Quaternized cholic acid polyurethane modified polyvinyl chloride material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of inorganic non-metallic materials, in particular to a quaternized cholic acid polyurethane modified polyvinyl chloride material, a preparation method and application. The quaternized cholic acid polyurethane polymer is based on a polyurethane elastomer developed by using cholic acid molecules with a rigid skeleton as a hard segment unit and flexible oligomeric ethylene glycol as a soft segment unit, hydroxyl on cholic acid polyurethane is quaternized to prepare cation modified cholic acid polyurethane, and the cation modified cholic acid polyurethane simulates amphiphilic characteristics of natural peptides. The quaternized cholic acid polyurethane is introduced into a polyvinyl chloride (PVC) matrix as an antibacterial agent, so that the growth of microorganisms such as bacteria and molds can be effectively inhibited, the antibacterial property is achieved, bacteria breeding on the inner surface of a pipeline is avoided, and the composite material is endowed with better biocompatibility and antibacterial property; meanwhile, the quaternized cholic acid polyurethane can effectively improve the strength and toughness of the PVC material; wide application prospects are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic non-metallic materials, and particularly relates to a quaternized cholic acid polyurethane modified polyvinyl chloride material, a preparation method and an application thereof. Background Art

[0002] Polyvinyl chloride (PVC), as a widely used thermoplastic, is widely used in fields such as pipelines, packaging, and construction due to its excellent mechanical properties, chemical stability, and good processability. However, PVC materials lack antibacterial properties in the application of water pipelines and are prone to growing bacteria such as Escherichia coli ATCC 25922 in humid environments, resulting in surface contamination and odor generation of the materials, affecting the hygiene and service life of the products, and posing a potential threat to human life and health.

[0003] To solve this problem, it is necessary to develop PVC composite materials with antibacterial functions. Quaternized cholic acid polyurethane has the potential to become an ideal antibacterial modifier for polyvinyl chloride due to its unique structure and excellent antibacterial properties. Quaternary ammonium cations have strong positive charges and can undergo electrostatic interactions with negatively charged components (such as phospholipids) on the bacterial cell membrane, destroying the integrity of the bacterial cell membrane. The destruction of the cell membrane causes the leakage of bacterial cell contents, ultimately leading to the death of bacteria.

[0004] Cholic acid, as a natural bioactive molecule, has good biocompatibility and antibacterial properties. Introducing quaternized cholic acid polyurethane into polyvinyl chloride materials not only endows the materials with antibacterial functions but also improves their mechanical properties and broadens the application fields. Therefore, the preparation and development of quaternized cholic acid polyurethane modified polyvinyl chloride materials with antibacterial properties have broad application prospects. Summary of the Invention

[0005] The purpose of the present invention is to provide a quaternized cholic acid polyurethane modified polyvinyl chloride material, a preparation method and an application thereof, so as to solve the problems that PVC materials lack antibacterial properties in the application of water pipelines, are prone to growing bacteria in humid environments, resulting in surface contamination and odor generation of the materials, affecting the hygiene and service life of the products, and posing a potential threat to human life and health.

[0006] To achieve the above purpose, the present invention adopts the following technical scheme: A quaternized cholic acid polyurethane modified polyvinyl chloride material, wherein the polyvinyl chloride material comprises the following raw materials in parts by weight: 60 - 80 parts of polyvinyl chloride, 5 - 20 parts of quaternized cholic acid polyurethane, 3 - 10 parts of compatibilizer, 2 - 10 parts of nano filler, 0.5 - 1.5 parts of coupling agent, 3 - 5 parts of plasticizer, 1 - 5 parts of heat stabilizer, 0.5 - 3 parts of lubricant, 0.5 - 2 parts of antioxidant, 0.5 - 2 parts of pigment, and 0.5 - 2 parts of light stabilizer.

[0007] Further, the preparation method of the quaternized cholic acid polyurethane is as follows:

[0008] S11. React cholic acid with ethylene glycol. The reaction product is precipitated with ice water, filtered by suction, and dried under vacuum to obtain solid powder cholate ethylene glycol ester. Dissolve phenyl chloroformate in anhydrous tetrahydrofuran to obtain a first solution. Dissolve cholate ethylene glycol ester in anhydrous tetrahydrofuran, and then add anhydrous pyrrole to obtain a second solution. Under the condition of an ice-water bath, drop the first solution into the second solution, raise the temperature to room temperature, react, filter by suction, concentrate by rotary evaporation, dilute with chloroform, wash, and then obtain an organic phase. Concentrate the organic phase by rotary evaporation, purify by silica gel column chromatography, and dry under vacuum to obtain white solid powder cholic acid activated ester. The structural formula of the cholic acid activated ester is:

[0009]

[0010] S12. Dissolve the cholic acid activated ester in an organic solvent, add diethylene glycol diamine and triethylamine to react, dilute with an organic solvent, wash with a sodium bicarbonate solution, concentrate by rotary evaporation, and dry under vacuum to obtain light yellow powder solid CA-EG-PU. The structural formula of CA-EG-PU is:

[0011]

[0012] S13. Dissolve CA-EG-PU in an organic solvent and add triethylamine, and then drop it into a tetrahydrofuran solution of bromoacetyl bromide. After the reaction, filter by suction, precipitate with excess ether, and dry under vacuum to obtain the product CA-EG-Br. React CA-EG-Br and trimethylamine in N,N-dimethylformamide, precipitate with excess tetrahydrofuran, and dry under vacuum to obtain brown-yellow solid powder CA-EG-Br + , the CA-EG-Br of the present invention + has the structural formula:

[0013]

[0014] Further, in the above S11, the dosage of ethylene glycol is 5-15 times the volume of the mass of cholic acid; catalyzed by concentrated hydrochloric acid, the reaction temperature is 75-85 °C, and the reaction time is 1-3 h; the anhydrous tetrahydrofuran in the first solution is 2-3 times the volume of the mass of cholic acid; the phenyl chloroformate is 1-2 times the mass of cholic acid; in the second solution, the dosage of anhydrous tetrahydrofuran is 5-15 times the volume of the mass of cholic acid, and the molar ratio of anhydrous pyrrole to cholic acid is 2-5:1; the reaction time at room temperature is 10-20 h; the dosage of chloroform is 10-20 times the volume of the mass of cholic acid; wash once with a 5wt% sodium bisulfate solution and three times with a 5wt% sodium bicarbonate solution in sequence.

[0015] Furthermore, in the S12, the molecular weight of the double-terminated amino polyethylene glycol is 2000; the molar ratio of the bile acid activated ester, the double-terminated amino polyethylene glycol and the triethylamine is 1:0.5-5:1-5.

[0016] Furthermore, in the S12, the organic solvents used for reaction and dilution include chloroform, dichloromethane, ethyl acetate and dimethyl sulfoxide; the reaction temperature is 25-50°C, the reaction time is 30-60h; the concentration of the sodium bicarbonate solution is 2-10wt%; the amount of organic solvent used in the reaction is 6-12 times the mass of the bile acid activated ester, and the amount of organic solvent used for dilution is 40-100 times the mass of the bile acid activated ester.

[0017] Furthermore, in the S13, the organic solvent includes tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, xylene, toluene and dichloromethane, and the amount is 5 to 20 times the mass of CA-EG-PU; the ratio of the amount of triethylamine to CA-EG-PU is 2 to 6:1; bromoacetyl bromide is 40 times the molar amount of CA-EG-PU; the amount of tetrahydrofuran used for dissolution is 2 to 10 times the mass of CA-EG-PU; the reaction temperature is 10 to 30°C, and the reaction time is 15 to 25 hours; the amount of N,N-dimethylformamide is 10 to 30 times the mass of CA-EG-Br; the molar ratio of CA-EG-Br:trimethylamine is 1:10 to 50; the reaction temperature is 20 to 70°C, and the reaction time is 10 to 30 hours.

[0018] Furthermore, the compatibilizer includes maleic anhydride grafted PE, maleic anhydride grafted POE, maleic anhydride grafted EVA and chlorinated polyethylene; the nanofiller includes wollastonite, calcium carbonate, barium sulfate and titanium dioxide; the coupling agent is one of the silane coupling agents; the plasticizer includes acrylate polymer copolymer, epoxy soybean oil and diisooctyl phthalate; the heat stabilizer includes methyl tin mercaptan, base heat stabilizer and calcium stearate; the lubricant includes polyethylene wax, paraffin and stearic acid; the antioxidant includes phosphite and hindered phenol; the pigment includes iron oxide brown and titanium dioxide; the light stabilizer includes benzotriazole, benzophenone, nickel dithiocarbamate salt, salicylate, hindered amine, thiobisphenol and zinc oxide.

[0019] Furthermore, the acrylic ester polymer copolymer is methyl methacrylate / acrylate copolymer and acrylate / styrene copolymer; the salt-based heat stabilizer includes salt-based lead acetate and salt-based calcium carbonate; the hindered phenol includes bisphenol A, tri-tert-butylhydroxybenzene and di-tert-butyl-p-cresol; and the hindered amine includes Tinuvin770 and Tinuvin765.

[0020] The preparation method of quaternized bile acid polyurethane modified polyvinyl chloride material comprises the following steps:

[0021] S21. Mix polyvinyl chloride, polyurethane elastomer, compatibilizer, lubricant, and coupling agent evenly;

[0022] Mix and stir in a crusher at 1000 r / min for 1 - 3 minutes;

[0023] S22. Subsequently, add plasticizer, heat stabilizer, antioxidant, light stabilizer, nano filler, and pigment, and mix evenly to obtain a mixture;

[0024] Stir at 1000 r / min for 1 - 3 minutes until evenly mixed each time a raw material is added;

[0025] S23. Open mill and mold the mixture;

[0026] Process parameters for extrusion: The open mill temperature is 150 - 190 °C, and use a molding press for molding, with the molding temperature being 180 - 200 °C.

[0027] Application of quaternized cholic acid polyurethane - modified polyvinyl chloride material in water - conveying pipeline materials.

[0028] Advantages of the present invention:

[0029] 1. The synthesis method of the quaternized cholic acid polyurethane - modified polyvinyl chloride material required by the present invention is simple, the raw materials are easily available and the cost is low, the process operation is simple, and it is suitable for large - scale production;

[0030] 2. The quaternized cholic acid polyurethane - modified polyvinyl chloride material prepared by the present invention has excellent antibacterial properties; the introduction of quaternized cholic acid polyurethane endows the material with antibacterial function, which can effectively inhibit the growth of bacteria, reduce the attachment and reproduction of bacteria on the material surface, and reduce the risk of corruption and pollution caused by bacteria, and has a wide application prospect in the field of water - conveying pipeline materials;

[0031] 3. The quaternized cholic acid polyurethane - modified polyvinyl chloride composite material prepared by the present invention has a significant effect in improving the mechanical properties of polyvinyl chloride; the introduction of quaternized cholic acid polyurethane enhances the impact resistance and toughness of the material, making the composite material have better stability and long service life in complex environments. Specific embodiments

[0032] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention.

[0033] Materials used in the present invention: Cholic acid, 98%, from Aladdin Reagent Co., Ltd.; Ethylene glycol, >99%, from Aladdin Reagent Co., Ltd.; Phenyl chloroformate p-nitrophenyl ester, 90%, Bidepharm; Hydrochloric acid, analytical grade, from Guangzhou Chemical Reagent Factory; Pyridine, 99.8%, from Aladdin Reagent Co., Ltd.; THF, 99.5%, from Aladdin Reagent Co., Ltd.; Chloroform, analytical grade, from Guangzhou Chemical Reagent Factory; Sodium bisulfate, 95%, from Aladdin Reagent Co., Ltd.; Sodium bicarbonate, analytical grade, from Guangzhou Chemical Reagent Factory; Polyvinyl chloride, product number SG-5; Chloroform, specification: analytical grade, from Guangzhou Chemical Reagent Factory; Polyethylene glycol with amino groups at both ends, specification: 98%, from Aladdin Reagent Co., Ltd.; Triethylamine TEA, specification: chromatographic grade, from Aladdin Reagent Co., Ltd.; Tetrahydrofuran THF, specification: analytical grade, from Guangzhou Chemical Reagent Factory; Bromoacetyl bromide, specification: 97%, from Aladdin Reagent Co., Ltd.; Ether, specification: analytical grade, from Guangzhou Chemical Reagent Factory; DMF, specification: analytical grade, from Aladdin Reagent Co., Ltd.; Trimethylamine, specification: 30 wt% in water, from Aladdin Reagent Co., Ltd.; Chlorinated polyethylene, 99%, from Macklin; Calcium carbonate, from Aladdin Reagent Co., Ltd.; Silane coupling agent (vinyltriethoxysilane), from Aladdin Reagent Co., Ltd.; Diisooctyl phthalate DOP, reagent grade, 95%, from Macklin; Mercapto methyl tin, Sn: 19%, from Aladdin Reagent Co., Ltd.; Polyethylene wax, Mn 2000 - 3000, from Macklin; Triphenyl phosphite, 97%, from Macklin; Benzophenone, chemical pure, from Aladdin Reagent Co., Ltd.

[0034] In the examples of the present invention, the quaternized cholic acid polyurethane is prepared by the following method:

[0035] (1) Preparation of cholic acid activated ester CA-NC:

[0036] Put 6 g of cholic acid into a 250 mL round-bottom flask, add 60 mL of ethylene glycol, stir and dissolve at 350 rpm in an 80 °C oil bath; slowly add 1 mL of concentrated hydrochloric acid as a catalyst, and continue stirring and reacting at 80 °C for 2 h; after the reaction is completed, cool to room temperature, and slowly pour the reaction solution into excess ice water while stirring, filter by suction to collect the precipitated white flocculent substance, and vacuum dry at 40 °C and a vacuum degree of 0.01 Mpa for 24 h to obtain the solid powder cholic acid ethylene glycol ester CA-EG.

[0037] Subsequently, the obtained CA-EG above was dissolved in 50 mL of anhydrous THF, and 3.57 mL of anhydrous pyridine was added as an acid-binding agent (to neutralize the protons in the reaction system and reduce the influence of acid on the reaction); 10 g of phenyl p-nitrophenyl carbonate was dissolved in 16.67 mL of anhydrous THF and slowly added dropwise to the above solution. Stirring was carried out at 350 rpm in an ice-water bath. After the addition was completed, the mixture was returned to room temperature and stirred at 350 rpm for 14 h; filtration was carried out under 0.01 MPa to obtain the filtrate. After rotary evaporation at 30 °C, it was diluted with 100 mL of chloroform, washed once with 5 wt% sodium bisulfate solution and three times with 5 wt% sodium bicarbonate solution in sequence. The organic phase was concentrated by rotary evaporation at 30 °C, purified by silica gel column chromatography, and vacuum dried at 40 °C under a vacuum of 0.01 Mpa to obtain a white solid powder CA-NC; the preparation process of CA-NC is as follows:

[0038]

[0039] (2) The cholate-activated ester CA-NC was dissolved in chloroform, and the mass ratio of chloroform to CA-NC was 10:1; diaminopolyethylene glycol (molecular weight 2000) and TEA were added, and the molar ratio of CA-NC:diaminopolyethylene glycol:TEA was 1:1.5:2.5; stirring reaction was carried out at 350 rpm at room temperature for 24 h. Without changing the stirring intensity, the temperature was raised to 50 °C and stirring reaction was continued for 24 h; after the reaction was completed, it was diluted with chloroform, and the mass ratio of chloroform to CA-NC was 50:1; it was washed three times with sodium bicarbonate solution (mass fraction 5 wt%), concentrated by rotary evaporation at 40 °C, and then vacuum dried at 40 °C under a vacuum of 0.01 Mpa to obtain a light yellow powder solid CA-EG-PU; the structural formula of CA-EG-PU is:

[0040]

[0041] (3) CA-EG-PU was dissolved in anhydrous THF, and the mass ratio of anhydrous THF to CA-EG-PU was 10:1. Triethylamine (acid-binding agent) with three times the molar amount of CA-EG-PU was added and dropped into a THF solution of bromoacetyl bromide with 30 times the molar amount of CA-EG-PU. The amount of THF used was 5 times the mass of CA-EG-PU; after reacting at room temperature for 18 h, filtration was carried out to obtain the filtrate, which was precipitated three times with excess ether, and the precipitate was vacuum dried to obtain CA-EG-Br; after the obtained product was dissolved in DMF, DMF was 20 times the mass of CA-EG-Br and added to the flask. Trimethylamine with 35 times the molar amount of CA-EG-Br was added. The reaction system was stirred at 50 °C and 350 rpm for 24 h, then precipitated in excess tetrahydrofuran, and the precipitate was vacuum dried to obtain a brownish-yellow solid powder CA-EG-Br + , with a yield of 63%; the structural formula of CA-EG-Br + is:

[0042]

[0043] Example 1

[0044] The quaternized cholic acid polyurethane modified polyvinyl chloride material is prepared with the following weight ratios: 70 parts of polyvinyl chloride, 10 parts of quaternized cholic acid polyurethane, 5 parts of chlorinated polyethylene, 3 parts of nano calcium carbonate, 2 parts of silane coupling agent, 5 parts of diisooctyl phthalate, 2 parts of mercapto methyl tin, 0.5 part of polyethylene wax, 0.5 part of triphenyl phosphite, 0.5 part of iron oxide brown, and 0.5 part of benzophenone.

[0045] The following preparation method is adopted:

[0046] a. Weigh each raw material according to the proportion and set aside. Add five raw materials, namely polyvinyl chloride, quaternized cholic acid polyurethane, chlorinated polyethylene (compatibilizer), polyethylene wax (lubricant), and vinyltriethoxysilane (silane coupling agent), into a multi-functional pulverizer and stir at 1000 r / min for 3 min until evenly mixed;

[0047] b. Subsequently, add diisooctyl phthalate (plasticizer), mercapto methyl tin (heat stabilizer), triphenyl phosphite (antioxidant), benzophenone (light stabilizer), nano calcium carbonate (nano filler), and iron oxide brown (pigment) in sequence. Stir at 1000 r / min for 3 min until evenly mixed after adding each raw material;

[0048] c. Knead and mold the mixture.

[0049] The process parameters for extrusion: The kneading temperature is 180 °C, and a molding press is used for molding. The molding temperature is 190 °C.

[0050] Example 2

[0051] The quaternized cholic acid polyurethane modified polyvinyl chloride material is prepared with the following weight ratios: 65 parts of polyvinyl chloride, 15 parts of quaternized cholic acid polyurethane, 5 parts of chlorinated polyethylene, 3 parts of nano calcium carbonate, 2 parts of silane coupling agent, 5 parts of diisooctyl phthalate, 2 parts of mercapto methyl tin, 0.5 part of polyethylene wax, 0.5 part of triphenyl phosphite, 0.5 part of iron oxide brown, and 0.5 part of benzophenone.

[0052] The following preparation method is adopted:

[0053] a. Weigh each raw material according to the proportion and set aside. Add five raw materials, namely polyvinyl chloride, quaternized cholic acid polyurethane, chlorinated polyethylene (compatibilizer), polyethylene wax (lubricant), and vinyltriethoxysilane (silane coupling agent), into a multi-functional pulverizer and stir at 1000 r / min for 3 min until evenly mixed;

[0054] b. Subsequently, diisooctyl phthalate (plasticizer), mercaptomethyltin (heat stabilizer), triphenyl phosphite (antioxidant), benzophenone (light stabilizer), nano calcium carbonate (nano filler), and iron oxide brown (pigment) were added in sequence. Each time a raw material was added, it was stirred at 1000 r / min for 3 min until evenly mixed;

[0055] c. The mixture was open-milled and molded by compression molding.

[0056] The process parameters for extrusion: The open-milling temperature was 170 °C, and a compression molding machine was used for compression molding. The compression molding temperature was 180 °C.

[0057] Example 3

[0058] A quaternized cholic acid polyurethane-modified polyvinyl chloride material was prepared using the following weight ratios: 75 parts of polyvinyl chloride, 5 parts of quaternized cholic acid polyurethane, 5 parts of chlorinated polyethylene, 3 parts of nano calcium carbonate, 2 parts of silane coupling agent, 5 parts of diisooctyl phthalate, 2 parts of mercaptomethyltin, 0.5 part of polyethylene wax, 0.5 part of triphenyl phosphite, 0.5 part of iron oxide brown, and 0.5 part of benzophenone.

[0059] The following preparation method was adopted:

[0060] a. Weigh each raw material according to the ratio and set it aside. Five raw materials, namely polyvinyl chloride, quaternized cholic acid polyurethane, chlorinated polyethylene (compatibilizer), polyethylene wax (lubricant), and vinyltriethoxysilane (silane coupling agent), were added to a multi-functional pulverizer and stirred at 1000 r / min for 3 min until evenly mixed;

[0061] b. Subsequently, diisooctyl phthalate (plasticizer), mercaptomethyltin (heat stabilizer), triphenyl phosphite (antioxidant), benzophenone (light stabilizer), nano calcium carbonate (nano filler), and iron oxide brown (pigment) were added in sequence. Each time a raw material was added, it was stirred at 1000 r / min for 3 min until evenly mixed;

[0062] c. The mixture was open-milled and molded by compression molding.

[0063] The process parameters for extrusion: The open-milling temperature was 190 °C, and a compression molding machine was used for compression molding. The compression molding temperature was 200 °C.

[0064] Comparative Example 1

[0065] Prepare a methyl methacrylate-butadiene-styrene copolymer (MBS)-modified polyvinyl chloride material using the following weight ratios: 70 parts of polyvinyl chloride, 10 parts of MBS, 5 parts of chlorinated polyethylene, 3 parts of nano calcium carbonate, 2 parts of silane coupling agent, 5 parts of diisooctyl phthalate, 2 parts of mercapto methyl tin, 0.5 part of polyethylene wax, 0.5 part of triphenyl phosphite, 0.5 part of iron oxide brown, and 0.5 part of benzophenone.

[0066] In the comparative example, the common PVC material toughening agent MBS was used to replace quaternized cholanic acid polyurethane.

[0067] Adopt the following preparation method:

[0068] a. Weigh each raw material according to the ratio and set aside. Add five raw materials, namely polyvinyl chloride, MBS, chlorinated polyethylene (compatibilizer), polyethylene wax (lubricant), and vinyltriethoxysilane (silane coupling agent), into a multi-functional pulverizer and stir at 1000 r / min for 3 min until evenly mixed;

[0069] b. Subsequently, add diisooctyl phthalate (plasticizer), mercapto methyl tin (heat stabilizer), triphenyl phosphite (antioxidant), benzophenone (light stabilizer), nano calcium carbonate (nano filler), and iron oxide brown (pigment) in sequence. Stir at 1000 r / min for 3 min until evenly mixed after adding each raw material;

[0070] c. Carry out open rolling on the mixture and then carry out compression molding.

[0071] The process parameters of the extrusion: The open rolling temperature is 180 °C, and compression molding is carried out using a compression molding machine. The compression molding temperature is 190 °C.

[0072] Comparative Example 2

[0073] Prepare a cholanic acid polyurethane CA-EG-PU-modified polyvinyl chloride material using the following weight ratios: 70 parts of polyvinyl chloride, 10 parts of CA-EG-PU, 5 parts of chlorinated polyethylene, 3 parts of nano calcium carbonate, 2 parts of silane coupling agent, 5 parts of diisooctyl phthalate, 2 parts of mercapto methyl tin, 0.5 part of polyethylene wax, 0.5 part of triphenyl phosphite, 0.5 part of iron oxide brown, and 0.5 part of benzophenone.

[0074] In the comparative example, unquaternized CA-EG-PU was used to replace quaternized cholanic acid polyurethane.

[0075] Adopt the following preparation method:

[0076] a. Weigh each raw material according to the proportion for standby. Add five raw materials, namely polyvinyl chloride, CA-EG-PU, chlorinated polyethylene (compatibilizer), polyethylene wax (lubricant), and vinyltriethoxysilane (silane coupling agent), into a multi-functional grinder and stir at 1000 r / min for 3 min until evenly mixed.

[0077] b. Subsequently, add diisooctyl phthalate (plasticizer), mercapto methyltin (heat stabilizer), triphenyl phosphite (antioxidant), benzophenone (light stabilizer), nano calcium carbonate (nano filler), and iron oxide brown (pigment) in sequence. Stir at 1000 r / min for 3 min until evenly mixed each time a raw material is added.

[0078] c. Carry out open rolling on the mixture and then perform compression molding.

[0079] The process parameters for extrusion: The open rolling temperature is 180 °C, and compression molding is carried out using a compression molding machine with a compression molding temperature of 190 °C.

[0080] Antibacterial performance: The antibacterial performance of the examples and comparative examples was characterized by the plate counting method.

[0081] After measuring the OD value at λ = 600 nm by an enzyme-labeled instrument to determine the bacterial concentration, it was gradually diluted to 2×106 CFU / mL with sterile PBS; in addition, a sample solution with a concentration of 1 mg / mL was prepared with sterile PBS and then diluted into a series of sample solutions with concentration gradients.

[0082] Take 100 μL of each sample solution and mix it with an equal volume of Escherichia coli ATCC 25922 bacterial solution, place it in a shaker at 37 °C and incubate at a rotation speed of 220 rpm for 2 h; then take 10 μL of the mixed solution and drop it on an agar plate, spread it evenly with a disposable sterile spreading rod, and place the plate upside down in a mold incubator at 37 °C for 14 h.

[0083] Each experiment was repeated 3 times, and the bacterial solution without sample treatment was set as the positive control group; count the number of bacterial colonies on the plate and calculate the antibacterial rate.

[0084] Mechanical property test: At room temperature, the mechanical properties of the examples and comparative examples were tested using a universal testing machine, and the notched cantilever beam impact strength was measured using a falling weight test device with a tensile rate of 10 mm / min.

[0085] The test results of the composites prepared in Examples 1 - 3 and Comparative Examples 1 - 2 are shown in Table 1.

[0086] Table 1 Antibacterial and Mechanical Property Tests of Polyvinyl Chloride Composites

[0087]

[0088] Conclusion: The quaternized cholic acid polyurethane modified polyvinyl chloride material provided by the present invention exhibits excellent antibacterial performance, and also has good tensile strength, toughness and impact strength. The antibacterial performance of the quaternized cholic acid polyurethane modified polyvinyl chloride material is superior to that of the MBS modified polyvinyl chloride material and the non-quaternized CA-EG-PU modified polyvinyl chloride material.

[0089] In Example 2, the content of quaternized cholic acid polyurethane is the highest, and the quaternized group destroys the bacterial cell membrane through positive charges; the non-quaternized CA-EG-PU relies on the weak antibacterial property of cholic acid itself, and the effect is limited; in Comparative Example 1, there is almost no antibacterial property, and MBS does not contain antibacterial groups and only relies on the physical barrier effect on the material surface.

[0090] The tensile strength is the highest in Example 3, where the content of polyvinyl chloride is the highest and the rigidity is strong; the impact strength is the highest in Comparative Example 1. MBS is a mature toughening agent for PVC materials and can efficiently absorb impact energy. In terms of mechanical properties, the quaternized cholic acid polyurethane modified polyvinyl chloride material is comparable to the MBS modified polyvinyl chloride material, realizing the organic combination of the antibacterial function of the material and the excellent properties of PVC materials.

[0091] The present invention is not limited to the above best implementation mode. Anyone can obtain various other forms of products under the inspiration of the present invention. However, no matter what changes are made in its shape or structure, as long as it has the same or similar technical solutions as the present application, it falls within the protection scope of the present invention.

Claims

1. A quaternary ammonium bile acid polyurethane modified polyvinyl chloride material, characterized in that: The polyvinyl chloride material comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride, 5-20 parts of quaternized cholic acid polyurethane, 3-10 parts of a compatibilizer, 2-10 parts of a nanofiller, 0.5-1.5 parts of a coupling agent, 3-5 parts of a plasticizer, 1-5 parts of a heat stabilizer, 0.5-3 parts of a lubricant, 0.5-2 parts of an antioxidant, 0.5-2 parts of a pigment, and 0.5-2 parts of a light stabilizer.

2. The quaternized bile acid polyurethane modified polyvinyl chloride material according to claim 1, characterized in that: The preparation method of the quaternized bile acid polyurethane is: S11, reacting bile acid with ethylene glycol, precipitating the reaction product with ice water, filtering, and vacuum drying to obtain solid powder bile acid ethylene glycol ester; dissolving nitrochloroformic acid phenyl ester in anhydrous tetrahydrofuran to obtain a first solution; dissolving bile acid ethylene glycol ester in anhydrous tetrahydrofuran, and then adding anhydrous pyrrole to obtain a second solution; under ice-water bath conditions, dropwise adding the first solution to the second solution, heating to room temperature for reaction, filtering, rotary evaporation, diluting with chloroform, washing to obtain an organic phase, rotary evaporation, purifying by silica gel column chromatography, and vacuum drying to obtain a white solid powder bile acid activated ester; the structural formula of the bile acid activated ester is: S12, dissolving the activated bile acid ester in an organic solvent, adding double-terminated amino polyethylene glycol and triethylamine to react, diluting with an organic solvent, washing with a sodium bicarbonate solution, concentrating by rotary evaporation, and drying in vacuo to obtain a light yellow powder solid CA-EG-PU, the structural formula of which is: S13, dissolving CA-EG-PU in an organic solvent and adding triethylamine, and then dripping into a tetrahydrofuran solution of bromoacetyl bromide; after the reaction, filtering, precipitating with excessive ether, and vacuum drying to obtain the product CA-EG-Br; reacting CA-EG-Br and trimethylamine in N,N-dimethylformamide, precipitating with excessive tetrahydrofuran, and vacuum drying to obtain a brown solid powder CA-EG-Br + , the present invention CA-EG-Br + The structural formula is:

3. The quaternized bile acid polyurethane modified polyvinyl chloride material according to claim 2, characterized in that: In the S11, the amount of ethylene glycol is 5 to 15 times the volume of the mass of bile acid; concentrated hydrochloric acid is used as a catalyst, the reaction temperature is 75 to 85°C, and the reaction time is 1 to 3 hours; the volume of anhydrous tetrahydrofuran in the first solution is 2 to 3 times the mass of bile acid; the volume of p-nitrochloroformic acid phenyl is 1 to 2 times the mass of bile acid; in the second solution, the amount of anhydrous tetrahydrofuran is 5 to 15 times the volume of the mass of bile acid, and the molar ratio of anhydrous pyrrole to bile acid is 2 to 5:1; the reaction time at room temperature is 10 to 20 hours; the amount of chloroform is 10 to 20 times the volume of the mass of bile acid; washing is performed once with a 5wt% sodium bisulfate solution and three times with a 5wt% sodium bicarbonate solution.

4. The quaternized bile acid polyurethane modified polyvinyl chloride material according to claim 2, characterized in that: In the S12, the molecular weight of the double-terminated amino polyethylene glycol is 2000; the molar ratio of the bile acid activated ester, the double-terminated amino polyethylene glycol and the triethylamine is 1:0.5-5:1-5.

5. The quaternized bile acid polyurethane modified polyvinyl chloride material according to claim 2, characterized in that: In the S12, the organic solvents used for reaction and dilution include chloroform, dichloromethane, ethyl acetate and dimethyl sulfoxide; the reaction temperature is 25-50° C., the reaction time is 30-60 h; the concentration of the sodium bicarbonate solution is 2-10 wt %; the amount of the organic solvent used in the reaction is 6-12 times the mass of the bile acid activated ester, and the amount of the organic solvent used for dilution is 40-100 times the mass of the bile acid activated ester.

6. The quaternized bile acid polyurethane modified polyvinyl chloride material according to claim 2, characterized in that: In the S13, the organic solvent includes tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, xylene, toluene and dichloromethane, and the amount is 5 to 20 times the mass of CA-EG-PU; the ratio of the amount of triethylamine to CA-EG-PU is 2 to 6:1; bromoacetyl bromide is 40 times the molar amount of CA-EG-PU; the amount of tetrahydrofuran used for dissolution is 2 to 10 times the mass of CA-EG-PU; the reaction temperature is 10 to 30°C, and the reaction time is 15 to 25 hours; the amount of N,N-dimethylformamide is 10 to 30 times the mass of CA-EG-Br; the molar ratio of CA-EG-Br: trimethylamine is 1:10 to 50; the reaction temperature is 20 to 70°C, and the reaction time is 10 to 30 hours.

7. The quaternary ammonium bile acid polyurethane modified polyvinyl chloride material according to claim 1, characterized in that: The compatibilizer includes maleic anhydride grafted PE, maleic anhydride grafted POE, maleic anhydride grafted EVA and chlorinated polyethylene; the nanofiller includes wollastonite, calcium carbonate, barium sulfate and titanium dioxide; the coupling agent is one of the silane coupling agents; the plasticizer includes acrylate polymer copolymer, epoxy soybean oil and diisooctyl phthalate; the heat stabilizer includes methyl tin mercaptan, base heat stabilizer and calcium stearate; the lubricant includes polyethylene wax, paraffin and stearic acid; the antioxidant includes phosphite and hindered phenol; the pigment includes iron oxide brown and titanium dioxide; the light stabilizer includes benzotriazole, benzophenone, nickel dithiocarbamate salt, salicylate, hindered amine, thiobisphenol and zinc oxide.

8. The quaternized bile acid polyurethane modified polyvinyl chloride material according to claim 7, characterized in that: The acrylic ester polymer copolymers are methyl methacrylate / acrylate copolymers and acrylate / styrene copolymers; the salt-based heat stabilizers include salt-based lead acetate and salt-based calcium carbonate; the hindered phenols include bisphenol A, tri-tert-butylhydroxybenzene and di-tert-butyl-p-cresol; and the hindered amines include Tinuvin770 and Tinuvin765.

9. The method for preparing the quaternary ammonium bile acid polyurethane modified polyvinyl chloride material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S21, mixing polyvinyl chloride, polyurethane elastomer, compatibilizer, lubricant and coupling agent; Mix well in a grinder at 1000r / min for 1 to 3 minutes; S22, then adding a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a nanofiller, and a pigment, and mixing them to obtain a mixture; Each time a raw material is added, stir at 1000r / min for 1 to 3 minutes until it is evenly mixed; S23, refining the mixture and molding it; Extrusion process parameters: the refining temperature is 150-190°C, and the molding is performed using a molding machine at a molding temperature of 180-200°C.

10. The use of the quaternized bile acid polyurethane modified polyvinyl chloride material according to any one of claims 1 to 8, characterized in that: The quaternized bile acid polyurethane modified polyvinyl chloride material is used in water pipeline materials.

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