A polyurethane with poly(quaternary ammonium phosphonate copper) on its side chain and its preparation method thereof

Abstract

This invention provides a polyurethane with poly(quaternary ammonium phosphonate copper) side chains, prepared by using bis(hydroxypropyl tertiary ammonium phosphonate copper) as a functional polyol, through addition polymerization with polyisocyanates and quaternization reaction with alkylating agents. The tertiary amine group in the bis(hydroxypropyl tertiary ammonium phosphonate copper) molecular structure is characterized by quaternization reactions with halogenated hydrocarbons, and also acts as a catalyst for the addition reaction of its hydroxypropyl group with polyisocyanates, as well as an N-ligand for complexing copper ions. Furthermore, the low solubility of copper phosphonate in water allows for the formation of a polyurethane composite material with macromolecular side chains that chelate copper ions, achieving a slow-release effect of copper ions in aqueous systems. Furthermore, the quaternary ammonium cations generated by the nucleophilic substitution reaction between the tertiary amine group in the poly(hydroxypropyl tertiary aminophosphonate copper) molecular structure and halogenated hydrocarbons have hydrophilic, water-absorbing, surfactant, antibacterial and bacteriostatic functions. Combined with the phosphonate ions generated by the dissociation of copper phosphonate in water, they pair to form two phosphonium zwitterionic structural units, which is of great significance for improving the antibacterial and bacteriostatic efficacy, biocompatibility, and hydrophilicity of polyurethane.

Description

Technical Field

[0001] This invention relates to a multifunctional polyurethane and its preparation method, particularly to a functional polyurethane with multiple (quaternary ammonium phosphonate copper) on its side chains and its preparation method. The functional polyurethane possesses ionic conductivity and slow-release copper ion properties, while also exhibiting hydrophilic and water-absorbing properties, as well as antibacterial and bacteriostatic functions, belonging to the field of functional composite materials. Background Technology

[0002] 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 and polyisocyanates, and are typical block copolymers. Products come in a wide variety of forms, including polyurethane elastomers, polyurethane fibers, polyurethane foams, polyurethane films, polyurethane coatings, polyurethane adhesives, polyurethane hydrogels, and polyurethane prepolymers. Compared with other polymer materials, polyurethane materials have advantages such as easy molecular structure design, tunable performance, good processability, diverse processing methods, excellent mechanical properties, diverse product types, and wide application fields. Functional modification of polyurethane materials, thereby maintaining their excellent properties while endowing them with unique biological, optoelectronic, electromagnetic, thermal, and other physical or chemical properties, has become a major method for expanding the variety and application fields of polyurethane materials. Over the past century, common polyurethane functionalization methods have included blending modification, chemical copolymerization, interpenetrating polymer networks, and surface modification. Among these, bonding or compounding functional materials with polyurethane materials at the molecular level not only fully utilizes the properties of each component but also achieves uniform distribution, material stability, and synergistic performance effects. Therefore, professionals are well aware that 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 zwitterion pairs to give it hydrophilic, ion exchange, and antibacterial functions has never ceased. In currently available literature, the raw materials for functionalizing polyurethane are mainly small-molecule N-methyldiethanolamine, dimethylolpropionic acid, ethylenediamine ethanesulfonic acid, 2-mercaptoethanol, N-(2-hydroxyethyl)iminodiacetic acid, 3-(N-methyl-N,N-diethanolammonium)-propanesulfonic acid inner salt, and 3-(N,N,N-triethanolammonium)-propanesulfonic acid inner salt. The above mainly involves introducing anions / cations or some ligands into polyurethane materials through end-capping or chain extension methods of polyurethane prepolymers, thus limiting the current functionalization modification of polyurethane. Therefore, in the past decade or so, attention has shifted to the research and development of functionalized polymer polyols.

[0003] Professionals are well aware that polymer polyol molecules have a high degree of design freedom, which has led 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 immobilized crown compound materials for ionseparation,Tetrahedron, 53(1997)1343-1360;Click-ligation of coumarin topolyether polyols for polyurethane foams,Polym. Int., 62(2013)783-790;Detection of uranium with a wireless sensing method by using salophen asreceptor and magnetic nanoparticles as signal-amplifying tags,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.Based on this, in order to further expand the variety of functional polyurethane materials, the inventors used a novel bis(hydroxypropyl tertiary aminophosphonate copper) as a functional polyol to prepare ion-conducting polyurethane composite materials with bis(quaternary ammonium phosphonate copper) on the side chains, which have the characteristics of slow-release copper ions, hydrophilic and water-absorbing properties, and antibacterial and bacteriostatic functions. The bis(hydroxypropyl tertiary aminophosphonate copper) has the structure shown in general formula (I) or general formula (II).

[0004]

[0005] In general formula (Ⅰ) or general formula (Ⅱ), R1 and R2 are respectively selected from C1 to C2. 18 hydrocarbon group, Select C1~C 18 Hydroxyl group, where Q is selected from H or OH atoms.

[0006] As is well known to those skilled in the art, the tertiary amine group in the bis(hydroxypropyl tertiary aminophosphonate copper) molecular structure of this invention is characterized by quaternization reactions with haloalkanes, and also acts as a catalyst for the addition polymerization reaction of the hydroxypropyl group with polyisocyanates, as well as an N-ligand for complexing copper ions. Secondly, the low solubility of copper phosphonate in water allows for the formation of polyurethane composites with chelated copper ions on their macromolecular side chains, resulting in the slow release of copper ions in water. Furthermore, the quaternary ammonium cation generated by the nucleophilic substitution reaction of the tertiary amine group in the bis(hydroxypropyl tertiary aminophosphonate copper) molecular structure with haloalkanes possesses hydrophilic, water-absorbing, surfactant, and antibacterial / bacteriostatic functions. Combined with the phosphonate ions generated by the dissociation of copper phosphonate in water, these cations pair to form two phosphonium zwitterionic structural units, which is of great significance for improving the antibacterial / bacteriostatic efficacy, biocompatibility, and hydrophilicity of polyurethane. In summary, the reaction of bis(hydroxypropyl tertiary ammonium phosphonate copper) as a functional polyol with polyisocyanates produces poly(quaternary ammonium phosphonate copper) ion-conducting polyurethane composites with side chains that possess diverse biological, physical, and chemical properties and functions. Summary of the Invention

[0007] This invention provides a polyurethane with poly(quaternary ammonium phosphonate copper) side chains, which is prepared by the following steps: In a reaction vessel, organic solvent, polymeric polyol, catalyst, and bis(hydroxypropyl tertiary ammonium phosphonate copper) are weighed in the following proportions: 5-50 parts by mass of bis(hydroxypropyl tertiary ammonium phosphonate copper), 5-50 parts by mass of polymeric polyol, polyisocyanate, 5-50 parts by mass of chain extender, 0-1.5 parts by mass of catalyst, and 50-500 parts by mass of organic solvent. Under N2 protection, the mixture is stirred until homogeneous. Then, polyisocyanate is added to the reaction vessel, and the temperature of the material inside the reaction vessel is controlled at 50-90°C. The mixture is stirred for 2-6 hours. A chain extender is added, and the mixture is stirred for another 2-6 hours to complete the polymerization reaction. Then, an alkylating agent is added, and the temperature of the material inside the reaction vessel is controlled at 20-120°C. The mixture is stirred for another 2-20 hours to complete the quaternization reaction. The temperature of the material system in the reaction vessel is lowered to room temperature. After filtration, washing, and drying, the polyurethane with poly(quaternary ammonium phosphonate copper) side chains is obtained.

[0008] The polyurethane with poly(quaternary ammonium phosphonate copper) on its side chain described in this invention can also be prepared by the following staged polymerization process: Solution ①, composed of organic solvent, polymer polyol, bis(hydroxypropyl tertiary ammonium phosphonate copper), and catalyst, is prepared according to the following mass ratios: 5-50 parts of bis(hydroxypropyl tertiary ammonium phosphonate copper), 5-50 parts of polymer 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, polymer polyol, and chain extender; an appropriate amount of polyisocyanate is added to solution ①, and N... 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; the solution ② is added to the first-stage polyurethane solution, and after mixing evenly, the remaining amount of polyisocyanate is added. Under N2 protection, the temperature is controlled at 50~90℃, and the reaction is stirred for 2~6 hours to obtain the second-stage polyurethane solution; an alkylating agent is added to the second-stage polyurethane solution, and the temperature is controlled at 20~120℃. The reaction is continued for 2~20 hours, and the temperature of the material system in the reactor is reduced to room temperature. After separation, washing, and drying, the polyurethane with poly(quaternary ammonium phosphonate copper) on the side chain is obtained.

[0009] 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, bis(hydroxypropyl tertiary aminophosphonate copper) and chain extender is controlled in the range of 0.86 to 1.24, preferably 0.95 to 1.05;

[0010] The bis(hydroxypropyl tertiary aminophosphonate copper) has the structure shown in general formula (I) or general formula (II):

[0011]

[0012] In general formula (Ⅰ) or general formula (Ⅱ), R1 and R2 are respectively selected from C1 to C2. 18 hydrocarbon group, Select C1~C 18 For the alkylene group, Q can be H or OH.

[0013] The polymer polyol refers to one or more of the following: polyether polyol, polyester polyol, polyolefin polyol, vegetable oil polyol, or organosilicon polyol.

[0014] 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.

[0015] The catalyst refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, di(dodecyl sulfide)dibutyltin, or dibutyltin diacetate.

[0016] 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 dihydroxyamine; wherein the alkyl group refers to C1-C6. 18 Hydrocarbon group.

[0017] The N-alkylamine polyoxyethylene ether has the structure shown in general formula (Ⅲ):

[0018]

[0019] In general formula (Ⅲ), R3 is selected from H or methyl, and R4 is selected from C1 to C2. 18 The hydrocarbon group, where the sum of p and q is selected from natural numbers between 2 and 200;

[0020] The dihydroxyamine has the structure shown in general formula (Ⅳ):

[0021]

[0022] In general formula (Ⅳ), R3 is selected from H or methyl, and R4 is selected from C1 to C2. 18 Hydrocarbon group.

[0023] 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.

[0024] The alkylating agent has the structure shown in general formula (V):

[0025]

[0026] In the general formula (V), Y is selected from C1 to C2. 18 hydrocarbon group or X is selected from Cl, Br, I or p-CH3C6H4SO2, where n is selected from a natural number between 0 and 200, and R5 is selected from C1 to C2. 18 Hydrocarbon group; the amount of the alkylating agent used is 0.5 to 1.5 times the sum of the molar number of N atoms in bis(hydroxypropyl tertiary aminophosphonate copper) and the chain extender.

[0027] The bis(hydroxypropyl tertiary aminophosphonate copper) is prepared by the following method: a solvent and aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate are added to a reaction vessel and stirred to disperse evenly. The pH value of the material in the reaction vessel is adjusted to between 7.0 and 8.5 using an appropriate amount of alkaline or acidic aqueous solution. The temperature of the material in the reaction vessel is controlled to -10 to 90°C. A glycidyl tertiary amine solution is slowly added to the reaction vessel and stirred for 2 to 4 hours. Then, a copper salt solution is added, and at the same time, an appropriate amount of alkaline aqueous solution is used to adjust the pH value of the material in the reaction vessel to gradually rise to between 7.5 and 11.0. After rotary evaporation to concentrate and precipitate solid substances, the rotary evaporation concentration is 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, bis(hydroxypropyl tertiary aminophosphonate copper) with the structure shown in general formula (I) or general formula (II) is obtained.

[0028] The mass ratio of aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate, glycidyl tertiary amine, and solvent is 100:50~500:50~2000.

[0029] The structure of the bis(hydroxypropyl tertiary aminophosphonate copper) shown in general formula (I) or general formula (II);

[0030]

[0031] In general formula (Ⅰ) or general formula (Ⅱ), R1 and R2 are respectively selected from C1 to C2. 18 hydrocarbon group, Select C1~C 18For the alkylene group, Q can be H or OH.

[0032] The aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate has the structure shown in general formula (VI), general formula (VI-1) or general formula (VI-2):

[0033]

[0034] The alkyl group in the aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate refers to the alkyl group in general formula (VI), general formula (VI-1) or general formula (VI-2). The Select C1~C 18 The alkylene group, Q is selected from H or OH, and M is selected from Na or K.

[0035] The glycidyl tertiary amine solution refers to a solution prepared by dissolving the glycidyl tertiary amine in a solvent to a mass percentage concentration of 10-60%, wherein the glycidyl tertiary amine has the structure shown in general formula (VII):

[0036]

[0037] In general formula (VII), R1 and R2 are selected from C1 to C2 respectively. 18 Hydrocarbon group.

[0038] The alkaline aqueous solution refers to one of the following: sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, caustic soda aqueous solution, or potassium hydroxide aqueous solution with a mass percentage concentration of 10-30%.

[0039] 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%.

[0040] The copper salt solution refers to one of the following: copper nitrate aqueous solution, copper chloride aqueous solution, copper bromide aqueous solution, copper sulfate aqueous solution, or copper p-toluenesulfonate aqueous solution, with a pH value of 4.5-6.5 and a mass percentage concentration of 10-60%; the amount of the copper salt used is 1-2 times the molar amount of aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate.

[0041] 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.

[0042] Compared with the prior art, the beneficial effects of the poly(quaternary ammonium phosphonate copper) polyurethane on the side chain of the present invention are:

[0043] ① The raw materials for preparing polyurethane with poly(quaternary ammonium phosphonate copper) on the side chain as described in this invention are mostly 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.

[0044] ②The polyurethane with poly(quaternary ammonium phosphonate) on the side chain of the present invention releases copper ions at a rate that is almost constant over several months in a stable water system.

[0045] ③ The raw material ratio for preparing the macromolecular side-chain linked poly(quaternary ammonium phosphonate copper) polyurethane of the present invention can be adjusted within a wide range. The poly(phosphonium ammonium zwitterionic) polyurethane that produces the slow-release copper ions can exhibit various types of products such as water-absorbing swelling type, water-dispersible type, and water-soluble type. It is suitable for ion-conducting polyurethanes with slow-release copper ion characteristics, hydrophilic water absorption, antibacterial and bacteriostatic functions required in various environments. Detailed Implementation

[0046] To further illustrate the present invention, specific examples are provided to facilitate a better understanding of its content. Therefore, the poly(quaternary ammonium phosphonate copper) polyurethanes with side chains not listed in the examples should not be considered as limitations on the scope of protection of the present invention.

[0047] Example 1: Preparation of bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-1)

[0048] Weigh 33.0 g of alendronate monosodium trihydrate (sold by Anhui Kaichao Biotechnology Co., Ltd.) and disperse it in 6.7 g of deionized water. Place the mixture into a reaction vessel. Use an 18% (w / w) sodium hydroxide solution to adjust the pH of the material in the reaction vessel to between 7.0 and 7.5, and control the temperature of the material in the reaction vessel to 15-20°C. Slowly add 4.1 g of a 1:1 (w / w) mixture of N-glycidyl dimethylamine and ethanol to the reaction vessel. Stir the reaction for 2 hours to increase the temperature of the material in the reaction vessel. The material temperature was raised to 55-60℃, and the reaction was stirred for 1.5 hours. Then, 20 mL of a 1.0 M copper sulfate aqueous solution with a pH of 5.5 was slowly added. At the same time, a 18% caustic soda aqueous solution was used to adjust the pH of the material in the reactor from 7.0-7.5 to ≥10.0. 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, 6.53 g of blue powder product (Ⅰ-1) was obtained.

[0049] TGA analysis of the blue powdery product (Ⅰ-1) showed that: before 100℃, the thermal weight loss was not significant; from around 125℃, the thermal weight loss became significant; between 20 and 250℃, the thermal weight loss was approximately 10.37%, which should be attributed to the loss of water of crystallization; between 250 and 450℃, the thermal weight loss was approximately 43.17%, which should be attributed to the thermal decomposition loss of organic components in the blue powdery product (Ⅰ-1); there was still 46.52% black residue up to 700℃, which should be the black residue of copper phosphate and carbon residue produced by the thermal decomposition of the blue powdery product (Ⅰ-1). Elemental analysis (%) of the blue powdery product (Ⅰ-1): C 28.87, H 5.53, Cl 4.08, 7.03, P 10.67, consistent with the designed molecular formula C 14 H 31 The calculated values ​​of C 29.27, H 5.44, N 7.31, and P 10.78 for N3O9P2Cu2 are basically consistent, indicating that the blue powdery product (Ⅰ-1) contains four molecules of water of crystallization. The IR (KBr pellet, cm⁻¹) of the blue powdery product (Ⅰ-1) is also consistent with these values. -1 The peaks 3437, 3308, 2936, 2863, 1536, 1436, 1361, 1256, 1106, 1024, 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, DMSO-d6, ẟ): 1.44 (m, 2H), 1.68 (m, 2H), 2.02–2.05 (m, 3H), 2.27 (s, 12H), 2.34–2.37 (m, 6H), 2.68 (m, 4H), 3.71 (m, 2H). Based on the above analytical and characterization results, the blue powdery product (Ⅰ-1) is confirmed to possess the bis(hydroxypropyl tertiary aminophosphonate copper) structural characteristics shown in formula (Ⅰ-1).

[0050]

[0051] Example 2 Preparation of bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-2)

[0052] Following the preparation method and procedures of Example 1, N-glycidyl dimethylamine was replaced with N-glycidyl-N,N-diallylamine to obtain a blue powder product (Ⅰ-2). Using analytical characterization methods similar to those of Example 1, it was confirmed that the blue powder product (Ⅰ-2) possesses the bis(hydroxypropyl tertiary aminophosphonate copper) structural characteristics shown in formula (Ⅰ-2):

[0053] .

[0054] Example 3 Preparation of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-1) with side chains

[0055] Weigh 15 g of dehydrated N,N-dimethylformamide, 0.06 g of dibutyltin dilaurate, and 3 g of dehydrated bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-1) into a reactor. Under N2 protection, maintain the temperature at 60-80℃ and stir until homogeneous. Add 2.5 g of toluene diisocyanate to the reactor and stir for 2 hours for addition polymerization. Then add 6 g of dehydrated polyethylene glycol-2000 and mix well. Finally, add the remaining 0.55 g of toluene diisocyanate to the reactor. Continue stirring for 2 hours to carry out the addition polymerization reaction. Add a mixture of 0.23 g of 1,4-butanediol, 2.5 g of benzyl chloride and 20 g of tetrahydrofuran. Control the temperature at 80-100°C and stir for 12 hours. Lower the temperature of the material system in the reactor to room temperature. After separation, obtain a light blue-green resin (Ⅰ-1). Use chloroform to perform Soxhlet extraction on the pulverized light blue-green resin for 24 hours. Then send it to a vacuum drying oven at 50-55°C to dry for 24 hours to obtain polyurethane (Ⅰ-1) with poly(quaternary ammonium phosphonate copper) on the side chain.

[0056] TGA analysis of polyurethane (Ⅰ-1) with poly(quaternary ammonium phosphonate copper) side chains showed that: before 130℃, the thermogravimetric loss was not significant; it became obvious around 145℃, slowing down to 250℃, with a weight loss rate of 14.23%, which should be attributed to the thermal decomposition weight loss of the quaternary ammonium cation; after 250℃, the weight loss accelerated until 450℃, then slowed down again, with a weight loss rate of 67.07%, which should be attributed to the thermal decomposition of the polyurethane macromolecular chain; there was still 17.52% black residue up to 700℃, which should be the black carbon residue and copper phosphate remaining after the thermal decomposition of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-1) with poly(quaternary ammonium phosphonate copper) side chains. IR (KBr tablet, cm -1 The absorption peaks 3451, 3340, 2937, 2863, 1737, 1643, 1538, 1446, 1368, 1258, 1108, 1024, and 927 are attributed to the characteristic vibrational absorption peaks of NH, OH, methylCH, methyleneCH, C=O, CN, P=O, CO, and PO, respectively. Based on the above analytical and characterization results, it is confirmed that the light blue-green resin (Ⅰ-1) possesses the schematic structure of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-1) with side chains as shown in formula (Ⅰ-1):

[0057]

[0058] Example 4 Preparation of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-2) with side chains

[0059] Following the preparation method and operating steps of Example 3, bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-1) in Example 1 was replaced with bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-2), and polyethylene glycol-2000 was replaced with polyethylene glycol-200, yielding a light blue-green resin (Ⅰ-2). TGA analysis of the light blue-green resin (Ⅰ-2) showed that the thermal weight loss was not significant before 120°C, but became obvious from around 125°C, increasing to 21°C. The thermal weight loss slows down at 3℃, with a rate of 15.07%, which should be attributed to the thermal decomposition weight loss of quaternary ammonium cations. After 225℃, the thermal weight loss accelerates until 375℃, at which point it slows down again, with a rate of 60.14%, which should be attributed to the thermal decomposition of the polyurethane macromolecular chain structure. There is still 13.29% black residue up to 700℃, which should be the black carbon residue and copper phosphate remaining after the thermal decomposition of the light blue-green resin (Ⅰ-2). The IR spectrum of the light blue-green resin (Ⅰ-2) is similar to that of polyurethane (Ⅰ-1) with poly(quaternary ammonium cation copper phosphonate) on its side chains. Based on the above analytical and characterization results, it is confirmed that the light blue-green resin (Ⅰ-2) has the schematic structure of polyurethane (Ⅰ-2) with poly(quaternary ammonium phosphonate copper) on its side chains as shown in formula (Ⅰ-2).

[0060]

[0061] Example 5 Preparation of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-3) with side chains

[0062] Following the preparation method and operating steps of Example 3, bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-1) in Example 1 was replaced with bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-2), toluene diisocyanate was replaced with isophorone diisocyanate, polyethylene glycol-2000 was replaced with polyethylene glycol-200, and 1,4-butanediol was replaced with polyetheramine AC1202, and a light blue-green resinous product (Ⅰ-3) was also obtained. Using the same analytical method as in Example 3, it was determined that the light blue-green resinous product (Ⅰ-3) has a poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-3) schematic structure on the side chain of formula (Ⅰ-3):

[0063]

[0064] Example 6 Preparation of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-4) with side chains

[0065] Following the preparation method and operating steps of Example 3, the toluene diisocyanate in Example 1 was replaced with isophorone diisocyanate, and benzyl chloride was replaced with bromododecane, to obtain a light blue resinous product (I-4). Using the same analytical method as in Example 3, it was determined that the light blue resinous product (I-4) has a poly(quaternary ammonium phosphonate copper) polyurethane (I-4) schematic structure on the side chain of formula (I-4):

[0066]

[0067] Example 7 Preparation of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-5) with side chains

[0068] 140 g of dehydrated N,N-dimethylformamide, 0.58 g of dibutyltin dilaurate, and 30 g of dehydrated bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-1) were weighed sequentially into a reaction vessel. Under N2 protection, the temperature was controlled at 70-80℃, and the mixture was stirred until homogeneous. 25 g of toluene diisocyanate was added to the reaction vessel, and the polymerization reaction was carried out for 4 hours. Then, 40 g of polyethylene glycol-2000 was added and mixed well. Finally, the remaining 4.5 g of toluene diisocyanate was added to the reaction vessel. Continue stirring for 2 hours to carry out the addition polymerization reaction. Add 2.5 g of N-dodecyl-N,N-diethanolamine and 25 g of benzyl chloride. Control the temperature at 80~100℃ and stir for 12 hours. Lower the temperature of the material system in the reactor to room temperature. After separation, obtain light blue-green resin (Ⅰ-5). Use chloroform to perform Soxhlet extraction on the pulverized light blue-green resin for 24 hours. Then send it to a vacuum drying oven at 50~55℃ to dry for 24 hours to obtain polyurethane (Ⅰ-5) with poly(quaternary ammonium phosphonate copper) on the side chain.

[0069] Example 8 Preparation of poly(quaternary ammonium phosphonate copper) polyurethane (Ⅰ-6) with side chains

[0070] Weigh 140 g of dehydrated N,N-dimethylformamide, 0.64 g of dibutyltin dilaurate, and 30 g of dehydrated bis(hydroxypropyl tertiary aminophosphonate copper) (Ⅰ-1) into a reactor. Under N2 protection, maintain the temperature at 70-80℃ and stir until homogeneous. Add 27 g of toluene diisocyanate to the reactor and stir for 4 hours for addition polymerization. Then add 35 g of polyethylene glycol-2000 and mix well. Finally, add the remaining 6.5 g of toluene diisocyanate to the reactor. Isocyanate was added and stirred for 2 hours for addition polymerization. Then, 3.8 g of 1,4-butanediol and 75 g of bromododecane were added. The temperature was controlled at 80-100℃ and the reaction was stirred for 20 hours. The temperature of the material system in the reactor was lowered to room temperature. The earth-colored resin (Ⅰ-6) was obtained by separation. The pulverized earth-colored resin was subjected to Soxhlet extraction with chloroform for 24 hours. Then, it was dried in a vacuum drying oven at 50-55℃ for 24 hours to obtain polyurethane (Ⅰ-6) with poly(quaternary ammonium phosphonate copper) on the side chain.

[0071] Example 9: Characteristics of poly(quaternary ammonium phosphonate copper) polyurethane with side chains in Examples 3-8

[0072] The water absorption properties of polyurethanes with poly(quaternary ammonium phosphonate copper) side chains in Examples 3-8 were determined according to GB / T8810-1988, the method for determining the water absorption rate of polyurethane foam. 3.0000 grams of 20-mesh polyurethane granules with poly(quaternary ammonium phosphonate copper) side chains in Examples 3-8 were weighed, immersed in 50 ml of deionized water, shaken at room temperature for 72 hours, filtered out, centrifuged and dried at 2000 rpm for 3 minutes, and weighed again (W). The water absorption rate of the poly(quaternary ammonium phosphonate copper) polyurethanes with side chains in Examples 3-8 was calculated according to formula (W-3) / 3. The results are shown in Table 1.

[0073] Table 1. Water absorption rates of poly(quaternary ammonium phosphonate copper) polyurethanes with side chains in Examples 3-8

[0074] Example 3 4 5 6 7 8 Water absorption rate (%) 173 298 dispersion 151 342 203

[0075] The antibacterial properties of polyurethane with poly(quaternary ammonium phosphonate) side chains in Examples 3-8 were determined according to the operating procedures specified in GB / T31402-2015 Test Method for Antibacterial Properties of Plastic Surfaces. 3.0000 g of 20-mesh polyurethane granules with poly(quaternary ammonium phosphonate) side chains from Examples 3-8 were weighed and mixed with 5.0 mL of a 1×10⁻⁶ solution. 6 CFU / mL Staphylococcus aureus (S. aureus) or Escherichia coli (E. coli) suspensions were combined and added to 95 mL of phosphate buffer containing 0.1% Tween-80. After incubation at 37°C with shaking for 24 hours, the total number of remaining viable bacteria was counted, and the antibacterial properties of poly(quaternary ammonium phosphonate copper) polyurethane with side chains were quantitatively evaluated. The results are shown in Table 1.

[0076] Table 2. Antibacterial properties of poly(quaternary ammonium phosphonate copper) polyurethanes with side chains in Examples 3-8

[0077] Example 3 4 5 6 7 8 Staphylococcus aureus kill rate (%) 94.5 98.2 100 100 100 100 E. coli eradication rate (%) 94.1 98.3 100 100 100 100

[0078] 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 shall fall within the protection scope of the appended claims.

Claims

1. A polyurethane with poly(quaternary ammonium phosphonate copper) on its side chains, which is prepared by the following steps: In a reaction vessel, organic solvent, polymeric polyol, catalyst, and bis(hydroxypropyl tertiary ammonium phosphonate copper) are weighed in the following proportions: 5-50 parts by mass of bis(hydroxypropyl tertiary ammonium phosphonate copper), 5-50 parts by mass of polymeric polyol, 5-50 parts by mass of polyisocyanate, 0-10 parts by mass of chain extender, 0-1.5 parts by mass of catalyst, and 50-500 parts by mass of organic solvent. Under N2 protection, after stirring evenly, polyisocyanate is added to the reaction vessel. The temperature of the material inside the reaction vessel is controlled at 50-90°C, and the reaction is carried out for 2-6 hours. Then, chain extender is added, and the reaction is continued with stirring for another 2-6 hours to complete the polymerization reaction. Then, alkylating agent is added, and the temperature of the material inside the reaction vessel is controlled at 20-120°C. After stirring for another 2-20 hours, the quaternization reaction is stopped. The temperature of the material system in the reaction vessel is lowered to room temperature. After filtration, washing, and drying, the polyurethane with poly(quaternary ammonium phosphonate copper) on its side chains is obtained; characterized in that… The bis(hydroxypropyl tertiary aminophosphonate copper) has the structure shown in general formula (I) or general formula (II): In general formula (I) or general formula (II), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, Selected from C1~C 18 Hydroxyl group, Q is selected from or OH; 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, bis(hydroxypropyl tertiary aminophosphonate copper) and chain extender is controlled between 0.86 and 1.

24.

2. A polyurethane with poly(quaternary ammonium phosphonate copper) side chains according to claim 1, characterized in that... The polymer polyol refers to one or more of the following: polyether polyol, polyester polyol, polyolefin polyol, vegetable oil polyol, or organosilicon polyol.

3. A polyurethane with poly(quaternary ammonium phosphonate copper) side chains according to claim 1, characterized in that... 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.

4. A polyurethane with poly(quaternary ammonium phosphonate copper) side chains according to claim 1, characterized in that... The catalyst refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, di(dodecyl sulfide)dibutyltin, or dibutyltin diacetate.

5. A polyurethane with poly(quaternary ammonium phosphonate copper) side chains according to claim 1, characterized in that... 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 dihydroxyamine; wherein the alkyl group refers to C1-C6. 18 hydrocarbon group; in N-Hydromethylamine polyoxyethylene ethers have the structure shown in general formula (Ⅲ): In general formula (Ⅲ), R3 is selected from H or methyl, and R4 is selected from C1 to C2. 18 The hydrocarbon group, where the sum of p and q is selected from natural numbers between 2 and 200; The dihydroxyamine has the structure shown in general formula (Ⅳ): In general formula (Ⅳ), R3 is selected from H or methyl, and R4 is selected from C1 to C2. 18 Hydrocarbon group.

6. A polyurethane with poly(quaternary ammonium phosphonate copper) 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.

7. A polyurethane with poly(quaternary ammonium phosphonate copper) side chains according to claim 1, characterized in that... The alkylating agent has the structure shown in general formula (V): In the general formula (V), Y is selected from C1 to C2. 18 hydrocarbon group or X is selected from Cl, Br, I or p-CH3C6H4SO2, where n is selected from a natural number between 0 and 200, and R5 is selected from C1 to C2. 18 Hydrocarbon group; the amount of the alkylating agent used is 0.5 to 1.5 times the sum of the molar number of N atoms in bis(hydroxypropyl tertiary aminophosphonate copper) and the chain extender.

8. A polyurethane with poly(quaternary ammonium phosphonate copper) side chains according to claim 1, characterized in that... The bis(hydroxypropyl tertiary aminophosphonate copper) is prepared by the following method: a solvent and aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate are added to a reaction vessel and stirred to disperse evenly. The pH value of the material in the reaction vessel is adjusted to between 7.0 and 8.5 using an appropriate amount of alkaline aqueous solution or acidic aqueous solution. The temperature of the material in the reaction vessel is controlled to -10 to 90°C. A glycidyl tertiary amine solution is slowly added to the reaction vessel and stirred for 2 to 4 hours. Then, a copper salt solution is added, and an appropriate amount of alkaline aqueous solution is used to adjust the pH value of the material in the reaction vessel to gradually rise to between 7.5 and 11.

0. When the solid substance is precipitated by rotary evaporation, the rotary evaporation concentration is 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, bis(hydroxypropyl tertiary aminophosphonate copper) with the structure shown in general formula (I) or general formula (II) is obtained. In general formula (I) or general formula (II), R1 and R2 are selected from C1 to C2 respectively. 18 hydrocarbon group, Selected from C1~C 18 Hydroxyl group, Q is selected as H or OH; The mass ratio of aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate, glycidyl tertiary amine, and solvent is 100:50~500:50~2000. The aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate has the structure shown in general formula (VI), general formula (VI-1) or general formula (VI-2): The alkyl group in the aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate refers to the alkyl group in general formula (VI), general formula (VI-1) or general formula (VI-2). The Select C1~C 18 Hydroxyl group, Q is selected from H atom or OH, M is selected from Na or K; The glycidyl tertiary amine solution refers to a solution prepared by dissolving the glycidyl tertiary amine in a solvent to a mass percentage concentration of 10-60%, wherein the glycidyl tertiary amine has the structure shown in general formula (VII): In the general formula (Ⅶ), R1 and R2 are selected from C1~C1, respectively. 18 hydrocarbon group; The alkaline aqueous solution refers to one of the following: sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, caustic soda aqueous solution, or potassium hydroxide aqueous solution with a mass percentage concentration of 10-30%. The acidic aqueous solution refers to one of the following: hydrogen chloride aqueous solution, hydrogen bromide aqueous solution, nitric acid aqueous solution, sulfuric acid aqueous solution, or p-toluenesulfonic acid aqueous solution with a mass percentage concentration of 10-30%. The copper salt solution refers to one of the following: copper nitrate aqueous solution, copper chloride aqueous solution, copper bromide aqueous solution, copper sulfate aqueous solution, or copper p-toluenesulfonate aqueous solution, with a pH value of 4.5-6.5 and a mass percentage concentration of 10-60%; the amount of the copper salt used is 1-2 times the molar amount of aminoalkyl bisphosphonic acid or aminoalkyl bisphosphonate. 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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