Bactericidal flame-retardant additive

Abstract

The invention relates to a bactericidal flame-retardant additive, which is characterized in that polyguanidine is used as a bactericidal functional main body, and water-insoluble polyguanidine organic acid salt is prepared by carrying out salt forming reaction on guanidyl and organic acid with flame-retardant property; the water-insoluble polyguanidine organic acid salt is used as an additive of a polymer product, and the polymer product with bactericidal and flame-retardant functions is prepared through solution or melt mixing processing molding.

Description

Technical Field

[0001] The invention relates to an additive with bactericidal and flame-retardant functions, belonging to a functional additive for polymer products. Background Art

[0002] The development of polymer products with bactericidal function has become another hot spot in the industry. At present, the main ways to make polymer products acquire bactericidal function are through monomer copolymerization modification and adding bactericides. The latter has become a common method due to its wide application range and quick effect. The bactericides that can be added to polymer products mainly include inorganic antibacterial agents and organic antibacterial agents. Inorganic antibacterial agents include nanomaterials of specific metals and their compounds and nanocarbon materials, such as nanosilver, nanocopper, graphene, etc. Their scope of application is often limited, and due to limited compatibility with polymers, the addition amount is not high and there are problems of loss, and there are risks such as environmental damage. Organic antibacterial agents mainly include cationic antibacterial agents containing quaternary ammonium salts, such as DC-5700, which are used for the surface treatment of polymer products such as cellulose with active hydroxyl groups and amino groups. There are currently few varieties and cannot meet the strong market demand. In recent years, polyguanidine disinfectants have been widely used in the sterilization of various water bodies due to their advantages such as high efficiency, non-toxicity, and a wide spectrum of bactericidal activity. They have antibacterial effects on Gram-positive and Gram-negative bacteria as well as fungi. The -NH and -NH2 in the guanidine group can dissociate into ammonium cations in water, bind to microbial cell membrane proteins, inhibit the synthesis of liposomes in the membrane, cause bacterial apoptosis, and achieve sterilization. Polyguanidine is often made into small molecule salts for sale. It is a small molecule inorganic acid salt of a series of oligomers with guanidine groups on the main chain of the molecule. The main commercial varieties include polyhexamethylene monoguanidine, polyhexamethylene biguanide, and polyaminopropyl biguanide. The small molecule inorganic acids are mainly hydrochloric acid, phosphoric acid, and gluconic acid. Polyguanidine salts are easily soluble in water, while pure polyguanidine is easily disturbed by environmental factors and cannot exist stably in solid polymer products. Therefore, water-insoluble polyguanidine derivatives are developed to allow them to stay in polymer products for a long time, which is expected to obtain efficient bactericides that can be added to polymer products, giving polymer products long-term bactericidal functions. In the field of polymer synthesis, organic acids and organic ammonia are often used to react to prepare water-insoluble salts, such as the salt-forming reaction of adipic acid and hexamethylenediamine. Therefore, a water-insoluble organic acid-polyguanidine salt can be obtained by reacting an organic acid with a large hydrophobic part with polyguanidine to form a salt. At the same time, guanidine-containing compounds themselves have flame retardancy and can be used to make water-soluble flame retardant products, and polyguanidine is naturally flame retardant due to its high density of NH groups. If an organic acid, a synthetic precursor of an organic flame retardant, is selected to treat polyguanidine, a polymer additive with a composite flame retardant and bactericidal function can be prepared, which can be used to prepare polymer products with long-lasting bactericidal and flame retardant functions.

[0003] Therefore, the present invention selects a reactive flame retardant precursor organic acid and a water-soluble polyguanidine salt for salt-forming reaction to obtain a water-insoluble organic acid-polyguanidine salt, which is applied to the production and processing of polymers to obtain a polymer product with long-lasting antibacterial and flame-retardant functions. Summary of the invention

[0004] The purpose of the present invention is to prepare a bactericidal flame retardant additive in view of the deficiencies of the prior art.

[0005] The technical solution of the present invention is summarized as follows:

[0006] 1. A bactericidal flame retardant additive, characterized in that polyguanidine is used as the main body of bactericidal function, and a water-insoluble polyguanidine organic acid salt is prepared by a salt-forming reaction between a guanidine group and an organic acid with flame retardant properties; the water-insoluble polyguanidine organic acid salt is used as an additive for polymer products, and is processed and formed by solution or melt mixing to obtain a polymer product with bactericidal flame retardant function;

[0007] The polyguanidine is one or more of polyhexamethyleneguanidine (I), polyhexamethylenebiguanidine (II) and polyaminopropylbiguanide (III), and its chemical structure is as follows:

[0008]

[0009] The organic acid having flame retardant properties is one or more of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (IV), diphenylphosphinate (V) and 2-carboxyethylphenylphosphinate (VII), and its chemical structure is as follows:

[0010]

[0011] In the above structural formula, R1=C n H 2n+1 , R2=C n H 2n+1 , n is an integer between 0 and 4, and the positions of R1 and R2 on the benzene ring are ortho, meta or para to the hypophosphite group;

[0012] The salt-forming reaction is to dissolve the organic acid with flame retardant properties in one or more of solvent water, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and / or N-methylpyrrolidone, and react with a water-soluble polyguanidine salt aqueous solution to obtain a water-insoluble polyguanidine salt; the water-soluble polyguanidine salt includes one or more of hydrochloride, phosphate, gluconate, sulfate, nitrate, carbonate, sulfite, formates and acetates;

[0013] The polymer is one or more of polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, polyacrylonitrile, polyetheretherketone, polyvinyl chloride, polyethylene, polyethylene-vinyl acetate, polyethylene-vinyl alcohol, polypropylene, polystyrene, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polycarbonate, polystyrene-butadiene-acrylonitrile, polymethyl methacrylate, polyamide-6, polyamide-8, polyamide-66, polyamide-10, polyamide-610, polyamide-1010, polyamide-1212, polyamide-6T, epoxy resin, and polyurethane;

[0014] The solvent used in the mixed solution is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, acetone, ethyl acetate, tetrahydrofuran, toluene, xylene, dichloromethane, chloroform and carbon tetrachloride.

[0015] 2. According to claim 1, in the salt-forming reaction of the polyguanidine with the organic acid having flame retardant properties, the molar ratio of the NH group or NH2 group in the polyguanidine to the acid radical group in the acid is 0.8 to 1.1:1;

[0016] The mass ratio of the bactericidal flame retardant additive to the polymer when mixed is 0.4-15; 85-99.6. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a photo of a culture dish showing colony growth on pure polypropylene film in an E. coli sterilization experiment; Figure 2 Photo of the culture dish showing the colony growth of pure polysulfone membrane in the Staphylococcus aureus bactericidal experiment; Figure 3 This is a photo of the culture dish showing the colony growth of sample 1 in the E. coli sterilization experiment in Example 9; Figure 4 This is a photo of the culture dish showing the colony growth of sample 2 in the E. coli sterilization experiment in Example 10; Figure 5 This is a photo of the culture dish showing the colony growth of sample 3 in the E. coli sterilization experiment; Figure 6 This is a photo of the colony growth culture dish of sample 4 in the Staphylococcus aureus bactericidal experiment; Figure 7 This is a photo of the colony growth culture dish of sample 5 in the Staphylococcus aureus bactericidal experiment; Figure 8 This is a photo of the culture dish showing the colony growth of sample 6 in the E. coli sterilization experiment; Fig. 9 This is a photo of the culture dish showing the colony growth of sample 7 in the E. coli sterilization experiment; Fig.10 This is a photo of the colony growth culture dish of sample 8 in the E. coli sterilization experiment. Example

[0018] Synthesis of Hydrophobic Polyguanidine

[0019] Example 1

[0020] 2.9 g of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (IV) was mixed with 25 mL of N-methylpyrrolidone and added to a solution prepared by 6 g of polyhexamethyleneguanidine (I) hydrochloride and 53 g of water. The mixture was stirred for 6 h, and the white solid was collected by filtration. The filter cake was washed with pure water for 3 times and dried under vacuum at 40°C to obtain 5.1 g of a white solid with a yield of 52.4%, which was recorded as product 1.

[0021] Example 2

[0022] 66g of polyhexamethylene biguanide (II) nitrate aqueous solution with a mass concentration of 25wt% was added dropwise to a mixture of 2-carboxyethylphenylphosphorous acid (VII, 3.9g) and 35mL N,N-dimethylformamide. The mixture was stirred for 4h, and the white solid was collected by filtration. The filter cake was washed with pure water 3 times, and the filter cake was vacuum dried at 50°C to obtain 12.3g of white solid with a yield of 55.2%, which was recorded as product 2.

[0023] Example 3

[0024] Mix di(2-methyl)phenylphosphorous acid (V, 8 g) with 70 g of N,N-dimethylacetamide, add a solution prepared by 20 g of polyaminopropyl biguanide (III) sulfate, 5 g of polyhexamethylene biguanide (II) sulfate and 150 g of water, and stir for 6 h. Filter the white solid and wash it three times with pure water. Dry the filter cake under vacuum at 40°C to obtain 17.5 g of white solid with a yield of 56.5%, which is recorded as product 3.

[0025] Example 4

[0026] 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (IV, 4 g), di(3-methyl)phenylphosphite (V, 4 g) were mixed with 80 g of water and 20 g of N,N-dimethylacetamide, and a solution prepared by 10 g of polyhexamethyleneguanidine (I) hydrochloride and 100 g of water was added, and stirred for 6 h. The white solid was filtered and washed with pure water for 3 times, and the filter cake was vacuum dried at 40°C to obtain 8.5 g of white solid with a yield of 47.2%, which was recorded as product 4.

[0027] Example 5

[0028] 12g of diphenylphosphite (V) was mixed with 60mL of N,N-dimethylformamide, and 65g of polyhexamethyleneguanidine (I) hydrochloride aqueous solution with a content of 15wt% was added. The mixture was stirred for 5h, filtered, and the filter cake was washed with pure water for 3 times. The filter cake was dried under vacuum at 40°C to obtain 9.4g of a white solid with a yield of 43.4%, which was recorded as product 5.

[0029] Example 6

[0030] 90g of di(4-methyl)phenylphosphite (V) was mixed with 300mL of N,N-dimethylacetamide, and 600mL of 20wt% polyhexamethylene biguanide (II) phosphate aqueous solution was added. The mixture was stirred for 4h, filtered and washed with pure water for 3 times, and the filter cake was dried under vacuum at 50°C to obtain 92g of a white solid with a yield of 53.9%, which was recorded as product 6.

[0031] Example 7

[0032] 70g of di(4-tert-butyl)phenylphosphite (V) was mixed with 300mL of water, and 600mL of a mixed aqueous solution of polyhexamethyleneguanidine (I) gluconate and polyhexamethylenebiguanide (II) gluconate with a content of 20wt% was added. The mixture was stirred for 4h, filtered and washed with pure water for 3 times, and the filter cake was dried under vacuum at 50°C to obtain 92g of a white solid with a yield of 48.4%, which was recorded as product 7.

[0033] Example 8

[0034] 50g of diphenylphosphite (V), 45g of 2-carboxyethylphenylphosphite (VII) and 500g of dimethyl sulfoxide were mixed, and 1000g of polyaminopropyl biguanide (III) sulfate aqueous solution with a mass concentration of 10% was added, and stirred for 6h. The white solid was filtered, and the filter cake was washed with pure water for 3 times, and the filter cake was vacuum dried at 40°C to obtain 96g of white solid with a yield of 50.5%, which was recorded as product 8.

[0035] Mixed processing of bactericidal flame retardants and polymers

[0036] Example 9

[0037] 8.54 g of polysulfone and 0.26 g of the product 1 in Example 1 were dissolved in 31.2 g of N, N-dimethylformamide, stirred at room temperature for 24 h until completely dissolved, and allowed to stand at room temperature for degassing for 12 h. The degassed mixed solution was poured onto a clean glass plate, a 200 μm thick film was scraped off, the film was immersed in pure water to solidify into a film, rinsed, and then immersed in pure water for storage to obtain a polysulfone ultrafiltration membrane with a sterilization function, which was recorded as sample 1.

[0038] Example 10

[0039] 5g of product 2 in Example 2, 2g of product 3 in Example 3, 1400g of polypropylene resin particles and an appropriate amount of antioxidant were fully stirred and mixed, added to the feed port of a twin-screw extruder, granulated under the conditions of a screw speed of 50r / min, a feed port temperature of 200°C, a feed cooling temperature of 30°C, and a pelletizer speed of 11.4r / min, and the slices were dried by blast at 60°C for 5h to obtain a sterilization masterbatch. The sterilization masterbatch was heated and melted, and a hollow fiber membrane with an outer diameter of 1.2mm and an inner diameter of 0.8mm was prepared by a melt spinning film making machine and washed with pure water to obtain a polypropylene hollow fiber membrane with a sterilization function, which was recorded as sample 2.

[0040] Embodiment 11

[0041] 48 g of product 3 in Example 3, 1200 g of nylon-6 and an appropriate amount of antioxidant are fully stirred and mixed, and spun through a melt spinneret at a feed port temperature of 285°C, a mold heating of 295°C and a cooling temperature of 35°C. The fiber felt is collected and cleaned to obtain a nylon-6 melt-blown non-woven fabric with a sterilization function, which is recorded as Sample 3.

[0042] Example 12

[0043] 25g of product 4 in Example 4, 100g of product 7 in Example 7 and 1600g of polyethylene-vinyl alcohol resin were melt-extruded by a twin screw, and pelletized under the conditions of screw speed 60r / min, feed port temperature 180°C, feed cooling temperature 25°C, and pelletizer speed 11.5r / min. The masterbatch was dried at 50°C for 6h. The dried masterbatch was scraped by a melt scraping machine to prepare a polyethylene-vinyl alcohol film with a sterilization function, which was recorded as sample 4.

[0044] Embodiment 13

[0045] 90 g of product 5 in Example 5 and 1500 g of nylon-66 were dissolved in 4 L of formic acid to prepare a spinning solution, which was allowed to stand for degassing. The solution was added to a syringe and placed on the propulsion pump of an electrospinning machine for electrospinning. The fiber felt was collected and dried to obtain a nylon-66 non-woven fabric with a bactericidal function, which was recorded as sample 5.

[0046] Embodiment 14

[0047] 240g of polyvinylidene fluoride was dissolved in a mixed solvent of 1600g of N, N-dimethylacetamide and N-methylpyrrolidone (volume ratio 3:1), stirred at room temperature for 12h until completely dissolved, and a mixed powder of 20g of product 6 in Example 6 and 5g of product 8 in Example 8 was added to the system, stirred for 6h until product 6 and polyvinylidene fluoride were completely mixed, and left to stand at room temperature for degassing for 12h. The mixed solution after degassing was transferred to a solution spinning kettle, and a hollow fiber membrane was spun using pure water as a coagulation bath and water as a core liquid. The polyvinylidene fluoride hollow fiber membrane with bactericidal function was obtained by washing with pure water, which was recorded as sample 6.

[0048] Embodiment 15

[0049] 80g of product 7 in Example 7 and 1300g of polystyrene-butadiene-acrylonitrile were fully stirred and added to a twin-screw extruder for extrusion granulation. The processing parameters were a feed port temperature of 210°C, a feed cooling temperature of 25°C, and a pelletizer speed of 12.5r / min. The masterbatch was dried at 40°C for 5h. The dried masterbatch was scraped by a melt scraping machine to prepare a polystyrene-butadiene-acrylonitrile film with a sterilization function, which was recorded as sample 7.

[0050] Example 16

[0051] 40g of product 1 in Example 1, 40g of product 8 in Example 8 and 1000g of polyacrylonitrile were dissolved in 4L of dimethyl sulfoxide to prepare a spinning solution, vacuum degassing was performed, and the spinning solution was poured into the storage kettle of the solution spinning machine, and dry-wet spinning was performed with water as a coagulation bath. The fibers were collected by winding and washed to obtain polyacrylonitrile fibers with bactericidal function, which was recorded as sample 8.

[0052] Flame retardant performance test of additives

[0053] Embodiment 15

[0054] 100g of product 1 in Example 1 was mixed evenly with 1000g of polypropylene in a mixer, and melt-plasticized and extruded by a twin-screw extruder to prepare a flame retardant modified masterbatch. The prepared masterbatch was made into a specimen by an injection molding machine for flame retardant testing. The combustion grade of the specimen was tested by a UL-94 combustion tester. The limiting oxygen index of pure polypropylene was 18.6%, and the limiting oxygen index after modification was 26.5%.

[0055] Example 16

[0056] 100g of product 3 in Example 3, 100g of product 4 in Example 4 and 25g of product 6 in Example 6 were mixed with 1500g of nylon 6 and stirred for 20 minutes, melt-plasticized and extruded by a twin-screw extruder to prepare a flame-retardant modified masterbatch. The prepared masterbatch was made into a specimen by an injection molding machine for flame retardant testing. The flame retardant properties of the specimen were tested using a UL-94 combustion test machine. The limiting oxygen index of pure nylon 6 was 23.4%, and the limiting oxygen index after modification was 31.2%.

Claims

1. A bactericidal flame retardant additive, characterized in that polyguanidine is used as the main body of bactericidal function, and a water-insoluble polyguanidine organic acid salt is prepared by a salt-forming reaction between a guanidine group and an organic acid with flame retardant properties; the water-insoluble polyguanidine organic acid salt is used as an additive for polymer products, and is processed and formed by solution or melt mixing to obtain a polymer product with bactericidal flame retardant function; The polyguanidine is one or more of polyhexamethyleneguanidine (I), polyhexamethylenebiguanidine (II) and polyaminopropylbiguanide (III), and its chemical structure is as follows: The organic acid having flame retardant properties is one or more of 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (IV), diphenylphosphinate (V) and 2-carboxyethylphenylphosphinate (VII), and its chemical structure is as follows: In the above structural formula, R1=C n H 2n+1 , R2=C n H 2n+1 , n is an integer between 0 and 4, and the positions of R1 and R2 on the benzene ring are ortho, meta or para to the hypophosphite group; The salt-forming reaction is to dissolve the organic acid with flame retardant properties in one or more of solvent water, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and / or N-methylpyrrolidone, and react with a water-soluble polyguanidine salt aqueous solution to obtain a water-insoluble polyguanidine salt; the water-soluble polyguanidine salt includes one or more of hydrochloride, phosphate, gluconate, sulfate, nitrate, carbonate, sulfite, formates and acetates; The polymer is one or more of polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinylidene chloride, polytetrafluoroethylene, polyacrylonitrile, polyetheretherketone, polyvinyl chloride, polyethylene, polyethylene-vinyl acetate, polyethylene-vinyl alcohol, polypropylene, polystyrene, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polycarbonate, polystyrene-butadiene-acrylonitrile, polymethyl methacrylate, polyamide-6, polyamide-8, polyamide-66, polyamide-10, polyamide-610, polyamide-1010, polyamide-1212, polyamide-6T, epoxy resin, and polyurethane; The solvent used in the mixed solution is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, acetone, ethyl acetate, tetrahydrofuran, toluene, xylene, dichloromethane, chloroform and carbon tetrachloride.

2. According to claim 1, in the salt-forming reaction of the polyguanidine with the organic acid having flame retardant properties, the molar ratio of the NH group or NH2 group in the polyguanidine to the acid radical group in the acid is 0.8 to 1.1:1; The mass ratio of the bactericidal flame retardant additive to the polymer when mixed is 0.4-15:85-99.6.

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