product, which was then dissolved in methanol again 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 moisture to obtain the final product PSt 72 -P4VP 720 -PPEGMA8-(SO3) 80 , the number average molecular weight of the resin was 65000 and the dispersity index was 1.7 as tested by DMF phase gel permeation chromatography;

[0041] (3) According to PSt 72 -P4VP 720 -PPEGMA8-(SO3) 80and THF in a mass ratio of 0.01:9, the polymer concentration is 1 mg / mL, poured into a polytetrafluoroethylene rectangular mold, and after the solvent evaporates completely, placed in a 60°C constant temperature and humidity chamber for heat treatment for 24 hours to remove residual tetrahydrofuran, and after cooling to room temperature, peeled off from the polytetrafluoroethylene plate to obtain an ion permeable membrane;

[0042] Test the ion permeability of the membrane in aqueous solution with different ions (Na + ,K + ,Ca + Mg + ) and compared it with the ion permeability of the polymer membrane without sulfonate modification. Figure 4 , wherein (a) is a bar graph of different ion pass rates, and (b) is a bar graph of different ion pass rate ratios. It can be seen from the figure that the ion permeable membrane prepared by the present invention has a good pass rate for different ions. Further, the sulfonate-modified ion permeable membrane prepared by the present invention has a better ion permeability for different ions than the ion permeability of the polymer membrane without sulfonate modification; and Figure 2 The nuclear magnetic resonance hydrogen spectrum accurately characterizes the chemical structure of the polymer resin, so the ion permeable membrane prepared by the present invention can meet the use requirements of hemodialysis membranes, glucose sensor films, etc.

[0043] Example 2

[0044] The present 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 parts by weight of polyethylene glycol monomethyl ether methacrylate (molecular weight 300) (PEGMA) and 32.0 parts by weight of tetrahydrofuran (THF) were mixed, and then 0.06 parts by weight of azobisisobutyronitrile was added, and the residual air in the system was removed by degassing with argon. The reaction bottle was sealed, and a 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, and the reaction was stopped; 500 parts by weight of methanol was added to the reaction product to dissolve and dilute it, and then a white solid product was precipitated in water. The precipitated white solid product was cut into small pieces with scissors, and then immersed in pure water, washed, and vacuum dried to obtain a polymer intermediate PLMA 72 -P4VP 720 -PPEGMA8;

[0046] (2) PLMA-P4VP-PPEGMA, 1,3-propane sultone and THF were mixed evenly in a mass ratio of 10:0.1:10, placed in a single-mouth round-bottom flask, and reacted at 90°C for 12 hours; after the reaction was completed, ether was used for precipitation and the solvent ether was removed to obtain a white solid product, which was then dissolved in methanol again 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 moisture to obtain the final product PLMA 72 -P4VP 720 -PPEGMA8-(SO3) 80 , through DMF phase gel permeation chromatography test, the number average molecular weight of the resin is 84000, and the dispersity index is 1.9;

[0047] Figure 3 The hydrogen nuclear magnetic resonance spectrum accurately characterized the chemical structure of the polymer resin in this example, indicating that the synthesis was successful.

[0048] Example 3

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

[0050] (1) 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 are mixed, and then 0.15 parts by mass of potassium persulfate are added, and the mixture is stirred at high speed (1000 rpm) to be uniformly mixed so that the monomers are emulsified in water, and the residual air in the system is removed by degassing with argon gas, and 0.06 parts by mass of N,N,N',N'-tetramethylethylenediamine is immediately added and the reaction bottle is sealed, and a polymerization reaction is initiated at room temperature, and the reaction product gradually precipitates out until the amount of precipitation no longer increases, and the reaction is stopped; the aqueous solution of the above polymer product is removed, the solid product is rinsed with a large amount of deionized water, and the white solid product is cut into small pieces with scissors, immersed in pure water, washed, and vacuum dried to obtain a polymer intermediate PSt-P4VP-PHEA;

[0051] (2) PSt-P4VP-PHEA, 1,3-propane sultone and THF were mixed evenly in a mass ratio of 10:0.1:10, placed in a single-mouth round-bottom flask, and reacted at 90°C for 24 hours; after the reaction was completed, ether was used for precipitation and the solvent ether was removed to obtain a white solid product, which was then dissolved in methanol again 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 moisture to obtain the final product PSt 72 -P4VP 720 -PHEA8-(SO3) 80, through DMF phase gel permeation chromatography test, the number average molecular weight of the resin is 36000 and the dispersity index is 2.0.

[0052] Example 4

[0053] (1) 2.9 parts by mass of styrene (St), 30.0 parts by mass of 4-vinylpyridine (4VP), 0.9 parts by mass of polyethylene glycol monomethyl ether methacrylate (molecular weight 300) (PEGMA) and 30.1 parts by mass of tetrahydrofuran were mixed, and then 0.12 parts by mass of azobisisobutyronitrile was added, and the residual air in the system was removed by degassing with argon gas. The reaction bottle was sealed, and a 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, and the reaction was stopped; 300 parts by mass of methanol was added to the reaction product to dissolve and dilute it, and then a white solid product was precipitated in water. The precipitated white solid product was cut into small pieces with scissors, immersed in pure water, washed, and vacuum dried to obtain a polymer intermediate PSt 36 -P4VP 360 -PPEGMA4;

[0054] (2) PSt-P4VP-PPEGMA, 2-ethoxy-1,3,2-dioxaphospholane-2-oxide and THF were mixed uniformly in a mass ratio of 10:1:10, placed in a single-mouth round-bottom flask, and reacted at 90° C. for 12 hours; after the reaction was completed, ether was used for precipitation and the solvent ether was removed to obtain a white solid product, which was then dissolved in methanol again 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 moisture to obtain the final product PSt 72 -P4VP 720 -PPEGMA8-(PO4) 80 , tested by DMF phase gel permeation chromatography, the number average molecular weight of the resin is 158900 and the dispersity index is 1.5.

[0055] The various embodiments are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to in detail.

[0056] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be 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 present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a high-flux ion permeable polymer resin, characterized in that: The specific steps include: (1) using a hydrophobic monomer, a functional monomer and a hydrophilic monomer as raw materials, adding an initiator and conducting a polymerization reaction to obtain a polymer intermediate; (2) After the polymer intermediate is reacted with lactone, a high-flux ion-permeable polymer resin can be obtained.

2. The method for preparing a high flux ion permeable polymer resin according to claim 1, characterized in that: The mass ratio of the hydrophobic monomer, the functional monomer, the hydrophilic monomer and the initiator in step (1) is 2.8-9.5:29.8-98.6:0-3.0:0.06-0.20; The polymerization reaction is divided into thermally initiated polymerization and redox initiated polymerization, wherein the conditions for the thermally initiated polymerization are: reacting at 60-70° C. for 6-24 hours, and the conditions for the redox initiated polymerization are: reacting at room temperature for 6-24 hours.

3. The method for preparing a high-flux ion permeable polymer resin according to claim 1, characterized in that: The hydrophobic monomer in step (1) includes styrene or lauryl methacrylate; The functional monomer includes 4-vinylpyridine; The hydrophilic monomer includes polyethylene glycol monomethyl ether methacrylate or hydroxyethyl acrylate; The initiator is an azo thermal initiator or a redox initiator, wherein the azo thermal initiator includes azobisisobutyronitrile or azobisisovaleronitrile, and the redox initiator is a combination of potassium persulfate KPS and N,N,N',N'-tetramethylethylenediamine TEMED, and the mass ratio of the KPS to the TEMED is 0.10-1.35:0.06-0.

86.

4. The method for preparing a high-flux ion permeable polymer resin according to claim 1, characterized in that: The polymerization reaction in step (1) further comprises 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 further comprises re-precipitating, washing and drying the precipitate after the reaction is completed to obtain the polymer intermediate.

5. The method for preparing a high flux ion permeation polymer resin according to claim 1, characterized in that: The mass ratio of the polymer intermediate to the lactone in step (2) is 10:0-1; The reaction conditions are: reacting at 60-110° C. for 3-24 hours.

6. The method for preparing a high flux ion permeable polymer resin according to claim 1, characterized in that: The lactone in step (2) includes sultone or phosphorus lactone.

7. The method for preparing a high flux ion permeable polymer resin according to claim 1, characterized in that: The reaction in step (2) further comprises a solvent, wherein the solvent is tetrahydrofuran or water, the mass ratio of the tetrahydrofuran to the polymer intermediate is 5-15:6-20, and the mass ratio of the water to the polymer intermediate is 200-1000:6-20; The reaction also includes re-precipitating, washing and drying the precipitate after the reaction is completed to obtain the high-flux ion permeation polymer resin.

8. A high flux ion permeation polymer resin obtained by the preparation method according to any one of claims 1 to 7.

9. Use of a high flux ion permeation polymer resin obtained by the preparation method according to any one of claims 1 to 7 in the preparation of a film.

10. The use according to claim 9, characterized in that: The film includes a hemodialysis membrane or an insulin sensor membrane.

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