A skin-friendly antibacterial foaming material and its application in footwear products

Abstract

The present invention discloses a skin-friendly antibacterial foaming material and its application in footwear products, and relates to the technical field of polymer materials. When preparing the skin-friendly antibacterial foaming material, the present invention first reacts tetramethyltetravinylcyclotetrasiloxane and a flame retardant to obtain a flame-retardant cyclosiloxane, reacts 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride to obtain a capping agent, and the flame-retardant cyclosiloxane and octamethylcyclotetrasiloxane are ring-opening polymerized, the functionalized polysiloxane obtained by capping the end-capping agent, and then hollow silica is loaded with a foaming agent and grafted with chitosan quaternary ammonium salt; finally, polyetheramine, furan-2,5-dimethyl dicarboxylate, 3,5-diaminobenzenesulfonic acid, and dimethyl malonate are polymerized to obtain a modified polyamide, the modified polyamide and the functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt are blended and foamed to obtain the skin-friendly antibacterial foaming material. The skin-friendly antibacterial foaming material prepared by the invention has excellent flame retardant, antibacterial and self-repairing properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a skin-friendly antibacterial foaming material and application thereof in footwear products. Background Art

[0002] As people's demands for quality of life continue to rise, the comfort, skin-friendliness, and durability of footwear have become a focus of consumer attention. As one of the most important engineering plastics, polyamide foam has excellent mechanical and elastic properties and holds great promise in the footwear industry.

[0003] Traditional footwear materials, during long-term use, often face problems such as bacterial growth and varying degrees of wear and tear. These problems not only affect the service life of the shoes, but may also pose a potential threat to the wearer's health. In addition, in some usage environments, such as outdoor campfires and working environments under high temperature and high voltage, sparks can easily cause shoes to burn, posing a safety hazard. Therefore, the development of a new foam material that combines antibacterial, flame retardant and self-healing properties has become an important research direction in the field of footwear products. Summary of the Invention

[0004] The object of the present invention is to provide a skin-friendly antibacterial foaming material and its application in footwear products, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] The invention discloses a skin-friendly antibacterial foaming material, which is prepared by blending and foaming modified polyamide prepared by polymerization of polyetheramine, dimethyl furan-2,5-dicarboxylate, 3,5-diaminobenzenesulfonic acid and dimethyl malonate, functionalized polysiloxane, modified silicon dioxide and chitosan quaternary ammonium salt.

[0007] As an optimization, the functionalized polysiloxane is first obtained by reacting tetramethyltetravinylcyclotetrasiloxane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain flame-retardant cyclosiloxane, ring-opening polymerization of the flame-retardant cyclosiloxane and octamethylcyclotetrasiloxane, and then end-capping with a capping agent.

[0008] As an optimization, the capping agent is prepared by reacting 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride.

[0009] As an optimization, the modified silica is prepared by loading a foaming agent onto hollow silica, which is then modified with 3-aminopropyltriethoxysilane to obtain amino silica, reacting the amino silica with succinic anhydride to obtain carboxylated silica, which is then grafted with chitosan quaternary ammonium salt.

[0010] A method for preparing a skin-friendly antibacterial foaming material comprises the following steps:

[0011] (1) Tetramethyltetravinylcyclotetrasiloxane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and chloroform are mixed in a mass ratio of 1:(0.5-0.7):(20-30), heated to 65-70° C. and refluxed for 5-10 min, azobisisobutyronitrile (0.01-0.02 times the mass of tetramethyltetravinylcyclotetrasiloxane) is added, reacted for 6-7 h, chloroform is removed by vacuum rotary evaporation, and dried at 60° C. for 6-7 h to obtain a flame retardant cyclosiloxane;

[0012] (2) Octamethylcyclotetrasiloxane and flame retardant cyclosiloxane are mixed in a mass ratio of 1:(0.3-0.5), heated to 80°C under nitrogen protection, mixed for 1 hour, 0.02%-0.03% of the mass of octamethylcyclotetrasiloxane in a 25wt% tetramethylammonium hydroxide aqueous solution is added, and then 0.3%-0.4% of the mass of octamethylcyclotetrasiloxane in a blocking agent is added, and the temperature is continued to be raised to 110-120°C, reacted for 2-3 hours, and then continued to be heated to 150°C, reduced to 2-2.5KPa, and reacted for 3-4 hours to obtain functionalized polysiloxane;

[0013] (3) Under nitrogen protection, polyetheramine and 3,5-diaminobenzenesulfonic acid are mixed in a mass ratio of 1:(0.2-0.3) to obtain a diamine mixture, dimethyl malonate and dimethyl furan-2,5-dicarboxylate are mixed in a mass ratio of 1:(0.2-0.3) to obtain a diacid methyl ester mixture, and the diamine mixture and the diacid methyl ester mixture are stirred uniformly in a molar ratio of 1:1, wherein the molar ratio refers to the molar ratio of the amino group in the diamine mixture to the methyl ester group in the diacid methyl ester mixture, the stirring speed is 200-300 r / min, the reaction is carried out at 120° C. for 30-40 min, the temperature is raised to 230-240° C., and the reaction is carried out at 300 Pa for 2-2.5 h to obtain a modified polyamide;

[0014] (4) The supported silica and toluene are mixed in a mass ratio of 1:(50-60), ultrasonically dispersed at 40 Hz, 3-aminopropyltriethoxysilane (10-12 times the mass of the supported silica) is added, heated to 100-110°C, refluxed for 22-24 hours, cooled to room temperature, filtered and washed with pure water 3-4 times, and dried at 60°C for 6-8 hours to obtain amino silica; amino silica, succinic anhydride, 4-dimethylaminopyridine and dichloromethane are mixed in a mass ratio of 1:(3-4):(0.7-0.9):(100-150), stirred at room temperature for 10-12 hours, filtered and washed with ethanol 3-4 times, and dried at 60°C for 6-8 hours to obtain carboxylated silica;

[0015] (5) Carboxylated silica, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, and pure water were mixed at a mass ratio of 1:1:(150-160) for 30 minutes, N-hydroxysuccinimide of the same mass as the carboxylated silica was added and stirred for 30 minutes to obtain a silica dispersion, chitosan quaternary ammonium salt of the same mass as the carboxylated silica and pure water were stirred at a mass ratio of 1:(150-160) at 60°C for 5-6 hours, and then added to the silica dispersion, stirred at 60°C for 10-12 hours, cooled to room temperature, stirred for 10-12 hours, filtered, and dried at 60°C for 6-8 hours to obtain modified silica;

[0016] (6) The modified polyamide was ground into modified polyamide powder using a ball mill, wherein the diameter of the grinding balls in the ball mill was 6 mm, the grinding time was 10 h, the ball-to-material mass ratio was 1:(1.1-1.2), and the speed of the ball mill was 500-600 r / min; the modified polyamide powder was added to a torque rheometer at 60 r / min and 190 ° C and stirred for 1 min, and then functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt were added and kneaded for 6 min, and then the material was discharged and placed in a foaming mold, and the foaming mold was placed in a high-temperature foaming machine for foaming, and kept warm at 180 ° C and 11 MPa for 7 min before demolding to obtain a skin-friendly and antibacterial foaming material.

[0017] As an optimization, the preparation method of the end-capping agent in step (2) is as follows: under nitrogen protection, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride are weighed in a mass ratio of 1:(2.1-2.2), 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and toluene are mixed in a mass ratio of 1:(30-40) to obtain solution A, maleic anhydride and toluene are mixed in a mass ratio of 1:(50-60) to obtain solution B, solution B is added dropwise to solution A at a dropping rate of 6 mL / min, the reaction is carried out at room temperature for 1-1.5 h, and then the temperature is raised to 80° C., acetic anhydride with a mass of 0.7-0.9 times that of maleic anhydride and pyridine with a mass of 0.5-0.7 times that of maleic anhydride are added, the reaction is continued for 3-4 h, and toluene is removed by vacuum rotary evaporation to obtain the end-capping agent.

[0018] As an optimization, the preparation method of the loaded silica in step (4) is as follows: polystyrene microspheres, hexadecyltrimethylammonium bromide, 25wt% ammonia water, and anhydrous ethanol are mixed in a mass ratio of 1:(0.3-0.5):(10-12):(100-150), ultrasonicated at 40Hz for 50-60min, and then 5-6 times the mass of tetraethyl orthosilicate of the polystyrene microspheres is added. The mixture is stirred for 8-10h at room temperature, filtered, dried at 60°C for 4-6h, and then calcined at 500°C for 6h to obtain hollow silica; the hollow silica is immersed in a foaming agent solution, stirred for 30min, ultrasonicated at 40Hz for 10-20min, allowed to stand for 24h, filtered, washed with methanol 3-4 times, and dried at 60°C for 6-8h to obtain loaded silica.

[0019] As an optimization, the foaming agent solution is prepared by mixing azodicarbonamide and dimethyl sulfoxide in a mass ratio of 1:(15-17); and the particle size of the polystyrene microspheres is 3 μm.

[0020] As an optimization, the amounts of the modified polyamide powder, functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt in step (6) are: by mass, 100 parts of modified polyamide powder, 1-2 parts of functionalized polysiloxane, 3-5 parts of modified silica, and 3-5 parts of chitosan quaternary ammonium salt.

[0021] As an optimization, the chitosan quaternary ammonium salt in step (5) and step (6) is hydroxypropyltrimethylammonium chloride chitosan with a substitution degree of 98%.

[0022] As an optimization, the polyetheramine in step (3) is polypropylene glycol bis(2-aminopropyl ether) with a molecular weight of 2000.

[0023] The present invention also provides an application of the skin-friendly antibacterial foam material prepared according to the preparation method of the skin-friendly antibacterial foam material in footwear products.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] When preparing the skin-friendly antibacterial material, the present invention comprises the following steps: first, tetramethyltetravinylcyclotetrasiloxane and a flame retardant are reacted to obtain a flame-retardant cyclosiloxane; 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride are reacted to obtain a capping agent; the flame-retardant cyclosiloxane and octamethylcyclotetrasiloxane are ring-opening polymerized; and functionalized polysiloxane is obtained by capping with the capping agent; hollow silica is loaded with a foaming agent and grafted with chitosan quaternary ammonium salt; and finally, a modified polyamide obtained by polymerizing polyetheramine, furan-2,5-dimethyl dicarboxylate, 3,5-diaminobenzenesulfonic acid and dimethyl malonate, the functionalized polysiloxane, the modified silica and the chitosan quaternary ammonium salt are blended and foamed to obtain the skin-friendly antibacterial foaming material.

[0026] First, the carbon-carbon double bond on tetramethyltetravinylcyclotetrasiloxane reacts with the phosphorus-hydrogen bond of the flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to form a flame-retardant cyclosiloxane. The amino groups at both ends of 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride are amidated and dehydrated to form a maleimide-terminated siloxane. The flame-retardant cyclosiloxane, octamethylcyclotetrasiloxane, and maleimide-terminated siloxane react to form a maleimide-terminated polysiloxane. The side chain of the polysiloxane contains a flame-retardant functional monomer, which can give the material excellent flame retardant properties.

[0027] Then, the hollow silica is loaded with a foaming agent, and the surface of the silica is carboxylated by modification with a silane coupling agent and succinic anhydride, and then chitosan quaternary ammonium salt is grafted to give the material good antibacterial properties. Since the surface of the silica carries a positive charge, it can also attract the positive and negative charges with the modified polyamide with a sulfonic acid structure in the main chain, thereby enhancing the compatibility of the silica and polyamide and enhancing the dispersibility of the silica in the polyamide. Since the pure foaming agent itself has a large particle size and poor compatibility with polyamide, it will lead to excessive local gas emission and lack of nucleation points in the polymer matrix. The silica-loaded foaming agent can not only enhance the wear resistance of the material, but also improve the dispersion of the foaming agent in the polyamide. The hollow silica microspheres can also serve as nucleation points for bubbles, thereby improving the uniformity of foaming.

[0028] Finally, a modified polyamide (polyetheramine, furan-2,5-dicarboxylic acid dimethyl ester, 3,5-diaminobenzenesulfonic acid, and dimethyl malonate) was blended with functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt for foaming to produce a skin-friendly, antibacterial foam material. The furan groups in the modified polyamide backbone not only form dynamic, reversible covalent bonds with the maleimide groups at both ends of the functionalized polysiloxane, imparting self-healing properties to the material, but also introduce cross-linking structures, altering the linear molecular chain structure of the polyamide, increasing melt strength, and improving shrinkage during foaming. The chitosan quaternary ammonium salt exhibits excellent biocompatibility and affinity with human skin, conferring excellent skin-friendly properties to the material. DETAILED DESCRIPTION

[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0030] The chitosan quaternary ammonium salt used in all the following examples and comparative examples is hydroxypropyltrimethylammonium chloride chitosan with a degree of substitution of 98%; the polystyrene microspheres have a particle size of 3 μm; and the polyetheramine is polypropylene glycol bis(2-aminopropyl ether) with a molecular weight of 2000.

[0031] Example 1

[0032] A skin-friendly antibacterial foaming material, the preparation method is as follows:

[0033] (1) Tetramethyltetravinylcyclotetrasiloxane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and chloroform were mixed in a mass ratio of 1:0.5:20, heated to 70°C and refluxed for 10 minutes, azobisisobutyronitrile (0.01 times the mass of tetramethyltetravinylcyclotetrasiloxane) was added, reacted for 7 hours, chloroform was removed by vacuum rotary evaporation, and dried at 60°C for 7 hours to obtain a flame retardant cyclosiloxane;

[0034] (2) Under nitrogen protection, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride were weighed in a mass ratio of 1:2.1, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and toluene were mixed in a mass ratio of 1:30 to obtain solution A, maleic anhydride and toluene were mixed in a mass ratio of 1:50 to obtain solution B, solution B was added dropwise to solution A at a dropping speed of 6 mL / min, and the reaction was carried out at room temperature for 1.5 h, then the temperature was raised to 80°C, and acetic anhydride and maleic acid in an amount 0.7 times the mass of maleic anhydride were added. pyridine 0.5 times the mass of anhydride, continue to react for 4 hours, and remove toluene by vacuum rotary evaporation to obtain a blocking agent; octamethylcyclotetrasiloxane and flame retardant cyclosiloxane are mixed in a mass ratio of 1:0.3, under nitrogen protection, heated to 80°C, mixed for 1 hour, 25wt% tetramethylammonium hydroxide aqueous solution with a mass of 0.02% of octamethylcyclotetrasiloxane is added, and then 0.3% of the blocking agent by mass of octamethylcyclotetrasiloxane is added, and the temperature is continued to be raised to 120°C, reacted for 3 hours, and then continued to be heated to 150°C, reduced to 2.5KPa, and reacted for 4 hours to obtain functionalized polysiloxane;

[0035] (3) Under nitrogen protection, polyetheramine and 3,5-diaminobenzenesulfonic acid are mixed in a mass ratio of 1:0.2 to obtain a diamine mixture, dimethyl malonate and dimethyl furan-2,5-dicarboxylate are mixed in a mass ratio of 1:0.2 to obtain a diacid methyl ester mixture, and the diamine mixture and the diacid methyl ester mixture are stirred uniformly in a molar ratio of 1:1, wherein the molar ratio refers to the molar ratio of the amino group in the diamine mixture to the methyl ester group in the diacid methyl ester mixture, the stirring speed is 300 r / min, the reaction is carried out at 120° C. for 40 min, the temperature is raised to 240° C., and the reaction is carried out at 300 Pa for 2.5 h to obtain a modified polyamide;

[0036] (4) Azodicarbonamide and dimethyl sulfoxide were mixed in a mass ratio of 1:15 to obtain a foaming agent solution; polystyrene microspheres, hexadecyltrimethylammonium bromide, 25wt% ammonia water, and anhydrous ethanol were mixed in a mass ratio of 1:0.3:10:100, and after ultrasonication at 40 Hz for 60 min, ethyl orthosilicate (5 times the mass of the polystyrene microspheres) was added, and the mixture was stirred for 10 h at room temperature, filtered, dried at 60 ° C for 6 h, and calcined at 500 ° C for 6 h to obtain hollow silica; the hollow silica was immersed in the foaming agent solution, stirred for 30 min, ultrasonicated at 40 Hz for 20 min, allowed to stand for 24 h, filtered, and washed with methanol 4 times , dried at 60°C for 8h to obtain supported silica; the supported silica and toluene were mixed in a mass ratio of 1:50, ultrasonically dispersed at 40Hz, 3-aminopropyltriethoxysilane 10 times the mass of the supported silica was added, heated to 110°C, refluxed for 24h, cooled to room temperature, filtered and washed 4 times with pure water, and dried at 60°C for 8h to obtain amino silica; amino silica, succinic anhydride, 4-dimethylaminopyridine and dichloromethane were mixed in a mass ratio of 1:3:0.7:100, stirred at room temperature for 12h, filtered and washed 4 times with ethanol, and dried at 60°C for 8h to obtain carboxylated silica;

[0037] (5) Carboxylated silica, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, and pure water were mixed at a mass ratio of 1:1:150 for 30 minutes, N-hydroxysuccinimide of the same mass as the carboxylated silica was added and stirred for 30 minutes to obtain a silica dispersion, chitosan quaternary ammonium salt of the same mass as the carboxylated silica and pure water of the same mass ratio of 1:150 were stirred at 60°C for 6 hours, and then added to the silica dispersion, stirred at 60°C for 12 hours, cooled to room temperature, stirred for 12 hours, filtered, and dried at 60°C for 8 hours to obtain modified silica;

[0038] (6) The modified polyamide was ground into modified polyamide powder using a ball mill, wherein the diameter of the grinding balls in the ball mill was 6 mm, the grinding time was 10 h, the ball-to-material mass ratio was 1:1.1, and the speed of the ball mill was 600 r / min; 100 parts of modified polyamide powder, 1 part of functionalized polysiloxane, 3 parts of modified silica, and 3 parts of chitosan quaternary ammonium salt were weighed by mass; the modified polyamide powder was added to a torque rheometer at 60 r / min and 190 ° C and stirred for 1 min, and then functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt were added and kneaded for 6 min, then the material was discharged and placed in a foaming mold, and the foaming mold was placed in a high-temperature foaming machine for foaming. After being kept warm at 180 ° C and 11 MPa for 7 min, the mold was demolded to obtain a skin-friendly and antibacterial foaming material.

[0039] Example 2

[0040] A skin-friendly antibacterial foaming material, the preparation method is as follows:

[0041] (1) Tetramethyltetravinylcyclotetrasiloxane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and chloroform were mixed in a mass ratio of 1:0.6:25, heated to 67°C and refluxed for 8 minutes, azobisisobutyronitrile (0.015 times the mass of tetramethyltetravinylcyclotetrasiloxane) was added, reacted for 6.5 hours, chloroform was removed by vacuum rotary evaporation, and dried at 60°C for 6.5 hours to obtain a flame retardant cyclosiloxane;

[0042] (2) Under nitrogen protection, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride were weighed in a mass ratio of 1:2.15, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and toluene were mixed in a mass ratio of 1:35 to obtain solution A, maleic anhydride and toluene were mixed in a mass ratio of 1:55 to obtain solution B, solution B was added dropwise to solution A at a dropping rate of 6 mL / min, and the reaction was carried out at room temperature for 1.3 h, then the temperature was raised to 80°C, and acetic anhydride (0.8 times the mass of maleic anhydride) and maleic anhydride (0.05 times the mass of maleic anhydride) were added. .6 times of pyridine, continue to react for 3.5 hours, and remove toluene by vacuum rotary evaporation to obtain a blocking agent; octamethylcyclotetrasiloxane and flame retardant cyclosiloxane are mixed in a mass ratio of 1:0.4, under nitrogen protection, heated to 80°C, mixed for 1 hour, 0.025% by weight of octamethylcyclotetrasiloxane of 25wt% tetramethylammonium hydroxide aqueous solution, and then 0.35% by weight of octamethylcyclotetrasiloxane of the blocking agent are added, and the temperature is continued to be raised to 115°C, reacted for 2.5 hours, and then continued to be heated to 150°C, reduced pressure to 2.3KPa, and reacted for 3.5 hours to obtain functionalized polysiloxane;

[0043] (3) Under nitrogen protection, polyetheramine and 3,5-diaminobenzenesulfonic acid are mixed at a mass ratio of 1:0.25 to obtain a diamine mixture, dimethyl malonate and dimethyl furan-2,5-dicarboxylate are mixed at a mass ratio of 1:0.25 to obtain a diacid methyl ester mixture, and the diamine mixture and the diacid methyl ester mixture are stirred uniformly at a molar ratio of 1:1, wherein the molar ratio refers to the molar ratio of the amino group in the diamine mixture to the methyl ester group in the diacid methyl ester mixture, the stirring speed is 250 r / min, the reaction is carried out at 120° C. for 35 min, the temperature is raised to 235° C., and the reaction is carried out at 300 Pa for 2.3 h to obtain a modified polyamide;

[0044] (4) Azodicarbonamide and dimethyl sulfoxide were mixed in a mass ratio of 1:16 to obtain a foaming agent solution; polystyrene microspheres, hexadecyltrimethylammonium bromide, 25wt% ammonia water, and anhydrous ethanol were mixed in a mass ratio of 1:0.4:11:125, and ultrasonicated at 40 Hz for 55 min, and then 5.5 times the mass of polystyrene microspheres of tetraethyl orthosilicate was added. The mixture was stirred and reacted for 9 h at room temperature, filtered, dried at 60 ° C for 5 h, and calcined at 500 ° C for 6 h to obtain hollow silica; the hollow silica was immersed in the foaming agent solution, stirred for 30 min, ultrasonicated at 40 Hz for 15 min, allowed to stand for 24 h, filtered, and washed with methanol 3 times , dried at 60 ° C for 7 hours to obtain supported silica; the supported silica and toluene were mixed in a mass ratio of 1:55, ultrasonically dispersed at 40 Hz, 3-aminopropyltriethoxysilane 11 times the mass of the supported silica was added, heated to 105 ° C, refluxed for 23 hours, cooled to room temperature, filtered and washed 3 times with pure water, and dried at 60 ° C for 7 hours to obtain amino silica; amino silica, succinic anhydride, 4-dimethylaminopyridine and dichloromethane were mixed in a mass ratio of 1:3.5:0.8:125, stirred at room temperature for 11 hours, filtered and washed 4 times with ethanol, and dried at 60 ° C for 7 hours to obtain carboxylated silica;

[0045] (5) Carboxylated silica, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, and pure water were mixed at a mass ratio of 1:1:155 for 30 minutes, N-hydroxysuccinimide of the same mass as the carboxylated silica was added and stirred for 30 minutes to obtain a silica dispersion, chitosan quaternary ammonium salt of the same mass as the carboxylated silica and pure water of the same mass ratio of 1:155 were stirred at 60°C for 5.5 hours, and then added to the silica dispersion, stirred at 60°C for 11 hours, cooled to room temperature, stirred for 11 hours, filtered, and dried at 60°C for 7 hours to obtain modified silica;

[0046] (6) The modified polyamide was ground into modified polyamide powder using a ball mill, wherein the diameter of the grinding balls in the ball mill was 6 mm, the grinding time was 10 h, the ball-to-material mass ratio was 1:1.15, and the speed of the ball mill was 550 r / min; 100 parts of modified polyamide powder, 1.5 parts of functionalized polysiloxane, 4 parts of modified silica, and 4 parts of chitosan quaternary ammonium salt were weighed by mass; the modified polyamide powder was added to a torque rheometer at 60 r / min and 190 ° C and stirred for 1 min, and then functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt were added and kneaded for 6 min, then the material was discharged and placed in a foaming mold, and the foaming mold was placed in a high-temperature foaming machine for foaming. After being kept warm at 180 ° C and 11 MPa for 7 min, the mold was demolded to obtain a skin-friendly antibacterial foaming material.

[0047] Example 3

[0048] A skin-friendly antibacterial foaming material, the preparation method is as follows:

[0049] (1) Tetramethyltetravinylcyclotetrasiloxane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and chloroform were mixed in a mass ratio of 1:0.7:30, heated to 65°C and refluxed for 5 minutes, azobisisobutyronitrile (0.02 times the mass of tetramethyltetravinylcyclotetrasiloxane) was added, reacted for 6 hours, chloroform was removed by vacuum rotary evaporation, and dried at 60°C for 6 hours to obtain a flame retardant cyclosiloxane;

[0050] (2) Under nitrogen protection, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride were weighed in a mass ratio of 1:2.2, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and toluene were mixed in a mass ratio of 1:40 to obtain solution A, maleic anhydride and toluene were mixed in a mass ratio of 1:60 to obtain solution B, solution B was added dropwise to solution A at a dropping speed of 6 mL / min, reacted at room temperature for 1 h, then heated to 80°C, and acetic anhydride and maleic acid in an amount 0.9 times the mass of maleic anhydride were added. 0.7 times the mass of pyridine anhydride, continue to react for 3 hours, and remove toluene by vacuum rotary evaporation to obtain a blocking agent; octamethylcyclotetrasiloxane and flame retardant cyclosiloxane are mixed in a mass ratio of 1:0.5, under nitrogen protection, heated to 80°C, mixed for 1 hour, 0.03% of the mass of octamethylcyclotetrasiloxane in a 25wt% tetramethylammonium hydroxide aqueous solution, and then 0.4% of the mass of octamethylcyclotetrasiloxane The blocking agent is added and continued to heat to 110°C, react for 2 hours, continue to heat to 150°C, reduce the pressure to 2KPa, and react for 3 hours to obtain functionalized polysiloxane;

[0051] (3) Under nitrogen protection, polyetheramine and 3,5-diaminobenzenesulfonic acid are mixed in a mass ratio of 1:0.3 to obtain a diamine mixture, dimethyl malonate and dimethyl furan-2,5-dicarboxylate are mixed in a mass ratio of 1:0.3 to obtain a diacid methyl ester mixture, and the diamine mixture and the diacid methyl ester mixture are stirred uniformly in a molar ratio of 1:1, wherein the molar ratio refers to the molar ratio of the amino group in the diamine mixture to the methyl ester group in the diacid methyl ester mixture, the stirring speed is 200 r / min, the reaction is carried out at 120° C. for 30 min, the temperature is raised to 230° C., and the reaction is carried out at 300 Pa for 2 h to obtain a modified polyamide;

[0052] (4) Azodicarbonamide and dimethyl sulfoxide were mixed in a mass ratio of 1:17 to obtain a foaming agent solution; polystyrene microspheres, hexadecyltrimethylammonium bromide, 25wt% ammonia water, and anhydrous ethanol were mixed in a mass ratio of 1:0.5:12:150, and after ultrasonication at 40 Hz for 50 min, ethyl orthosilicate (6 times the mass of the polystyrene microspheres) was added, and the mixture was stirred for 8 h at room temperature, filtered, dried at 60 ° C for 4 h, and calcined at 500 ° C for 6 h to obtain hollow silica; the hollow silica was immersed in the foaming agent solution, stirred for 30 min, ultrasonicated at 40 Hz for 10 min, allowed to stand for 24 h, filtered, and washed with methanol 3 times , dried at 60 ° C for 6 hours to obtain supported silica; the supported silica and toluene were mixed in a mass ratio of 1:60, ultrasonically dispersed at 40 Hz, 3-aminopropyltriethoxysilane 12 times the mass of the supported silica was added, heated to 100 ° C, refluxed for 22 hours, cooled to room temperature, filtered and washed with pure water 3 times, and dried at 60 ° C for 6 hours to obtain amino silica; amino silica, succinic anhydride, 4-dimethylaminopyridine and dichloromethane were mixed in a mass ratio of 1:4:0.9:150, stirred at room temperature for 10 hours, filtered and washed with ethanol 3 times, and dried at 60 ° C for 6 hours to obtain carboxylated silica;

[0053] (5) Carboxylated silica, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, and pure water were mixed at a mass ratio of 1:1:160 for 30 minutes, N-hydroxysuccinimide of the same mass as the carboxylated silica was added and stirred for 30 minutes to obtain a silica dispersion, chitosan quaternary ammonium salt of the same mass as the carboxylated silica and pure water of the same mass ratio of 1:160 were stirred at 60°C for 5 hours, and then added to the silica dispersion, stirred at 60°C for 10 hours, cooled to room temperature, stirred for 10 hours, filtered, and dried at 60°C for 6 hours to obtain modified silica;

[0054] (6) The modified polyamide was ground into modified polyamide powder using a ball mill, wherein the diameter of the grinding balls in the ball mill was 6 mm, the grinding time was 10 h, the ball-to-material mass ratio was 1:1.2, and the speed of the ball mill was 500 r / min; 100 parts of modified polyamide powder, 2 parts of functionalized polysiloxane, 5 parts of modified silica, and 5 parts of chitosan quaternary ammonium salt were weighed by mass; the modified polyamide powder was added to a torque rheometer at 60 r / min and 190 ° C and stirred for 1 min, and then functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt were added and kneaded for 6 min, then the material was discharged and placed in a foaming mold, and the foaming mold was placed in a high-temperature foaming machine for foaming. After being kept warm at 180 ° C and 11 MPa for 7 min, the mold was demolded to obtain a skin-friendly and antibacterial foaming material.

[0055] Comparative Example 1

[0056] The difference between Comparative Example 1 and Example 2 is that step (1) is not included, and step (3) is modified as follows: under nitrogen protection, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride are weighed in a mass ratio of 1:2.15, 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and toluene are mixed in a mass ratio of 1:35 to obtain solution A, maleic anhydride and toluene are mixed in a mass ratio of 1:55 to obtain solution B, solution B is added dropwise to solution A at a dropping rate of 6 mL / min, the reaction is carried out at room temperature for 1.3 h, and then the temperature is raised to 80°C. Add acetic anhydride in an amount of 0.8 times the mass of maleic anhydride and pyridine in an amount of 0.6 times the mass of maleic anhydride, continue the reaction for 3.5 hours, and remove toluene by rotary evaporation under reduced pressure to obtain a capping agent; under nitrogen protection, heat octamethylcyclotetrasiloxane to 80°C, stir for 1 hour, add 25wt% tetramethylammonium hydroxide aqueous solution in an amount of 0.025% by mass of octamethylcyclotetrasiloxane, and then add 0.35% by mass of the capping agent of octamethylcyclotetrasiloxane, continue to heat to 115°C, react for 2.5 hours, continue to heat to 150°C, reduce the pressure to 2.3KPa, and react for 3.5 hours to obtain a functionalized polysiloxane.

[0057] Comparative Example 2

[0058] The difference between Comparative Example 2 and Example 2 is that step (5) is not included, and step (4) is modified as follows: azodicarbonamide and dimethyl sulfoxide are mixed in a mass ratio of 1:16 to obtain a foaming agent solution; polystyrene microspheres, hexadecyltrimethylammonium bromide, 25wt% ammonia water, and anhydrous ethanol are mixed in a mass ratio of 1:0.4:11:125, and after ultrasonication at 40 Hz for 55 min, 5.5 times the mass of polystyrene microspheres of tetraethyl orthosilicate are added, and the reaction is stirred for 9 h at room temperature. After filtering and drying at 60 ° C for 5 h, the mixture is calcined at 500 ° C for 6 h to obtain hollow silica; the hollow silica is immersed in the foaming agent solution, stirred for 30 min, ultrasonicated at 40 Hz for 15 min, allowed to stand for 24 h, filtered, washed three times with methanol, and dried at 60 ° C for 7 h to obtain modified silica.

[0059] Comparative Example 3

[0060] The difference between Comparative Example 3 and Example 2 is that step (2) is modified as follows: octamethylcyclotetrasiloxane and flame retardant cyclosiloxane are mixed in a mass ratio of 1:0.4, heated to 80°C under nitrogen protection, mixed for 1 hour, 25wt% tetramethylammonium hydroxide aqueous solution with a mass of 0.025% of octamethylcyclotetrasiloxane is added, and then 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane with a mass of 0.35% of octamethylcyclotetrasiloxane is added, and the temperature is continued to be raised to 115°C, reacted for 2.5 hours, and then heated to 150°C, reduced to 2.3KPa, and reacted for 3.5 hours to obtain functionalized polysiloxane.

[0061] Test Example 1

[0062] Flame retardant performance test

[0063] Test method: The limiting oxygen index of the foamed materials prepared in each embodiment and comparative example was tested according to ASTM D2863. The results are shown in Table 1.

[0064] Table 1

[0065] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 31.77 Comparative Example 1 22.43 Example 2 30.41 Comparative Example 2 31.36 Example 3 32.12 Comparative Example 3 30.69

[0066] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the skin-friendly antibacterial foam material prepared in the present invention has good flame retardant properties.

[0067] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 1, indicating that the carbon-carbon double bond on tetramethyltetravinylcyclotetrasiloxane reacts with the phosphine-hydrogen of the flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to form a flame-retardant cyclosiloxane, and the flame-retardant cyclosiloxane, octamethylcyclotetrasiloxane and maleimide-terminated siloxane react to form a polysiloxane. The side chain of the polysiloxane contains a flame-retardant functional monomer, which can give the material excellent flame retardant properties.

[0068] Test Example 2

[0069] Self-healing performance testing

[0070] Test Method: All examples and comparative examples were prepared according to GB / 6344-2008. The tensile strength of the samples was measured, denoted as η0. The samples were then cut, the cross sections aligned, and heated at 70°C for 30 minutes. The tensile strength was then measured again, denoted as η1. The self-healing efficiency, W, was calculated using the following formula: W = (η1 / η0) * 100%. The results are shown in Table 2.

[0071] Table 2

[0072] Self-repair efficiency (%) Self-repair efficiency (%) Example 1 95.41 Comparative Example 1 94.57 Example 2 94.67 Comparative Example 2 95.24 Example 3 95.11 Comparative Example 3 0

[0073] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the skin-friendly antibacterial foaming material prepared in the present invention has good self-repairing properties.

[0074] By comparison, the self-healing efficiency of Examples 1 to 3 was greater than that of Comparative Example 3, indicating that the modified polyamide prepared by polymerizing polyetheramine, dimethyl furan-2,5-dicarboxylate, 3,5-diaminobenzenesulfonic acid, and dimethyl malonate with functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt can produce a skin-friendly, antibacterial foam material. The furan groups in the modified polyamide backbone form dynamic, reversible covalent bonds with the maleimide groups at both ends of the functionalized polysiloxane, imparting self-healing properties to the material.

[0075] Test Example 3

[0076] Antibacterial performance testing

[0077] Test Method: The skin-friendly antibacterial foam materials prepared in the Examples and Comparative Examples were tested for their antibacterial rates using the shaking flask method according to the 2002 edition of the National Technical Specifications for Disinfection. Staphylococcus aureus was selected as the bacterial species. The results are shown in Table 3.

[0078] Table 3

[0079] Antibacterial rate / % Antibacterial rate / % Example 1 95.47 Comparative Example 1 96.04 Example 2 96.21 Comparative Example 2 32.41 Example 3 95.84 Comparative Example 3 95.31

[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 3, it can be found that the skin-friendly antibacterial foaming material prepared in the present invention has good antibacterial properties.

[0081] By comparison, the antibacterial rates of Examples 1 to 3 are better than that of Comparative Example 2, indicating that the hollow silica is loaded with a foaming agent, the surface of the silica is carboxylated by a silane coupling agent and succinic anhydride modification, and then chitosan quaternary ammonium salt is grafted thereon, giving the material good antibacterial properties.

[0082] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A skin-friendly antibacterial foaming material, characterized in that: The preparation method of the material is as follows: (1) Tetramethyltetravinylcyclotetrasiloxane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and chloroform are mixed in a mass ratio of 1:(0.5-0.7):(20-30), heated to 65-70°C and refluxed for 5-10 minutes, azobisisobutyronitrile (0.01-0.02 times the mass of tetramethyltetravinylcyclotetrasiloxane) is added, the reaction is continued for 6-7 hours, chloroform is removed by vacuum rotary evaporation, and the mixture is dried at 60°C for 6-7 hours to obtain a flame retardant cyclosiloxane; (2) Under nitrogen protection, weigh 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and maleic anhydride in a mass ratio of 1:(2.1-2.2), mix 1,3-bisaminopropyl-1,1,3,3-tetramethyldisiloxane and toluene in a mass ratio of 1:(30-40) to obtain solution A, mix maleic anhydride and toluene in a mass ratio of 1:(50-60) to obtain solution B, add solution B dropwise to solution A at a dropping rate of 6 mL / min, react at room temperature for 1-1.5 h, then heat to 80 ° C, add acetic anhydride (0.7-0.9 times the mass of maleic anhydride) and 0.5 times the mass of maleic anhydride. -0.7 times of pyridine, continue to react for 3-4 hours, and remove toluene by vacuum rotary evaporation to obtain a blocking agent; octamethylcyclotetrasiloxane and flame retardant cyclosiloxane are mixed in a mass ratio of 1: (0.3-0.5), and under nitrogen protection, the temperature is raised to 80°C, mixed for 1 hour, and 0.02%-0.03% of the mass of octamethylcyclotetrasiloxane is added. 25wt% tetramethylammonium hydroxide aqueous solution, and then 0.3%-0.4% of the mass of octamethylcyclotetrasiloxane is added. The blocking agent is continued to be heated to 110-120°C, reacted for 2-3 hours, and then continued to be heated to 150°C, reduced to 2-2.5KPa, and reacted for 3-4 hours to obtain functionalized polysiloxane; (3) Under nitrogen protection, polyetheramine and 3,5-diaminobenzenesulfonic acid are mixed in a mass ratio of 1:(0.2-0.3) to obtain a diamine mixture, dimethyl malonate and dimethyl furan-2,5-dicarboxylate are mixed in a mass ratio of 1:(0.2-0.3) to obtain a diacid methyl ester mixture, and the diamine mixture and the diacid methyl ester mixture are stirred uniformly in a molar ratio of 1:1, wherein the molar ratio refers to the molar ratio of the amino group in the diamine mixture to the methyl ester group in the diacid methyl ester mixture, the stirring speed is 200-300 r / min, the reaction is carried out at 120°C for 30-40 min, the temperature is raised to 230-240°C, and the reaction is carried out at 300 Pa for 2-2.5 h to obtain a modified polyamide; (4) Polystyrene microspheres, hexadecyltrimethylammonium bromide, 25wt% ammonia water, and anhydrous ethanol were mixed in a mass ratio of 1:(0.3-0.5):(10-12):(100-150), and after ultrasonication at 40 Hz for 50-60 min, 5-6 times the mass of polystyrene microspheres of ethyl orthosilicate was added. The mixture was stirred for 8-10 h at room temperature, filtered, dried at 60 ° C for 4-6 h, and calcined at 500 ° C for 6 h to obtain hollow silica; the hollow silica was immersed in a foaming agent solution and stirred for 30 min. The foaming agent solution was prepared by mixing azodicarbonamide and dimethyl sulfoxide in a mass ratio of 1:(15-17); ultrasonication was carried out at 40 Hz for 10-20 min, and the mixture was allowed to stand for 24 h. The mixture was filtered and washed with methanol 3-4 times, and dried at 60 ° C for 6-8 h to obtain supported silica; The supported silica and toluene are mixed in a mass ratio of 1:(50-60), and the mixture is uniformly dispersed by ultrasonication at 40 Hz. 3-aminopropyltriethoxysilane (10-12 times the mass of the supported silica) is added, and the mixture is heated to 100-110° C., refluxed for 22-24 hours, cooled to room temperature, filtered, washed with pure water 3-4 times, and dried at 60° C. for 6-8 hours to obtain amino silica; the amino silica, succinic anhydride, 4-dimethylaminopyridine, and dichloromethane are mixed in a mass ratio of 1:(3-4):(0.7-0.9):(100-150), stirred at room temperature for 10-12 hours, filtered, washed with ethanol 3-4 times, and dried at 60° C. for 6-8 hours to obtain carboxylated silica; (5) Carboxylated silica, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, and pure water were mixed at a mass ratio of 1:1:(150-160) for 30 minutes, N-hydroxysuccinimide of the same mass as the carboxylated silica was added and stirred for 30 minutes to obtain a silica dispersion, chitosan quaternary ammonium salt of the same mass as the carboxylated silica and pure water were stirred at a mass ratio of 1:(150-160) at 60°C for 5-6 hours, and then added to the silica dispersion, stirred at 60°C for 10-12 hours, cooled to room temperature, stirred for 10-12 hours, filtered, and dried at 60°C for 6-8 hours to obtain modified silica; (6) The modified polyamide was ground into modified polyamide powder using a ball mill, wherein the diameter of the grinding balls in the ball mill was 6 mm, the grinding time was 10 h, the ball-to-material mass ratio was 1:(1.1-1.2), and the speed of the ball mill was 500-600 r / min; the modified polyamide powder was added to a torque rheometer at 60 r / min and 190 °C and stirred for 1 min, and then functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt were added and kneaded for 6 min, then the material was discharged and placed in a foaming mold, and the foaming mold was placed in a high-temperature foaming machine for foaming. After being kept warm at 180 °C and 11 MPa for 7 min, the material was demolded to obtain a skin-friendly and antibacterial foaming material.

2. The skin-friendly antibacterial foaming material according to claim 1, characterized in that: The particle size of the polystyrene microspheres is 3 μm.

3. The skin-friendly antibacterial foaming material according to claim 1, characterized in that: The amount of the modified polyamide powder, functionalized polysiloxane, modified silica, and chitosan quaternary ammonium salt used in step (6) is as follows: 100 parts by mass of modified polyamide powder, 1-2 parts by mass of functionalized polysiloxane, 3-5 parts by mass of modified silica, and 3-5 parts by mass of chitosan quaternary ammonium salt.

4. The skin-friendly antibacterial foaming material according to claim 1, characterized in that: The chitosan quaternary ammonium salt in step (5) and step (6) is hydroxypropyltrimethylammonium chloride chitosan with a degree of substitution of 98%.

5. The skin-friendly antibacterial foaming material according to claim 1, characterized in that: The polyetheramine in step (3) is polypropylene glycol bis(2-aminopropyl ether) with a molecular weight of 2000.

6. Use of the skin-friendly antibacterial foaming material according to any one of claims 1 to 5 in footwear.