Polarized polyurethanes with phosphonium zwitterions on side chains and their electric field assisted preparation

Abstract

This invention provides a polarized polyurethane with phosphonium zwitterions on its side chains and its electric field-assisted preparation method. Specifically, a novel phosphonium zwitterionic polyol is used as a functional polyol, which is then mixed with a polymer polyol in a solvent. Under the action of a catalyst, it undergoes a stepwise addition polymerization reaction with a polyisocyanate, or after chain extension and end-capping with a chain extender, the mixture is cooled, undergoes phase transition precipitation, washes, and dries under the induction and assistance of an external electric field to prepare an oriented polarized polyurethane with phosphonium zwitterions on its side chains. The oriented polarized polyurethane with phosphonium zwitterions on its side chains has hydrophilic and water-absorbing properties, antibacterial and bacteriostatic functions, as well as photoelectric and pH-responsive functions.

Description

Technical Field

[0001] This invention relates to a photoelectric functional polyurethane and its preparation method, and particularly to a polarized polyurethane with phosphine ammonium zwitterions on its side chains and its electric field-assisted preparation method, belonging to the field of functional polymer materials. Background Technology

[0002] With the advancement of science and technology and the needs of social development, many types of functional polymer materials have emerged. Among them, zwitterionic polymers are a class of polymers whose polymer chains simultaneously contain both anionic and cationic groups, and whose total positive and negative charges are equal in the overall polymer material. Current research results indicate that zwitterionic polymers possess excellent properties such as multi-response characteristics (photoelectric, electromagnetic, and thermal), high thermal stability, high chemical stability, good biocompatibility, and resistance to biofouling. They have been widely used in fields such as artificial tissue sensors, capacitors, polymer electrolytes, membranes or membrane separation materials, antibacterial and antifouling coatings, anticoagulant materials, biomedical diagnostic materials, drug delivery carriers, and gene delivery carriers.

[0003] Professionals are well aware that zwitterionic polymers are primarily classified based on the types of anions and cations they contain. The cations in zwitterionic polymers include quaternary ammonium cations, quaternary phosphonium cations, and sulfonium cations, with quaternary ammonium cations being the most common. The anions in zwitterionic polymers include carboxylate anions, sulfonate anions, phosphate anions, and phosphonate anions, with phosphonate anions being the least common. Another classification method for zwitterionic polymers is based on the linkage pattern of the anion and cation groups in their polymer chains. This is because different linkage patterns of anion and cation groups on zwitterionic polymer chains significantly affect their photoelectric response characteristics, as well as the polymer chain stacking structure, polymer condensation state and macroscopic morphology, as well as their biological activity and application areas. Specifically, in zwitterionic polymers, the anionic and cationic groups can be: ① simultaneously distributed on the main chain, such as in natural phospholipids, but this is rare, and chemically synthesized varieties are also uncommon; ② the main chain is connected to one ionic group, while its counterionic group is connected to the side chain of the polymer, and chemically synthesized varieties are more common; or ③ both anionic and cationic groups in the polymer are connected to its side chain, which is rare in natural varieties, but most common in chemically synthesized varieties.

[0004] Polyurethanes (PUs) are a general term for a class of polymers whose main chain contains repeating urethane (-NHCOO-) units. They are typically produced by the addition polymerization of polyols or polymeric polyols with polyisocyanates, and are typical block copolymers. Products come in a variety of forms, including polyurethane elastomers, polyurethane fibers, polyurethane foams, polyurethane films, polyurethane coatings, polyurethane adhesives, polyurethane hydrogels, and polyurethane prepolymers. Compared with other polymeric materials, polyurethane materials have advantages such as easy molecular structure design, controllable performance, good processability, diverse processing methods, excellent mechanical properties, diverse product types, and wide application fields. In the polyurethane molecular chain structure, the long-chain components of polymeric polyols, such as polyether polyols, polyester polyols, polyolefin polyols, vegetable oil polyols, or silane polyols, possess good flexibility and elasticity, giving polyurethane rubbery or viscous fluid properties at room temperature. These are called the soft segment components of polyurethane. These soft segment components are the material basis for the good elasticity and low-temperature performance of polyurethane. In contrast to the soft segments, certain rigid-core polyisocyanates, such as toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, or triphenylmethane triisocyanate, exhibit strong polarity after addition polymerization with polymeric polyols, resulting in the -NHCOO- group. This leads to mutual attraction through short-range hydrogen bonding or an ordered π-π close-packing of aromatic nuclei, forming the rigid hard segment component of polyurethane. The hard segment component contributes to the high glass transition temperature and melting point of polyurethane. The soft and hard segments in polyurethane do not exist in isolation but are linked together by chemical bonds, forming an alternating block copolymer structure. This structure allows the soft and hard segments to complement and synergistically enhance each other's properties, jointly determining the overall performance of the polyurethane. Therefore, it is clear that understanding the properties of the soft and hard segments of polyurethane and their interrelationships at the molecular level is crucial for the design and development of novel polyurethane materials.

[0005] Functional modification of polyurethane, while maintaining its excellent properties, endows it with unique biological, photoelectric, electromagnetic, thermal, and other physical or chemical properties, and has become a major method for expanding the variety and application fields of polyurethane materials. Common polyurethane functionalization methods include blending modification, chemical copolymerization, interpenetrating polymer networks, and surface modification. Among these, bonding or compounding functional materials with polyurethane materials at the molecular level through bonding not only fully utilizes the properties of each component but also features uniform distribution, material stability, and synergistic performance. Therefore, researchers are well aware of the ongoing research into introducing cations, such as ammonium, sulfonium, and phosphonium cations, into the main chain or side chain structure of polyurethane; or introducing anions, such as sulfonic acid or carboxyl groups; or simultaneously introducing zwitterions to impart hydrophilicity, ion exchange function, and antibacterial function. In currently available literature, the raw materials used for functionalizing polyurethanes are mainly small-molecule N-methyldiethanolamine, dimethylolpropionic acid, ethylenediamine ethanesulfonic acid, mercaptoethanol, hydroxyethyliminooxalic acid, 3-(N-methyl-N,N-diethanolammonium)-propanesulfonic acid inner salt, and 3-(N,N,N-triethanolammonium)-propanesulfonic acid inner salt. Furthermore, the functionalization of polyurethanes is primarily achieved by end-capping or chain extension of the polyurethane prepolymer, introducing anions, cations, or ligands into the polyurethane material. This results in limitations and constraints in existing polyurethane functionalization modifications. Therefore, in the past decade or so, attention has shifted to the research and development of polymer polyol functionalization. Professionals are well aware of the high design freedom of polymer polyol molecules, leading to the development of functional polyols such as cationic polymer polyols, vegetable oil polyols, phosphorus-containing flame-retardant polyols, and organosilicon polyols for the preparation of functional polyurethanes.For example: CN02815856.3; CN03122339.7; CN201210125277.8; ZL2020112318383; Absorption by Polyurethane Foams: New Method of Separation, J. Chem. SOC. (A), (1970)1803-1805; Polymeric and immobilizedcrown compound materials for ion separation, Tetrahedron, 53 (1997) 1343-1360; Click-ligation of coumarin to polyether polyols for polyurethane foams, Polym. Int., 62 (2013) 783–790; Detection of uranium with a wireless sensing method by using salophen as receptor and magnetic nanoparticles as signal-amplifyingtags, J. Radioanal. Nucl. Chem., 298 (2013) 1393–1399; Polyurethane-based cation exchange composite membranes: Preparation, characterization and its application in development of ion-selective electrode for detection of copper(II), J. Ind. Eng. Chem., 29 (2015) 392–399; Design and performance of polyurethane-based deep eutectic gel electrolyte for lithium metal batteries, Huazhong University of Science and Technology, dissertation, 2023, etc., have been well received by the market.

[0006] Based on the specific examples of polyurethane functionalization described above, it can be seen that zwitterionic polyurethanes are most commonly made from: (1) polyols containing anions / cations paired with polyisocyanates containing cations / anions, which have not been reported or disclosed; (2) polyols containing both anions and cations paired with polyisocyanates, which have been reported or disclosed; and (3) polyols containing both anions and cations, or polyols containing both anions and cations, and polyisocyanates, which have been reported or disclosed. More specifically, zwitterionic polyurethanes with quaternary ammonium cations in the main chain and anionic groups attached to the side chains, as well as zwitterionic polyurethanes with quaternary ammonium cations + carboxyl anions, or quaternary ammonium cations + sulfonic acid anions in series on the side chains, are most common. However, zwitterionic polyurethanes with parallel anions and cations on one side chain are rarely reported or disclosed, or zwitterionic polyurethanes with anionic groups + cationic groups in series on their side chains have not been reported or disclosed. In view of this, based on a detailed study and summary of existing zwitterionic polyurethane varieties, as well as the varieties, chemical structures, properties, and application results of zwitterionic groups, and in accordance with molecular design principles and modern chemical preparation methods and technologies, the inventors proposed to design and synthesize a novel phosphonium ammonium zwitterionic polyol as one of the main raw materials, compounded with polymer polyol, and then reacted with polyisocyanate in a stepwise addition polymerization reaction, using an electric field to assist in the preparation of a novel polarized polyurethane material. Summary of the Invention

[0007] Specifically, in order to further expand the variety of functional polyurethane materials, the inventors used a novel phosphonium zwitterionic polyol as the functional polyol, and then mixed it with a polymer polyol in a solvent. Under the action of a catalyst, the polyol underwent a stepwise addition polymerization reaction with a polyisocyanate, or after chain extension and end-capping with a chain extender, the polyol was cooled, precipitated by phase change, washed, and dried under the induction and assistance of an external electric field to prepare a polarized polyurethane with phosphonium zwitterionic orientation on its side chains. The phosphonium zwitterionic polyol has the structure shown in general formula (Ⅰ).

[0008]

[0009] In general formula (Ⅰ), R1, R2, and R3 are selected from C1 to C1 respectively. 18 hydrocarbon group, Select C1~C 18 The alkylene group, Q is selected from H or OH, Y is selected from OH or OM; M is selected from Na, K or Li.

[0010] Those skilled in the art are well aware that the tertiary amine group in the phosphonium zwitterionic polyol molecule described in this application possesses pH-responsive characteristics and the ability to undergo quaternization reactions with halogenated hydrocarbons. It also acts as a catalyst for the stepwise addition polymerization reaction of the two secondary hydroxyl groups and one tertiary hydroxyl group in the phosphonium zwitterionic polyol molecule with polyisocyanates, and serves as an N-ligand for some heavy metal ions, bimetallic ions, and rare earth metal ions. Furthermore, the quaternary ammonium cation in the macromolecular structure of the phosphonium zwitterionic polyurethane possesses hydrophilic and water-absorbing properties, anion exchange, surfactant, and antibacterial / bacteriostatic functions. Additionally, the quaternary ammonium cation pairs with the phosphonate group in another segment to form two phosphonium betaine (or simply phosphonium zwitterionic) structural units, which is of great significance for improving the antibacterial / bacteriostatic efficacy, biocompatibility, and hydrophilicity of the polyurethane.

[0011] As is well known to those skilled in the art, the phosphonium zwitterionic polyol in this application is an amphoteric molecule with an inherent dipole moment and separated positive and negative charges. However, it is evident that, under electrostatic induction in the middle of an electrostatic field, its own dipole orientation aligns with the direction of the electrostatic field. In solution, its molecular dipole orientation, originally in a disordered state, transforms into a polarized orientation state with its molecular dipole orientation aligned, forming a layer-by-layer isotropic array. Furthermore, the disordered dipole orientation of the phosphonium zwitterionic polyol with an inherent dipole moment in solution is transformed into a polarized orientation through electric field induction, resulting in an ordered layered arrangement. Then, it undergoes in-situ stepwise addition polymerization or crosslinking with polyisocyanates in solution, solidifying this ordered stacking structure with inherent dipole molecular polarization orientation in polyurethane, forming a macroscopically polarized polyurethane material with electroactive characteristics. Alternatively, the phosphonium zwitterionic polyol with an inherent dipole moment and separated positive and negative charges, as described in this application, may be used. In solution, its molecular dipole orientation is initially disordered. It undergoes a stepwise addition polymerization or crosslinking reaction with polyisocyanates in the solution to obtain a polyurethane solution with phosphonium zwitterionic side chains. Then, an electrostatic field is applied to the polyurethane solution with phosphonium zwitterionic side chains, causing the inherent dipole direction to align with the electrostatic field direction, forming a compliantly aligned polarized state. After cooling, adding a poor solvent to induce a phase transition precipitation, separation, washing, and drying, this ordered stacking structure with inherently polarized molecular orientation is solidified in the polyurethane, forming the anisotropic macroscopically polarized polyurethane material described in this invention.

[0012] This invention provides a polarized polyurethane with phosphonium zwitterionic side chains, which is prepared by the following steps: According to the mass ratio of 5-50 parts of phosphonium zwitterionic polyol, 5-50 parts of polymeric polyol, 5-50 parts of polyisocyanate, 0-10 parts of chain extender, 0-1.5 parts of catalyst, and 50-500 parts of organic solvent, the organic solvent, polymeric polyol, catalyst, and phosphonium zwitterionic polyol are weighed into a reaction vessel. Under N2 protection, the mixture is stirred evenly, and then polyisocyanate is added to the reaction vessel. The temperature is controlled at 50-90°C, and the polymerization reaction is carried out for 2-6 hours. Then, the chain extender is added, and the polymerization reaction is continued with stirring for another 2-6 hours. After stirring is stopped, a 1V-10KV electrostatic field is applied to the reaction product system in the reaction vessel for 10-1000 minutes, while simultaneously lowering the temperature of the reaction product system in the reaction vessel to -20°C-25°C. The mixture is then subjected to solvent leaching, separation, washing, and drying to obtain the polarized polyurethane with phosphonium zwitterionic side chains.

[0013] The polarized polyurethane with phosphonium zwitterionic side chains described in this invention can also be prepared by the following staged polymerization process: Solution ①, composed of organic solvent, polymeric polyol, phosphonium zwitterionic polyol, and catalyst, is prepared according to the following mass ratios: 5-50 parts of phosphonium zwitterionic polyol, 5-50 parts of polymeric polyol, 5-50 parts of polyisocyanate, 0-10 parts of chain extender, 0-1.5 parts of catalyst, and 50-500 parts of organic solvent; and solution ②, composed of organic solvent, polymeric polyol, and chain extender; a portion of polyisocyanate is added to solution ①, and the mixture is prepared under N2 protection. The temperature is controlled at 50~90℃, and the reaction is stirred for 2~6 hours to obtain the first-stage polyurethane solution. Solution ② is added to the first-stage polyurethane solution, and after mixing evenly, the remaining amount of polyisocyanate is added. The reaction is continued to be carried out at the temperature and stirred for 2~6 hours to obtain the second-stage polyurethane solution. Stirring is stopped, and an electrostatic field of 1V~10KV is applied to the reaction product system in the reactor for 10~1000 minutes. At the same time, the temperature of the reaction product system in the reactor is lowered to -20℃~room temperature. After leaching with a poor solvent, separation, washing, and drying, polarized polyurethane with phosphine ammonium zwitterions on the side chain is obtained.

[0014] The ratio of the molar number of NCO contained in the polyisocyanate to the sum of the molar numbers of OH contained in the polymer polyol, the phosphonium zwitterionic polyol and the chain extender is controlled within the range of 0.75 to 1.25, preferably 1.00 to 1.05;

[0015] The phosphonium zwitterionic polyol has the structure shown in general formula (Ⅰ):

[0016]

[0017] In general formula (Ⅰ), R1, R2, and R3 are selected from C1 to C1 respectively.18 hydrocarbon group, Select C1~C 18 The alkylene group, Q is selected from H or OH, Y is selected from OH or OM; M is selected from Na, K or Li.

[0018] The polymer polyol refers to one or more of the following: polyether polyol, polyester polyol, polyolefin polyol, vegetable oil polyol, or organosilicon polyol.

[0019] The polyisocyanate refers to one of the following: toluene diisocyanate, diphenylmethane diisocyanate, hexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, and tris(4-phenylisocyanate) thiophosphate.

[0020] The catalyst refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, di(dodecyl sulfide)dibutyltin, or dibutyltin diacetate.

[0021] The chain extender refers to one or more of the following: 1,4-butanediol, trimethylolpropane, diethylene glycol, triethylene glycol, N-alkyldiethanolamine, N-alkylamine polyoxyethylene ether, N,N,Nʹ,Nʹ-tetra(2-hydroxyethyl)ethylenediamine, or dihydroxyalkylamine; wherein the alkyl group refers to C1-C6. 18 Hydrocarbon group.

[0022] The N-alkylamine polyoxyethylene ether has the structure shown in general formula (II):

[0023]

[0024] In general formula (II), R4 is selected from C1 to C2. 18 Hydrocarbon group, R5 is selected from H or methyl, and the sum of p and q is selected from natural numbers from 2 to 200;

[0025] The dihydroxyalkylamine has the structure shown in general formula (III):

[0026]

[0027] In general formula (Ⅲ), R4 is selected from C1 to C2. 18 The hydrocarbon group, R5, is selected from H or methyl.

[0028] The organic solvent refers to one or more of the following: acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, tetrahydrofuran, 1,4-dioxane, chloroform, chlorobenzene, petroleum ether with a boiling range of 60~120℃, hexane, cyclohexane, decahydronaphthalene, N,N-dimethylaniline, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0029] The unsuitable solvents refer to one or more of methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, or water.

[0030] The phosphonium zwitterionic polyol is prepared by the following method: The solvent and aminoalkyl bisphosphonate or aminoalkyl bisphosphonate, glycidyl quaternary ammonium, and solvent are added sequentially to a reaction vessel in a mass ratio of 100:50~500:50~2000. The mixture is stirred and dispersed evenly. An appropriate amount of alkaline or acidic aqueous solution is used to adjust the pH of the material in the reaction vessel to between 7.0 and 8.5. The temperature of the material in the reaction vessel is controlled to -10 to 90°C. A glycidyl quaternary ammonium solution is slowly added to the reaction vessel. After stirring and reacting for 2 to 6 hours, an appropriate amount of alkaline or acidic aqueous solution is used to adjust the pH of the material in the reaction vessel to between 3.5 and 5.5. Then, rotary evaporation is performed to concentrate the solids. The rotary evaporation concentration is then stopped, and the temperature of the material in the reaction vessel is lowered to room temperature. After precipitation, filtration, recrystallization, and drying to constant weight, the phosphonium zwitterionic polyol with the structure shown in general formula (Ⅰ) is obtained.

[0031] The phosphonium zwitterionic polyol described therein has the structure shown in general formula (Ⅰ):

[0032]

[0033] In general formula (Ⅰ), R1, R2, and R3 are selected from C1 to C1 respectively. 18 hydrocarbon group, Select C1~C 18 The alkylene group, Q is selected from H or OH, Y is selected from OH or OM; M is selected from Na, K or Li.

[0034] The aminoalkyl bisphosphonic acid has the structure shown in general formula (V):

[0035] .

[0036] The aminoalkyl bisphosphonate has the structure shown in general formula (V-1) or general formula (V-2):

[0037] .

[0038] The alkyl group in the aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate refers to the alkyl group in general formula (V), general formula (V-1) or general formula (V-2). ,in Select C1~C 18 The alkylene group, Q is selected from H or OH, and M is selected from Na, K or Li.

[0039] The glycidyl quaternary ammonium solution refers to a solution prepared by dissolving the glycidyl quaternary ammonium in a solvent to a mass percentage concentration of 10-60%, wherein the glycidyl quaternary ammonium has the structure shown in general formula (VI):

[0040]

[0041] In the general formula (VI), R1, R2, and R3 are selected from C1 to C1 respectively. 18 hydrocarbon group, X - Select NO3 - Cl - ,Br - SO4 2- One of the following: or p-toluenesulfonate anion.

[0042] The alkaline aqueous solution refers to one of the following: sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, caustic soda aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, or lithium carbonate aqueous solution with a mass percentage concentration of 10-30%.

[0043] The acidic aqueous solution refers to one of the following: nitric acid aqueous solution, hydrogen chloride aqueous solution, hydrogen bromide aqueous solution, sulfuric acid aqueous solution, or p-toluenesulfonic acid aqueous solution with a mass percentage concentration of 10-30%.

[0044] The solvent refers to one or more of the following: water, methanol, ethanol, propanol, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, or hexamethylphosphoramide.

[0045] Compared with the prior art, the advantages of the polarized polyurethane with phosphonium zwitterions on the side chain described in this invention are:

[0046] ①The raw materials for preparing the polarized polyurethane with phosphine ammonium zwitterions on the side chain described in this invention are all commercially available products. The product yield is high in each step of the preparation process, the purification technology is simple and reliable, and the process is simple and easy to implement.

[0047] ② The raw material ratio for preparing the polarized polyurethane with phosphonium ammonium zwitterions on the side chain of the present invention can be adjusted within a wide range. The polarized polyurethane with phosphonium ammonium zwitterions on the side chain can exhibit various product types such as hydrophilic water-absorbing type, water-absorbing swelling type, water-dispersible type, and water-soluble type, and is suitable for electroactive polyurethanes with anisotropic characteristics required in various environments. Detailed Implementation

[0048] To further illustrate the present invention, specific examples are provided to facilitate a better understanding of its content. Therefore, the polarized polyurethanes with phosphine ammonium zwitterions on their side chains and their electric field-assisted preparation methods, not listed in the examples, should not be considered as limitations on the scope of protection of the present invention.

[0049] Example 1: Preparation of bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1)

[0050] 33.0 g of alendronate monosodium trihydrate sold by Anhui Kaichao Biotechnology Co., Ltd. was dispersed in 67 g of deionized water and fed into a reaction vessel. A 18% (w / w) sodium hydroxide aqueous solution was used to adjust the pH of the material in the reaction vessel to between 7.0 and 7.5, and the temperature of the material in the reaction vessel was controlled to 15-20°C. 45 g of a 2:1 mixture of N-glycidyl-N,N,N-trimethylammonium chloride / water was slowly added to the reaction vessel. The mixture was stirred for 2 hours, and the temperature of the material in the reaction vessel was increased to 55-60°C. The stirring continued for 1.5 hours. Then, 30% (w / w) hydrochloric acid was slowly added to adjust the pH of the material in the reaction vessel to 4.5-5.5. The mixture was then concentrated under negative pressure by rotary evaporation until white granules appeared. Concentration was stopped, and the temperature of the material in the reaction vessel was lowered to room temperature. After 24 hours of precipitation, filtration, recrystallization, and drying to constant weight, 54.8 g of a white powder product (Ⅰ-1) was obtained.

[0051] TGA analysis of the white powdery product (Ⅰ-1) showed that: before 125℃, the thermal weight loss was 13.5%, which should be attributed to the loss of water of crystallization; the thermal weight loss was significant near 125℃, with approximately 38.7% between 120 and 250℃, which should be attributed to the thermal decomposition of its quaternary ammonium salt; and approximately 33.3% between 250 and 450℃, which should be attributed to the thermal decomposition loss of organic components in the white powdery product (Ⅰ-1); there was still 14.5% black residue up to 700℃, which should be the black residue of carbon slag and phosphorus oxides produced by the thermal decomposition of the white powdery product (Ⅰ-1). Elemental analysis (%) of the white powdery product (Ⅰ-1): C 40.01, H 7.97, N 8.76, P 12.21, consistent with the designed molecular formula C 16 H 39The calculated values ​​of C 40.17, H 8.01, N 8.78, and P 12.95 for N3O9P2 are basically consistent, indicating that the white powdery product (Ⅰ-1) contains four molecules of water of crystallization. The IR (KBr tablet, cm⁻¹) of the white powdery product (Ⅰ-1) is also consistent with these values. -1 The peaks 3431, 3341, 2928, 2867, 1537, 1434, 1362, 1259, 1109, 1018, and 926 are attributed to the characteristic vibrational absorption peaks of OH, methylCH, methyleneCH, CN, P=O, CO, and PO, respectively. 1 ¹H-NMR (TMS as internal standard, D₂O, ẟ): 1.39 (m, 2H), 1.58 (m, 2H), 2.36–2.65 (m, 6H), 3.27 (s, 18H), 3.54 (m, 4H), 4.09 (m, 2H), 5.09 (m, 3H). Based on the above analytical and characterization results, the white powdery product (Ⅰ-1) is confirmed to possess the structural characteristics of the bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1) shown in formula (Ⅰ-1).

[0052]

[0053] After completing the ring-opening reaction of sodium alendronate with N-glycidyl-N,N,N-trimethylammonium chloride, the pH of the material in the reactor was adjusted to 8.5-9.5. Then, the mixture was concentrated under negative pressure by rotary evaporation until white granules appeared. The concentration was then stopped and the temperature of the material in the reactor was lowered to room temperature. After 24 hours of precipitation, filtration, recrystallization, and drying to constant weight, 60.1 g of white powder product (Ⅰ-2) was obtained.

[0054] TGA analysis of the white powdery product (Ⅰ-2) showed that: before 125℃, the weight loss was 14.1%, which should be attributed to the loss of water of crystallization; the weight loss was significant near 125℃, with approximately 36.4% weight loss between 120 and 250℃, which should be attributed to the thermal decomposition of its quaternary ammonium salt; and approximately 29.2% weight loss between 250 and 450℃, which should be attributed to the thermal decomposition loss of organic components in the white powdery product (Ⅰ-2); there was still 20.3% black residue up to 700℃, which should be the black residue of sodium phosphate and carbon residue produced by the thermal decomposition of the white powdery product (Ⅰ-2). Elemental analysis (%) of the white powdery product (Ⅰ-2): C 35.97, H 6.43, N 8.01, P 11.66, consistent with the designed molecular formula C 16 H 37 The calculated values ​​of C 36.79, H 6.95, N 8.04, and P 11.86 for N3O9P2Na2 are basically consistent, indicating that the white powdery product (Ⅰ-2) contains four molecules of water of crystallization. The IR (KBr tablet, cm⁻¹) of the white powdery product (Ⅰ-2) is also consistent with these values. -1The peaks 3423, 3302, 2932, 2873, 1541, 1437, 1363, 1261, 1106, 1023, and 927 are attributed to the characteristic vibrational absorption peaks of OH, methylCH, methyleneCH, CN, P=O, CO, and PO, respectively. 1 ¹H-NMR (TMS as internal standard, D₂O, ẟ): 1.41 (m, 2H), 1.59 (m, 2H), 2.34–2.67 (m, 6H), 3.28 (s, 18H), 3.55 (m, 4H), 4.08 (m, 2H), 5.02 (m, 3H). Based on the above analytical and characterization results, the white powdery product (Ⅰ-2) is confirmed to possess the structural characteristics of the bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-2) shown in formula (Ⅰ-2).

[0055]

[0056] Example 2 Preparation of bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-3)

[0057] Following the preparation method and procedures of Example 1, alendronate sodium trihydrate was replaced with 6-amino-1-hydroxyhexyl-1,1-bisphosphonic acid, and N-glycidyl-N,N,N-trimethylammonium chloride was replaced with N-glycidyl-N-benzyl-N,N-dimethylammonium chloride, yielding a white powder product (Ⅰ-3). Using analytical characterization methods similar to those in Example 1, it was confirmed that the white powder product (Ⅰ-3) possesses the structural characteristics of the bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-3) shown in formula (Ⅰ-3).

[0058] .

[0059] Example 3 Preparation of bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-4)

[0060] Following the preparation method and procedures of Example 1, N-glycidyl-N,N,N-trimethylammonium chloride was replaced with N-glycidyl-N-benzyl-N,N-diallylammonium chloride to obtain a white powder product (Ⅰ-4). Using analytical characterization methods similar to those in Example 1, it was confirmed that the white powder product (Ⅰ-4) possesses the structural characteristics of the bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-4) shown in Formula (Ⅰ-4):

[0061] .

[0062] Example 4 Preparation of polarized polyurethane (Ⅰ-1) with phosphonium zwitterions on the side chain

[0063] Weigh 8 g of dehydrated N,N-dimethylformamide, 0.06 g of dibutyltin dilaurate, and 1 g of dehydrated bis(hydroxypropyl quaternary ammonium phosphonate) (Ⅰ-1) into a reactor. Under N2 protection, maintain the temperature at 70-80℃ and stir until homogeneous. Add 2 g of toluene diisocyanate to the reactor and stir for 2 hours for addition polymerization. Then add 6 g of dehydrated polyethylene glycol-600 and mix well. Add the remaining 0.75 g of toluene diisocyanate to the reactor and continue stirring for 2 hours for addition polymerization. Finally, add 0.013 g of 1,4-butanediol and continue stirring at the same temperature for further reaction. After 4 hours, the addition polymerization product was slightly diluted with acetone. While still hot, the viscous portion of the addition polymerization product was poured onto the conductive surface of a 2*2cm ITO glass plate. Another ITO glass plate was then placed on top, conductive surface facing down, maintaining a 2.0mm gap between the two plates. The two ITO glass plates were connected to a 6-8V DC power supply until their temperature dropped to around 0℃. After approximately 1.5 hours, the power was cut off, the membrane was removed, and it was washed several times with methanol. It was then placed in a 50-55℃ vacuum drying oven and dried for 24 hours until constant weight was achieved, yielding a polyurethane (Ⅰ-1-a) membrane with phosphonium zwitterions on its side chains. Simultaneously, a polyurethane (Ⅰ-1-b) membrane with phosphonium zwitterions on its side chains without an applied external electric field was also obtained. The TGA curves of the two films (Ⅰ-1-a) and (Ⅰ-1-b) are basically consistent. Analysis shows that: before 190℃, the thermal weight loss is not significant; it becomes obvious around 225℃, slowing down at 300℃, with a weight loss rate of 4.3%, which should be attributed to the thermal decomposition weight loss of quaternary ammonium cations; after 300℃, the thermal weight loss accelerates until 450℃, then slows down again, with a weight loss rate of 85.5%, which should be attributed to the thermal decomposition of the polyurethane macromolecular chain structure; there is still 10.2% black residue up to 700℃, which should be the black carbon residue and phosphate remaining after the thermal decomposition of the polarized polyurethane (Ⅰ-1-a) with phosphonium amphoteric ions on its side chains. (IR(KBr tablet, cm⁻¹) of polarized polyurethane (Ⅰ-1-a) with phosphonium amphoteric ions on its side chains...) -1 The absorption peaks 3431, 3317, 2937, 2863, 1731, 1643, 1538, 1446, 1367, 1261, 1108, 1024, and 927 are attributed to the characteristic vibrational absorption peaks of NH, OH, methylCH, methyleneCH, C=O, C=C, CN, P=O, CO, and PO, respectively. Based on the above analytical and characterization results, the polarized polyurethane (Ⅰ-1-a) with phosphonium zwitterions on its side chains is confirmed to have the schematic structure shown in formula (Ⅰ-1):

[0064]

[0065] At room temperature, 1.0000 g of each of the two membranes, (Ⅰ-1-a) and (Ⅰ-1-b), were immersed in 50 mL of deionized water and shaken for 24 hours. After removal, the surface moisture was wiped off with absorbent paper, and the membranes were quickly weighed to obtain weights of 1.8872 g and 1.3667 g, respectively. The calculated water absorption rates were 88.72% and 36.67%, respectively. This indicates that the surface charge density of the polarized polyurethane (Ⅰ-1-a) with phosphonium zwitterions on its side chains is relatively higher than that of the non-polarized polyurethane (Ⅰ-1-b). It may also be that the ionic groups and the orderly arrangement of the soft and hard molecular chain segments of the polarized polyurethane (Ⅰ-1-a) result in more unobstructed channels for water molecule penetration.

[0066] Cu / (Ⅰ-1-a) membrane or (Ⅰ-1-b) membrane / Cu were stacked to form a battery pack with electrode / zwitterionic polyurethane / electrode. The impedance was measured using an HP4192A precision impedance analyzer under constant humidity conditions of 25±2℃ and 55%. The measured current frequency range was 5Hz~13MHz and the voltage was 1V. The room temperature conductivity of the (Ⅰ-1-a) membrane was 3.75 times that of the (Ⅰ-1-b) membrane.

[0067] Comparative Example 1: Preparation of Polarized Polyurethane (Ⅰ-1-1) with Phosphine Ammonium Zwitterions on its Side Chains

[0068] Following the preparation method and operating steps of Example 4, the 1 gram of bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1), 2 grams of toluene diisocyanate, and 6 grams of polyethylene glycol-600 in Example 4 were replaced with 3 grams of bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1), 2.4 grams of toluene diisocyanate, and 4.3 grams of polyethylene glycol-600, to obtain a polyurethane (Ⅰ-1-1-a) film with phosphonium zwitterions on its side chains and a polyurethane (Ⅰ-1-1-b) film with phosphonium zwitterions on its unpolarized side chains. The infrared spectra of the (Ⅰ-1-1-a) film and the (Ⅰ-1-1-b) film are the same as those of the (Ⅰ-1-1-a) film and the (Ⅰ-1-1-b) film, respectively, and their TGA curves are also basically the same. The difference lies in the water absorption rate: (Ⅰ-1-1-a) membrane has a water absorption rate of 365.4%, while (Ⅰ-1-1-b) membrane has a water absorption rate of 208.6%. At room temperature, the conductivity of (Ⅰ-1-1-a) membrane is 11.43 times that of (Ⅰ-1-1-b) membrane. These results indicate that in polarized polyurethanes with phosphonium zwitterionic side chains, a higher proportion of phosphonium zwitterionic polyols leads to more significant changes in water absorption rate and electric field polarization.

[0069] Example 5 Preparation of polarized polyurethane (Ⅰ-2) with phosphonium zwitterions on the side chain

[0070] Following the preparation method and operating steps of Example 4, bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1) in Example 4 was replaced with bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-2), and polyethylene glycol-600 was replaced with polyethylene glycol-2000, to obtain a polarized polyurethane (Ⅰ-2-a) film with phosphonium zwitterions on its side chains, and a polyurethane (Ⅰ-2-b) film with phosphonium zwitterions on its side chains without electric field polarization. The TGA analysis curves of the (Ⅰ-2-a) film and the (Ⅰ-2-b) film are basically the same as those of the (Ⅰ-1-a) film and the (Ⅰ-1-b) film; their infrared spectra are also basically similar. The difference is that the water absorption rate of the (Ⅰ-2-a) film is 102.5%, and the water absorption rate of the (Ⅰ-2-b) film is 65.8%. At room temperature, the conductivity of membrane (Ⅰ-2-a) is 4.68 times that of membrane (Ⅰ-2-b). These results indicate that, under the same conditions, membrane (Ⅰ-2-a) exhibits significantly higher polarizability and water absorption compared to membrane (Ⅰ-1-a). This suggests that the ionization activity of the sodium phosphonate fragment in membrane (Ⅰ-2-a) is significantly higher than that of the phosphonic acid fragment in membrane (Ⅰ-1-a).

[0071] Example 6 Preparation of polarized polyurethane (Ⅰ-3) with phosphonium zwitterions on the side chain

[0072] Following the preparation method and operating steps of Example 4, the bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1) in Example 4 was replaced with bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-3) to prepare a polarized polyurethane (Ⅰ-3-a) membrane with phosphonium zwitterions on its side chains, and a polyurethane (Ⅰ-3-b) membrane with phosphonium zwitterions on its side chains without electric field polarization. The TGA analysis curves of the (Ⅰ-3-a) and (Ⅰ-3-b) membranes are similar to those of the (Ⅰ-1-a) and (Ⅰ-1-b) membranes; their infrared spectra are also basically similar. The difference is that the water absorption rate of the (Ⅰ-3-a) membrane is 80.5%, and the water absorption rate of the (Ⅰ-3-b) membrane is 35.3%. At room temperature, the conductivity of the (Ⅰ-3-a) membrane is 5.75 times that of the (Ⅰ-3-b) membrane. The results above show that the field-induced polarization of the intrinsic dipole of the (Ⅰ-3-a) membrane is much higher than that of the (Ⅰ-1-a) membrane under the same conditions.

[0073] Example 7 Preparation of polarized polyurethane (Ⅰ-4) with phosphonium zwitterions on the side chain

[0074] Following the preparation method and operating steps of Example 4, the bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-1) in Example 4 was replaced with bis(hydroxypropyl quaternary ammonium phosphonate inner salt) (Ⅰ-4), resulting in a polarized polyurethane (Ⅰ-4-a) membrane with phosphonium zwitterions on its side chains, and a polyurethane (Ⅰ-4-b) membrane with phosphonium zwitterions on its side chains without electric field polarization. The TGA analysis curves of the (Ⅰ-4-a) and (Ⅰ-4-b) membranes are similar to those of the (Ⅰ-1-a) and (Ⅰ-1-b) membranes; their infrared spectra are also basically similar. The difference is that the water absorption rate of the (Ⅰ-4-a) membrane is 73.1%, and that of the (Ⅰ-4-b) membrane is 35.2%. At room temperature, the conductivity of the (Ⅰ-4-a) membrane is 2.03 times that of the (Ⅰ-4-b) membrane. The above results indicate that the polarization reduction of the (Ⅰ-4-a) membrane is more significant than that of the (Ⅰ-1-a) membrane under the same conditions. This may be because the spatial volume of the quaternary ammonium cations in the (Ⅰ-4-a) membrane is increased, making it more difficult for the electric field to induce polarization orientation. The above descriptions are all preferred embodiments of the present invention. For those skilled in the art, any modifications to the present invention in various equivalent forms without departing from the principle of the present invention are within the protection scope of the appended claims.

Claims

1. A polarized polyurethane with phosphonium zwitterionic side chains, which is prepared by the following steps: According to the mass ratio of 5-50 parts of phosphonium zwitterionic polyol, 5-50 parts of polymeric polyol, 5-50 parts of polyisocyanate, 0-10 parts of chain extender, 0-1.5 parts of catalyst, and 50-500 parts of organic solvent, organic solvent, phosphonium zwitterionic polyol, polymeric polyol, and catalyst are weighed into a reaction vessel. Under N2 protection, after stirring evenly, polyisocyanate is added to the reaction vessel. The temperature is controlled at 50-90°C, and the polymerization reaction is carried out for 2-6 hours. Then, the chain extender is added, and the polymerization reaction is continued with stirring for another 2-6 hours. After stirring is stopped, a 1V-10KV electrostatic field is applied to the reaction product system in the reaction vessel for 10-1000 minutes, while the temperature of the reaction product system in the reaction vessel is lowered to -20-25°C. After leaching with a poor solvent, separation, washing, and drying, polarized polyurethane with phosphonium zwitterionic side chains is obtained. The ratio of the molar number of NCO contained in the polyisocyanate to the sum of the molar numbers of OH contained in the polymer polyol, the phosphonium zwitterionic polyol and the chain extender is controlled within the range of 0.75 to 1.

25. The phosphonium zwitterionic polyol has the structure shown in general formula (Ⅰ): ； In general formula (Ⅰ), R1, R2, and R3 are selected from C1 to C1 respectively. 18 hydrocarbon group, Select C1~C 18 The alkylene group, Q is selected from H or OH, Y is selected from OH or OM; where M is selected from Na, K or Li. The polymer polyol refers to one or more of the following: polyether polyol, polyester polyol, polyolefin polyol, vegetable oil polyol, or organosilicon polyol. The polyisocyanate refers to one of the following: toluene diisocyanate, diphenylmethane diisocyanate, hexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, and tris(4-phenylisocyanate) thiophosphate. The catalyst refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, di(dodecyl sulfide)dibutyltin or dibutyltin diacetate; The chain extender refers to one or more of 1,4-butanediol, trimethylolpropane, diethylene glycol, triethylene glycol, N-alkyldiethanolamine, N-alkylamine polyoxyethylene ether, N,N,Nʹ,Nʹ-tetra(2-hydroxyethyl)ethylenediamine, or dihydroxyalkylamine; wherein the alkyl group refers to C1-C1. 18 hydrocarbon group; in N-Hydromethylamine polyoxyethylene ethers have the structure shown in general formula (II): ； In general formula (II), R4 is selected from C1 to C2. 18 Hydrocarbon group, R5 is selected from H or methyl, and the sum of p and q is selected from natural numbers from 2 to 200; The dihydroxyalkylamine has the structure shown in general formula (III): ； in In general formula (Ⅲ), R4 is selected from C1 to C2. 18 The hydrocarbon group, R5, is selected from H or methyl.

2. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 1, characterized in that... The organic solvent refers to one or more of the following: acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, tetrahydrofuran, 1,4-dioxane, chloroform, chlorobenzene, petroleum ether with a boiling range of 60~120℃, hexane, cyclohexane, decahydronaphthalene, N,N-dimethylaniline, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

3. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 1, characterized in that... The unsuitable solvents refer to one or more of methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, or water.

4. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 1, characterized in that... The phosphonium zwitterionic polyol is prepared by the following method: The solvent and aminoalkyl bisphosphonate or aminoalkyl bisphosphonate, glycidyl quaternary ammonium, and solvent are added sequentially to a reaction vessel in a mass ratio of 100:50~500:50~2000. The mixture is stirred and dispersed evenly. An appropriate amount of alkaline or acidic aqueous solution is used to adjust the pH of the material in the reaction vessel to between 7.0 and 8.

5. The temperature of the material in the reaction vessel is controlled to -10 to 90°C. A glycidyl quaternary ammonium solution is slowly added to the reaction vessel. After stirring and reacting for 2 to 6 hours, an appropriate amount of alkaline or acidic aqueous solution is used to adjust the pH of the material in the reaction vessel to between 3.5 and 5.

5. Then, rotary evaporation is performed to concentrate the solids. The rotary evaporation concentration is then stopped, and the temperature of the material in the reaction vessel is lowered to room temperature. After precipitation, filtration, recrystallization, and drying to constant weight, the phosphonium zwitterionic polyol with the structure shown in general formula (Ⅰ) is obtained. The phosphonium zwitterionic polyol described therein has the structure shown in general formula (Ⅰ): ； In general formula (Ⅰ), R1, R2, and R3 are selected from C1 to C1 respectively. 18 hydrocarbon group, Select C1~C 18 The alkylene group, Q is selected from H or OH, Y is selected from OH or OM; where M is selected from Na, K or Li. The aminoalkyl bisphosphonic acid has the structure shown in general formula (V): ； The aminoalkyl bisphosphonate has the structure shown in general formula (V-1) or general formula (V-2): ； The alkyl group in the aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate refers to the alkyl group in general formula (V), general formula (V-1) or general formula (V-2). The Select C1~C 18 The alkylene group, Q is selected from H or OH, and M is selected from Na, K or Li.

5. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 4, characterized in that... The glycidyl quaternary ammonium solution refers to a solution prepared by dissolving the glycidyl quaternary ammonium in a solvent to a mass percentage concentration of 10-60%, wherein the glycidyl quaternary ammonium has the structure shown in general formula (VI): ； In the general formula (VI), R1, R2, and R3 are selected from C1 to C1 respectively. 18 hydrocarbon group, X - Select NO3 - Cl - ,Br - SO4 2- One of the following: or p-toluenesulfonate anion.

6. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 4, characterized in that... The alkaline aqueous solution refers to one of the following: sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, caustic soda aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, or lithium carbonate aqueous solution with a mass percentage concentration of 10-30%.

7. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 4, characterized in that... The acidic aqueous solution refers to one of the following: nitric acid aqueous solution, hydrogen chloride aqueous solution, hydrogen bromide aqueous solution, sulfuric acid aqueous solution, or p-toluenesulfonic acid aqueous solution with a mass percentage concentration of 10-30%.

8. A polarized polyurethane with phosphonium zwitterions on its side chains according to claim 4, characterized in that... The solvent refers to one or more of the following: water, methanol, ethanol, propanol, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, or hexamethylphosphoramide.

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