Antibacterial super absorbent resin composite material and preparation method thereof
阅读说明：本技术 一种抗菌高吸水树脂复合材料及其制备方法 (Antibacterial super absorbent resin composite material and preparation method thereof ) 是由 陈洪祥 姜明君 殷敬华 于许杰 邢玉珊 马兰波 于 2021-10-15 设计创作，主要内容包括：本发明提供了一种抗菌高吸水树脂复合材料及其制备方法,该复合材料包括：高分子胍类抗菌剂0.2～2重量份；单链小分子季铵盐抗菌剂0.1～2重量份；双链小分子季铵盐抗菌剂0.1～2重量份；高吸水树脂94～99.6重量份；经共混复合、干燥工序制得。本发明通过抗菌剂的筛选与复配,提供了与高吸水树脂体系相容性好的抗菌剂复配物,该抗菌剂复配物易溶于水,利用高吸水树脂的吸水特性,将抗菌成分成功均匀复合入高吸水树脂内部。该抗菌剂复配物在高吸水树脂基体中能发挥出协同抗菌的作用,少量添加即有优异的杀菌效果,成本低廉。该抗菌高吸水树脂复合材料生产工艺简单,具有优异的抗菌功能性,且不会对原树脂的吸收性能带来不利影响。(The invention provides an antibacterial super absorbent resin composite material and a preparation method thereof, wherein the composite material comprises the following components: 0.2-2 parts by weight of a macromolecular guanidine antibacterial agent; 0.1-2 parts by weight of a single-chain small-molecule quaternary ammonium salt antibacterial agent; 0.1-2 parts by weight of a double-chain small-molecule quaternary ammonium salt antibacterial agent; 94-99.6 parts by weight of super absorbent resin; the material is prepared through the procedures of blending, compounding and drying. The invention provides the antibacterial agent compound with good compatibility with a super absorbent resin system through screening and compounding of the antibacterial agent, the antibacterial agent compound is easy to dissolve in water, and the antibacterial components are successfully and uniformly compounded into the super absorbent resin by utilizing the water absorption characteristic of the super absorbent resin. The antibacterial agent compound can play a role in synergistic antibacterial action in a super absorbent resin matrix, has excellent bactericidal effect when added in a small amount, and is low in cost. The antibacterial super absorbent resin composite material is simple in production process, has excellent antibacterial function, and does not bring adverse effects on the absorption performance of the original resin.)
1. An antibacterial super absorbent resin composite material, characterized by comprising:
2. the composite material of claim 1, wherein the polymeric guanidine antibacterial agent is selected from one or more of polyhexamethylene guanidine phosphate, polyhexamethylene guanidine hydrochloride, polyhexamethylene guanidine stearate, polyhexamethylene guanidine propionate, polyhexamethylene biguanide hydrochloride, polyaminopropyl biguanide, chitosan guanidine hydrochloride, or chitosan biguanide hydrochloride;
the super absorbent resin is selected from one of starch grafted acrylonitrile resin, starch grafted acrylic acid resin, starch grafted acrylamide resin, polyvinyl alcohol resin, polyacrylic acid (salt) resin, polyacrylamide resin, fiber grafted acrylonitrile resin, fiber grafted acrylic acid resin and fiber grafted acrylamide resin.
3. The composite material of claim 1, wherein the single chain small molecule quaternary ammonium salt antimicrobial agent is selected from one or more of benzyldimethyl [2- [2- [4- (1,1,3, 3-tetramethylbutyl) phenoxy ] ethoxy ] ethyl ] ammonium chloride, alkyl (C12-C18) dimethylbenzyl ammonium chloride, dodecyldimethylbenzyl ammonium bromide, alkyl (C12-C18) dimethylethylbenzylammonium chloride, octadecyldimethyl [3- (trimethoxysilyl) propyl ] ammonium chloride, octadecyltrimethyl ammonium chloride, dodecyltrimethylammonium chloride, hexadecylpyridinium chloride, or hexadecyltrimethylammonium bromide.
4. The composite material of claim 1, wherein the double-stranded small molecule quaternary ammonium salt is selected from one or more of bis-octyl dimethyl ammonium chloride, bis-octyl dimethyl ammonium bromide, bis-quinyl dimethyl ammonium chloride, bis-quinyl dimethyl ammonium bromide, or bis-dodecyl dimethyl ethylene diamine bromide.
5. A method for preparing the antibacterial super absorbent resin composite material as claimed in any one of claims 1 to 4, comprising:
A) mixing a macromolecular guanidine antibacterial agent, a single-chain micromolecular quaternary ammonium salt antibacterial agent, a double-chain micromolecular quaternary ammonium salt antibacterial agent and a solvent, and stirring to obtain an antibacterial agent mixed solution;
B) and blending and compounding the super absorbent resin and the mixed solution of the antibacterial agent, and drying to obtain the antibacterial super absorbent resin composite material.
6. The preparation method according to claim 5, wherein the mass ratio of the polymeric guanidine antibacterial agent, the single-chain small molecular quaternary ammonium salt antibacterial agent, the double-chain small molecular quaternary ammonium salt antibacterial agent and the solvent in the step A) is (0.67-20): (0.33-20): (0.33-20): (40 to 98.67).
7. The method according to claim 6, wherein the solvent in step A) is a mixture of water and ethanol; wherein, the weight ratio of the ethanol to the solvent is 5-20%.
8. The preparation method of claim 5, wherein the stirring temperature in the step A) is 5-30 ℃, the stirring speed is 500-3000 r/min, and the stirring time is 5-15 min.
9. The method according to claim 5, wherein the mixed solution of the antibacterial agent in step B) accounts for 5 to 30% by mass of the super absorbent resin.
10. The preparation method according to claim 5, wherein the compounding process in the step B) is to use equipment to spray the mixed antibacterial agent solution into the super absorbent resin matrix by pressure spraying;
the equipment for producing the antibacterial super absorbent resin composite material has a material fluidization function and a pressurized spraying device, and is selected from one of a boiling granulator or a high-efficiency coating machine; the liquid inlet speed of the mixed liquid of the antibacterial agent is 100-2000 mL/min, the spraying pressure is 0.1-0.5 MPa, the air inlet temperature is 60-90 ℃, the air outlet temperature is 40-80 ℃, and the mixing time is 30-120 min.
Technical Field
The invention relates to the technical field of materials, in particular to an antibacterial super absorbent resin composite material and a preparation method thereof.
Background
The super absorbent resin is a high molecular substance which contains strong hydrophilic groups such as hydroxyl, carboxyl and the like and has a moderately cross-linked three-dimensional network structure, and is widely applied to the field of disposable sanitary products, such as sanitary towels, paper diapers, nursing pads, diapers and the like. The super absorbent resin is generally produced by using an unsaturated vinyl monomer (e.g., acrylonitrile, acrylic acid and its salts, acrylamide, etc.) as a raw material, adding a crosslinking agent and an initiator, synthesizing a hydrogel through polymerization, and drying and pulverizing the hydrogel, and it is preferable to use resin particles having a particle diameter in the range of 150 μm or more and less than 850 μm. When the super absorbent resin meets water, water molecules are hydrated with a large number of hydrophilic groups on a polymer chain through hydrogen bonds, the hydrophilic groups begin to dissociate, the number of anions is increased, the super absorbent resin presents the property of polyelectrolyte, and the super absorbent resin can absorb water which is hundreds of times of the self weight. When the super absorbent resin is used, a large amount of body fluid and urine of a human body can be absorbed, and bacteria are easy to grow under proper temperature and humidity. With the high performance of disposable sanitary products, the super absorbent resin is also required to have some special functions, such as antibacterial function.
At present, the antibacterial modification method for the super absorbent resin mainly comprises a chemical synthesis method and a blending modification method. The chemical synthesis method is to add an antibacterial functional component in the synthesis stage of the hydrogel so that the antibacterial functional component is combined with the super absorbent resin matrix through the action of chemical bonds to achieve the aim of antibacterial modification. The Chinese patent application 201910932244.6 discloses a method for preparing antibacterial high-molecular water-absorbent resin, wherein the method uses acrylic acid as a polymerization monomer, chitosan as a doped antibacterial material, and graphite oxide as a grafting material, and the bactericidal rate of the prepared high-molecular water-absorbent resin is 83%. The antibacterial component is firmly combined in the matrix through chemical bonds by the method, and the defects of the method are mainly shown in that the preparation process needs free radical polymerization, the process condition requirement is higher, the batch stable production difficulty of products is higher, and the antibacterial rate is not high. The Chinese patent application 201911071287.6 discloses a method for preparing antibacterial salt-tolerant high-molecular water-absorbent resin, which is an antibacterial salt-tolerant high-molecular water-absorbent resin material prepared by acrylic acid polymerization initiated by free radicals, can separate and eliminate various inorganic salt components in urine, quickly discharge moisture and hot air, is dry and comfortable, inhibits bacteria, and prevents red buttocks of infants. The defects are mainly shown in that the process condition requirement of free radical initiation acrylic acid polymerization is high, the complex graphene antibacterial composition needs to be prepared, and the difficulty in realizing mass production is high. In addition, the invention of adding silver antibacterial agent in the process of synthesizing the super absorbent resin, such as Chinese patent application CN201410658347.5, and the nano silver antibacterial agent is added in the process of secondary crosslinking, so that the antibacterial super absorbent resin with excellent bactericidal effect is obtained. Although the antibacterial property of the silver ions is strong, the silver ions can be accumulated in a human body, so that potential safety risks exist; in addition, the material is easy to yellow after silver ions are added, and a polluting reducing agent is required to be used in the synthesis process, which limits the practical application of the silver-based antibacterial material. The chemical synthesis method generally has the defects of complicated production process, high cost, poor absorption performance and the like.
The blending modification of the high-molecular water-absorbent resin is to compound through the action of physical bonds (hydrogen bonds, electrostatic interaction, adsorption and the like), introduce functional modified substances into a high-molecular water-absorbent resin material matrix through a certain method and endow the material with functionality. The Chinese patent application 202010608979.6 discloses a preparation method of an antibacterial super absorbent resin, which realizes the compounding of an antibacterial agent and a super absorbent resin matrix by utilizing the adsorption effect of the super absorbent resin on a water phase system, and the method is simple to operate, but due to the compatibility problem of antibacterial components and the super absorbent resin matrix, a better antibacterial effect can be achieved only by adding a higher content of the antibacterial agent, for example, in the embodiment, the mass fraction of the added antibacterial agent is even up to 50%, and the obtained antibacterial super absorbent resin is high in cost, so that the practical application of the antibacterial super absorbent resin is limited.
Therefore, in order to solve one or more technical problems in the prior art, it is necessary to provide an antibacterial super absorbent resin composite material, which has good compatibility of each component, low addition amount of antibacterial components, excellent antibacterial performance, high safety and low cost.
Disclosure of Invention
In view of the above, the invention provides an antibacterial super absorbent resin composite material and a preparation method thereof, and the antibacterial super absorbent resin composite material provided by the invention has good compatibility of each component and excellent antibacterial functionality.
The invention provides an antibacterial super absorbent resin composite material, which comprises the following components:
0.2-2 parts by weight of a macromolecular guanidine antibacterial agent;
0.1-2 parts by weight of a single-chain small-molecule quaternary ammonium salt antibacterial agent;
0.1-2 parts by weight of a double-chain small-molecule quaternary ammonium salt antibacterial agent;
94-99.6 parts by weight of super absorbent resin;
the invention provides an antibacterial super absorbent resin composite material, which comprises 0.2-2 parts by weight of a macromolecular guanidine antibacterial agent; specifically, it may be 0.5 parts by weight, 1 part by weight, or 2 parts by weight, or a point value between any two of the above.
The polymeric guanidine antibacterial agents preferred in the present invention are readily soluble in water (solubility >100g/L), and may be polymeric monoguanidine antibacterial agents or polymeric biguanide antibacterial agents. The sterilization mechanism of the guanidine high-molecular polymer mainly comprises: strong cation guanidino group can be adsorbed on a negatively charged bacterial cell membrane through electrostatic interaction, and generates ion exchange with calcium and magnesium ions in the cell membrane, so that the structure of the cell membrane is damaged; secondly, the high molecular polymer can form a layer of film to seal the breathing passage of bacteria, thereby achieving the purpose of killing the bacteria.
The macromolecular guanidine antibacterial agent is selected from one or more of polyhexamethylene guanidine phosphate, polyhexamethylene guanidine hydrochloride, polyhexamethylene guanidine stearate, polyhexamethylene guanidine propionate, polyhexamethylene biguanide hydrochloride, polyaminopropyl biguanide, chitosan guanidine hydrochloride or chitosan biguanide hydrochloride.
The invention provides an antibacterial super absorbent resin composite material, which comprises 0.1-2 parts by weight of a single-chain small-molecule quaternary ammonium salt antibacterial agent; specifically, it may be 0.5 parts by weight, 1 part by weight, or 2 parts by weight, or a point value between any two of the above.
In the quaternary ammonium salt antibacterial agent, the cationic quaternary ammonium groups with positive charges can be selectively adsorbed by bacteria, and penetrate through the surface to enter cell membranes through the permeation and diffusion effects, so that the semi-permeation effect of the cell membranes is blocked, and the cationic quaternary ammonium groups further penetrate into cells to achieve the sterilization purpose.
The single-chain small-molecule quaternary ammonium salt antibacterial agent is easy to dissolve in water (solubility)>100 g/L). The single-chain small molecule quaternary ammonium salt antibacterial agent contains a quaternary ammonium group connected with C12～C18Preferably from benzyldimethyl [2- [2- [4- (1,1,3, 3-tetramethylbutyl) phenoxy ] 2]Ethoxy radical]Ethyl radical]Ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, dodecyl dimethyl ethyl benzyl ammonium chloride, octadecyl dimethyl [3- (trimethoxysilyl) propyl ] methyl]One or more of ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, hexadecyl pyridine ammonium chloride and hexadecyl trimethyl ammonium bromide; in the examples of the present invention, benzyldimethyl [2- [2- [4- (1,1,3, 3-tetramethylbutyl) phenoxy ] can be specifically selected]Ethoxy radical]Ethyl radical]Ammonium chloride, dodecyldimethylbenzylammonium bromide, and cetylpyridinium chloride.
The invention provides an antibacterial super absorbent resin composite material, which comprises 0.1-2 parts by weight of a double-chain small molecular quaternary ammonium salt antibacterial agent; specifically, it may be 0.5 parts by weight, 1 part by weight, or 2 parts by weight, or a point value between any two of the above.
The double-chain small-molecule quaternary ammonium salt antibacterial agent is easy to dissolve in water (solubility)>100 g/L). The double-chain small molecular quaternary ammonium salt antibacterial agent contains two quaternary ammonium groups, wherein the two quaternary ammonium groups are respectively connected with a C8～C12The carbon chain of (b) is preferably one or more selected from the group consisting of dioctyldimethylammonium chloride, dioctyldimethylammonium bromide, diquinoyldimethylammonium chloride, diquinoyldimethylammonium bromide and didodecyldimethylethylenediamine bromide. In the embodiment of the present invention, bis-quinyldimethylammonium chloride, bis-quinyldimethylammonium bromide, and bis-dodecyl-dimethylethylenediamine bromide may be specifically selected.
The invention provides an antibacterial super absorbent resin composite material which comprises 94-99.6 parts by weight of super absorbent resin.
The super absorbent resin is selected from one of starch grafted acrylonitrile, starch grafted acrylic acid, starch grafted acrylamide, polyvinyl alcohol, polyacrylic acid (salt), polyacrylamide, fiber grafted acrylonitrile, fiber grafted acrylic acid and fiber grafted acrylamide super absorbent resin.
The invention also provides a preparation method of the antibacterial super absorbent resin composite material, which comprises the following steps:
A) mixing a macromolecular guanidine antibacterial agent, a single-chain micromolecular quaternary ammonium salt antibacterial agent, a double-chain micromolecular quaternary ammonium salt antibacterial agent and a solvent, and stirring to obtain an antibacterial agent mixed solution;
B) and blending and compounding the super absorbent resin and the mixed solution of the antibacterial agent, and drying to obtain the antibacterial super absorbent resin composite material.
The antibacterial super absorbent resin composite material provided by the invention is prepared by mixing a macromolecular guanidine antibacterial agent, a single-chain micromolecular quaternary ammonium salt antibacterial agent, a double-chain micromolecular quaternary ammonium salt antibacterial agent and a solvent, and stirring to obtain an antibacterial agent mixed solution.
In the antibacterial agent mixed solution, the mass ratio of the high-molecular guanidine antibacterial agent, the single-chain small-molecular quaternary ammonium salt antibacterial agent, the double-chain small-molecular quaternary ammonium salt antibacterial agent and the solvent is preferably (0.67-20): (0.33-20): (0.33-20): (40-98.67); more preferably (1-18): (1-15): (1-13): (42-90);
the weight percentage of the high molecular guanidine antibacterial agent in the antibacterial agent mixed solution is preferably 0.67-20%; more preferably 1% to 18%; most preferably 1.5 to 15%.
In some embodiments provided in the present invention, the weight percentage of the polymeric guanidine antibacterial agent in the antibacterial agent mixture is preferably 2%; in some embodiments provided in the present invention, the weight percentage of the polymeric guanidine antibacterial agent in the antibacterial agent mixture is preferably 4.2%; in some embodiments provided in the present invention, the amount of the polymeric guanidine antimicrobial agent in the antimicrobial mixture is preferably 6% by weight.
The single-chain small molecular quaternary ammonium salt antibacterial agent in the antibacterial agent mixed solution accounts for 0.33-20% preferably; more preferably 1% to 15%; most preferably 1.3% to 10%.
In some embodiments provided in the present invention, the single-chain small-molecule quaternary ammonium salt preferably accounts for 1.3% of the weight of the antibacterial agent mixed solution; in some embodiments provided in the present invention, the single-chain small-molecule quaternary ammonium salt preferably accounts for 2% by weight of the antibacterial agent mixed solution; in some embodiments provided in the present invention, the single-chain small-molecule quaternary ammonium salt is preferably 6% by weight of the antibacterial agent mixed solution.
The weight percentage of the double-chain small molecular quaternary ammonium salt antibacterial agent in the antibacterial agent mixed solution is 0.33-20%. In some embodiments provided herein, the double-chain small molecule quaternary ammonium salt is preferably 1% to 13% by weight; most preferably 1% to 10%.
In some embodiments provided in the present invention, the double-chain small-molecule quaternary ammonium salt preferably accounts for 1% by weight of the antibacterial agent mixed solution; in some embodiments provided in the present invention, the double-chain small-molecule quaternary ammonium salt preferably accounts for 1.3% of the weight of the antibacterial agent mixed solution; in some embodiments provided in the present invention, the double-chain small-molecule quaternary ammonium salt preferably accounts for 3% by weight of the antibacterial agent mixed solution.
According to the invention, the antibacterial agent combination of the macromolecular guanidine antibacterial agent, the single-chain micromolecular quaternary ammonium salt and the double-chain micromolecular quaternary ammonium salt can exert a synergistic antibacterial effect in a super absorbent resin system, and the excellent antibacterial effect can be shown with low addition amount.
The solvent is a mixed solution of water and ethanol; wherein, the weight ratio of the ethanol to the solvent is 5-20%.
According to the invention, by using a mixed solvent of ethanol and water and selecting production equipment with fluidization and drying functions, the aggregation phenomenon caused after the resin particles absorb the water solution can be effectively avoided, and the antibacterial agent can be uniformly compounded into the super absorbent resin particles, so that the antibacterial super absorbent resin composite material can be obtained by one-step treatment.
The water in the solvent may be one of purified water, deionized water and soft water. The mixed solution of the antibacterial agent can be prepared by the conventional method in the field. Adding a high-molecular guanidine antibacterial agent, a single-chain small-molecular quaternary ammonium salt antibacterial agent and a double-chain small-molecular quaternary ammonium salt antibacterial agent with the formula weight into a solvent, stirring to a clear state, wherein the stirring temperature is preferably 5-30 ℃, the stirring speed is preferably 500-3000 r/min, and the stirring time is preferably 5-15 min. The micromolecule single-chain and double-chain quaternary ammonium salt antibacterial agent selected by the invention is easy to dissolve in water, but a large amount of bubbles are generated in the stirring and mixing process, and the adverse effect is caused in the compounding process between the antibacterial agent mixed solution and the super absorbent resin. The ethanol has certain capacity of eliminating bubbles, and the proper amount of the ethanol can reduce the phenomenon of large amount of bubbles in the stirring process without influencing the basic properties of the mixed liquid system of the antibacterial agent. In some embodiments provided herein, the ethanol comprises 8% by weight of the mixed solvent; in some embodiments provided herein, the ethanol comprises 10% by weight of the mixed solvent; in some embodiments provided herein, the ethanol comprises 12% by weight of the mixed solvent.
And compounding the super absorbent resin and the antibacterial agent mixed solution, and drying to obtain the antibacterial super absorbent resin composite material. The compounding process in the step B) is realized by production equipment, and specifically, the antibacterial agent mixed solution is compounded into the super absorbent resin matrix through pressure spraying.
The addition amount of the antibacterial agent mixed solution is preferably 5-30% of the weight ratio of the super absorbent resin matrix; more preferably 7% to 30%; most preferably 8% to 30%.
The antibacterial super absorbent resin composite material is compounded by taking a solvent as a medium, and the aim of uniform compounding cannot be achieved when the addition amount of an antibacterial agent mixed solution is too small; and if the amount is too large, aggregation of resin particles is caused and energy consumption is increased.
In some embodiments provided by the invention, the addition amount of the antibacterial agent mixed solution accounts for 10% of the weight ratio of the super absorbent resin matrix; in some embodiments provided by the invention, the addition amount of the antibacterial agent mixed solution accounts for 20% of the weight ratio of the super absorbent resin matrix; in some embodiments of the present invention, the antimicrobial mixture is added in an amount of 30% by weight of the superabsorbent resin matrix.
The production equipment has material fluidization function and a pressurized spraying device, can be standardized production equipment or modified production equipment without changing basic principles, and particularly can be a boiling granulator or a high-efficiency coating machine. A boiling granulator or a high-efficiency coating machine is mainly applied to the pharmaceutical industry, the basic principle of the technology is that powder materials are put into a hopper closed container, the powder is suspended to flow in a fluidized circulation mode under the action of hot air flow, uniform mixing is achieved, meanwhile, a mist-shaped binder is sprayed to wet the powder in the container, the powder is condensed into loose small particles, and the powder is efficiently dried by the hot air flow during granulation, so that moisture is continuously evaporated, the powder is continuously solidified to form ideal and uniform multi-micropore spherical particles, and three processes of mixing, granulating and drying are completed in the container at one time. In the present invention, the mixing and drying functions of the apparatus are mainly used. The super absorbent resin particles are fluidized in the container, and the mixed solution of the antibacterial agent is changed into fine atomized dispersed liquid drops through a pressure spraying system to collide and contact with the fluidized super absorbent resin particles. When the super absorbent resin is in contact with water, water molecules are hydrated with a large number of hydrophilic groups on a polymer chain through hydrogen bonds, so that water is rapidly absorbed into the resin, resin particles can swell and become sticky after absorbing water, and aggregation among the particles can be caused due to excessive local water absorption. In order to avoid the situation, the invention uses a mixed solvent of water and ethanol, the ethanol and the water are tightly combined through hydrogen bond action, and the strength of the mixed solvent is greater than the strength of the hydrogen bond between the super absorbent resin and the water, so that the mixed solution of the antibacterial agent can not quickly absorb the solution when contacting the super absorbent resin, but is uniformly dispersed on the surfaces of the resin particles; by utilizing the characteristic of different volatility of water and ethanol, when the antibacterial agent mixed solution is contacted with the resin particles, the ethanol is quickly evaporated under the action of hot air flow, so that the super absorbent resin particles uniformly absorb the residual antibacterial agent mixed solution; under the action of hot air flow, the water content is continuously evaporated, and finally the uniform composition of the antibacterial component and the super absorbent resin matrix is realized.
According to the invention, preferably, the liquid inlet speed of the antibacterial agent mixed liquid is 100-2000 mL/min, the spraying pressure is 0.1-0.5 MPa, the air inlet temperature is preferably 40-100 ℃, the air outlet temperature is preferably 40-80 ℃, and the treatment time is preferably 30-100 min. In the compounding process, the liquid inlet speed and the air inlet temperature of the mixed liquid of the antibacterial agent are key influencing factors. Too fast liquid inlet speed can increase aggregation among particles, too slow can prolong treatment time and increase energy consumption, and the liquid inlet speed is more preferably 300-1500 mL/min, and is more preferably 500-1000 mL/min. The evaporation speed of ethanol in the mixed solvent can be slowed down when the air inlet temperature is too low, the water can be evaporated too fast when the air inlet temperature is too high, the compounding process is influenced, and the air inlet temperature is preferably 50-90 ℃ and is preferably 60-80 ℃. In some embodiments provided in the present invention, the liquid inlet speed of the mixed liquid of the antibacterial agent is preferably 300mL/min, the spraying pressure is 0.3MPa, the air inlet temperature is preferably 65 ℃, the air outlet temperature is preferably 60 ℃, and the treatment time is preferably 50 min; in some embodiments provided in the present invention, the liquid inlet speed of the mixed liquid of the antibacterial agent is preferably 500mL/min, the spraying pressure is 0.2MPa, the air inlet temperature is preferably 70 ℃, the air outlet temperature is preferably 60 ℃, and the treatment time is preferably 70 min; in some embodiments provided in the present invention, the liquid inlet speed of the mixed liquid of the antibacterial agent is preferably 1000mL/min, the spraying pressure is 0.4MPa, the air inlet temperature is preferably 80 ℃, the air outlet temperature is preferably 70 ℃, and the treatment time is preferably 90 min.
The invention provides an antibacterial super absorbent resin composite material, which comprises the following components: 0.2-2 parts by weight of a macromolecular guanidine antibacterial agent; 0.1-2 parts by weight of a single-chain small-molecule quaternary ammonium salt antibacterial agent; 0.1-2 parts by weight of a double-chain small-molecule quaternary ammonium salt antibacterial agent; 94-99.6 parts by weight of super absorbent resin; the invention provides the antibacterial agent compound with good compatibility with a super absorbent resin system through screening and compounding of the antibacterial agent, the antibacterial agent compound is easy to dissolve in water, and the antibacterial component is successfully absorbed into the resin by utilizing the water absorption characteristic of the super absorbent resin. The antibacterial compound can play a role in synergistic antibacterial action in a super absorbent resin matrix, can show excellent bactericidal effect when added in a small amount, and is low in cost. The super absorbent resin swells and sticks after absorbing water, and can cause particle aggregation, thereby influencing the product performance. In the invention, a proper amount of ethanol is added into the solvent, and production equipment with the functions of fluidizing materials and heating is combined to successfully solve the aggregation problem among particles. The preparation method of the antibacterial super absorbent resin can obtain the antibacterial super absorbent resin particles meeting the actual use requirement through one-time treatment, has simple process and is easy to realize mass production.
Drawings
FIG. 1 results of the original super absorbent resin antibacterial test, (left) Staphylococcus aureus, (right) Escherichia coli;
FIG. 2 results of the antibacterial test of the antibacterial super absorbent resin of example 1, (left) Staphylococcus aureus, (right) Escherichia coli;
FIG. 3 results of the antibacterial test of the antibacterial super absorbent resin of example 2, (left) Staphylococcus aureus, (right) Escherichia coli;
FIG. 4 results of the antibacterial test of the antibacterial super absorbent resin of example 3, (left) Staphylococcus aureus, (right) Escherichia coli;
FIG. 5 results of antibacterial tests on the antibacterial super absorbent resin of comparative example 1, (left) Staphylococcus aureus, (right) Escherichia coli;
FIG. 6 results of antibacterial test of antibacterial super absorbent resin of comparative example 2, (left) Staphylococcus aureus, (right) Escherichia coli
FIG. 7 shows SEM representation results of the surface structure of (left) original super absorbent resin and (right) antibacterial super absorbent resin.
Detailed Description
To further illustrate the present invention, the following examples are given to describe the antibacterial super absorbent resin composite material provided by the present invention in detail.
Example 1
5kg of an antibacterial agent mixed solution is prepared, wherein the weight percentage of the polyhexamethylene monoguanidine phosphate is 6%, the weight percentage of the benzyl dimethyl [2- [2- [4- (1,1,3, 3-tetramethyl butyl) phenoxy ] ethoxy ] ethyl ] ammonium chloride is 6%, the weight percentage of the bis-quinyldimethylammonium chloride is 3%, and the weight percentage of the ethanol in the mixed solvent is 8%. The components with the formula ratio are stirred to be in a clear state at the temperature of 20 ℃, the stirring speed is 1000r/min, and the stirring time is 10 min. 50kg of polyacrylic acid super absorbent resin is weighed and added into a stock bin of a boiling granulator, and 5kg of the antibacterial agent mixed solution is added into a super absorbent resin matrix through a pressure liquid spraying system. Wherein the liquid inlet speed of the mixed liquid of the antibacterial agent is 300mL/min, and the spraying pressure is 0.3 MPa; the air inlet temperature is set to 65 ℃, and the air outlet temperature is set to 60 ℃. And compounding and drying for 50min to obtain the antibacterial super absorbent resin composite material.
Comparative example 1
5kg of an antibacterial agent mixed solution is prepared, wherein the weight percentage of the polyhexamethylene monoguanidine phosphate is 14.6%, the weight percentage of the benzyldimethyl [2- [2- [4- (1,1,3, 3-tetramethylbutyl) phenoxy ] ethoxy ] ethyl ] ammonium chloride is 0.2%, the weight percentage of the bis-quinyldimethylammonium chloride is 0.2%, and the weight percentage of the ethanol in the mixed solvent is 8%. The components with the formula ratio are stirred to be in a clear state at the temperature of 20 ℃, the stirring speed is 1000r/min, and the stirring time is 10 min. 50kg of polyacrylic acid super absorbent resin is weighed and added into a stock bin of a boiling granulator, and 5kg of the antibacterial agent mixed solution is added into a super absorbent resin matrix through a pressure liquid spraying system. Wherein the liquid inlet speed of the mixed liquid of the antibacterial agent is 300mL/min, and the spraying pressure is 0.3 MPa; the air inlet temperature is set to 65 ℃, and the air outlet temperature is set to 60 ℃. And compounding and drying for 50min to obtain the antibacterial super absorbent resin composite material.
Comparative example 2
5kg of an antibacterial agent mixed solution is prepared, wherein the weight percentage of the polyhexamethylene monoguanidine phosphate is 0.5%, the weight percentage of the benzyldimethyl [2- [2- [4- (1,1,3, 3-tetramethylbutyl) phenoxy ] ethoxy ] ethyl ] ammonium chloride is 9.5%, the weight percentage of the bis-quinyldimethylammonium chloride is 5%, and the weight percentage of the ethanol in the mixed solvent is 8%. The components with the formula ratio are stirred to be in a clear state at the temperature of 20 ℃, the stirring speed is 1000r/min, and the stirring time is 10 min. 50kg of polyacrylic acid super absorbent resin is weighed and added into a stock bin of a boiling granulator, and 5kg of the antibacterial agent mixed solution is added into a super absorbent resin matrix through a pressure liquid spraying system. Wherein the liquid inlet speed of the mixed liquid of the antibacterial agent is 300mL/min, and the spraying pressure is 0.3 MPa; the air inlet temperature is set to 65 ℃, and the air outlet temperature is set to 60 ℃. And compounding and drying for 50min to obtain the antibacterial super absorbent resin composite material.
Example 2
10kg of mixed solution of the antibacterial agent is prepared, wherein the weight percentage of the polyaminopropyl biguanide is 2%, the weight percentage of the dodecyl dimethyl benzyl ammonium bromide is 2%, the weight percentage of the bis-quinyl dimethyl ammonium bromide is 1%, and the weight percentage of the ethanol in the mixed solvent is 10%. The components with the formula ratio are stirred to be in a clear state at the temperature of 20 ℃, the stirring speed is 1500r/min, and the stirring time is 5 min. 50kg of polyacrylic acid super absorbent resin is weighed and added into a stock bin of a boiling granulator, and the 10kg of the antibacterial agent mixed solution is added into a super absorbent resin matrix through a pressure liquid spraying system. Wherein the liquid inlet speed of the mixed liquid of the antibacterial agent is 500mL/min, and the spraying pressure is 0.2 MPa; the air inlet temperature is set to 70 ℃, and the air outlet temperature is set to 60 ℃. And compounding and drying for 70min to obtain the antibacterial super absorbent resin composite material.
Example 3
24kg of antibacterial agent mixed solution is prepared, wherein the weight percentage of the chitosan biguanide hydrochloride is 4.2%, the weight percentage of the cetyl pyridinium chloride is 1.3%, the weight percentage of the didodecyl dimethyl ethylene diamine bromide is 1.3%, and the weight percentage of the ethanol in the mixed solvent is 12%. The components with the formula ratio are stirred to be in a clear state at 25 ℃, the stirring speed is 2000r/min, and the stirring time is 10 min. 80kg of partially hydrolyzed polyacrylamide super absorbent resin is weighed and added into a stock bin of a boiling granulator, and the 24kg of the mixed solution of the antibacterial agent is added into a super absorbent resin matrix through a pressure liquid spraying system. Wherein the liquid inlet speed of the mixed liquid of the antibacterial agent is 1000mL/min, and the spraying pressure is 0.4 MPa; the air inlet temperature is set to 80 ℃, and the air outlet temperature is set to 70 ℃. And compounding and drying for 90min to obtain the antibacterial super absorbent resin composite material.
Example 4
Performance testing
(1) And (3) testing antibacterial performance: the antibacterial performance test is carried out on the raw material of the super absorbent resin without antibacterial treatment, the antibacterial super absorbent resin composite materials prepared in the examples 1-3 and the comparative examples 1-2 according to GB 15979-2002 appendix C5 of hygienic Standard for Disposable sanitary articles. Staphylococcus aureus (ATCC6538) and Escherichia coli (8099) were used as test bacteria, and the 4 th generation of fresh slant culture was used for the test. The test results are shown in table 1. FIG. 1 shows the antibacterial test of crude resin material against Staphylococcus aureus and Escherichia coli. FIG. 2 shows the antibacterial test of the antibacterial composite material prepared in example 1 of the present invention against Staphylococcus aureus and Escherichia coli. FIG. 3 shows the antibacterial test of the antibacterial composite material prepared in example 2 of the present invention against Staphylococcus aureus and Escherichia coli. FIG. 4 is an antibacterial test of the antibacterial composite material prepared in example 3 of the present invention against Staphylococcus aureus and Escherichia coli. FIG. 5 is an antibacterial test of the antibacterial composite material prepared in comparative example 1 according to the present invention against Staphylococcus aureus and Escherichia coli. FIG. 6 is an antibacterial test of the antibacterial composite material prepared in comparative example 2 of the present invention against Staphylococcus aureus and Escherichia coli. The test results of the examples 1-3 show that the screened and compounded antibacterial agent has good compatibility with the super absorbent resin, and the prepared composite antibacterial material has excellent bactericidal effect, and the bactericidal rate is generally more than 99.9%; compared with the composite antibacterial agent, the sterilization rate of the composite material prepared in the comparative example 1 is less than 90%, and the sterilization rate of the composite material prepared in the comparative example 2 is 96.2%, which are obviously lower than the results of the examples 1-4. The test results show that the macromolecular guanidine antibacterial agent and the single-chain and double-chain micromolecular quaternary ammonium salt antibacterial agent are used in a composite way, have good compatibility with the super absorbent resin matrix, and can exert the synergistic antibacterial effect.
(2) And (3) testing the absorption performance: the measurement of the absorption capacity, water retention capacity and absorption capacity under pressure was carried out in accordance with GB/T22905-2008 "highly absorbent resin for diapers" on the basis of the raw highly absorbent resin without being subjected to the antibacterial treatment and the antibacterial highly absorbent resin samples prepared in examples 1 to 3. The test results are shown in table 2. The test result proves that the absorption performance of the antibacterial super absorbent resin composite material produced in the embodiment of the invention is similar to that of the original resin, and the absorption capacity is even slightly higher than that of the original resin. FIG. 7 is an SEM image of raw resin particles and composite particles prepared in example 1, in which the surface structures of the raw resin particles and the composite particles are not significantly different, indicating that the surface structures of the super absorbent resin particles are not adversely affected by the treatment process, and thus the absorption properties of the super absorbent resin are not affected.
(3) Testing the particle size distribution: the original samples of the super absorbent resin without the antibacterial treatment and the samples of the antibacterial super absorbent resin prepared in examples 1 to 3 were subjected to the measurement of the particle size distribution according to GB/T22905-2008 "super absorbent resin for diapers", and were sieved with a standard sieve, and the measurement results are shown in Table 3. The result shows that the particle size distribution of the antibacterial super absorbent resin composite material prepared by the invention is similar to that of the original resin, and the proportion of the particles with the particle size of more than 500 mu m is slightly higher than that of the original resin. If the actual application scene is sensitive to the larger-particle-size particles, the larger-particle-size particles can be removed through a screening device.
(4) And (3) testing the biocompatibility: the antibacterial super absorbent resin composite materials prepared in examples 1 to 3 were evaluated according to the standard GB/T16886.5-2017 "section 5 of biological evaluation of medical devices: the method recommended in the in vitro cytotoxicity test "requires evaluation of the biocompatibility of the extract, and confirmation of whether or not the extract extracted from the material after contact with L-929 mammalian fibroblasts can cause a toxic reaction. In the experiments of examples 1-3, the cell viability of the 100% sample group leachate was greater than 70% of the cell viability of the blank control group. Therefore, the leaching solution of the antibacterial super absorbent resin composite prepared in examples 1-3 has no potential cytotoxicity to L-929 cells.
TABLE 1 results of antibacterial property test of raw resin, examples and comparative examples
sample/Sterilization Rate
Staphylococcus aureus
Escherichia coli
Virgin resin
0
0
Example 1
>99.9％
>99.9％
Example 2
>99.9％
>99.9％
Example 3
>99.9％
>99.9％
Comparative example 1
<90％
<90％
Comparative example 2
95.3％
92.8％
Table 2 raw resin and example sample absorption property test results
TABLE 3 particle size distribution test results for virgin resins and example samples
Range of particle size
Virgin resin
Example 1
Example 2
Example 3
>500μm
0.09％
0.23％
0.22％
0.27％
>400μm
2.97％
2.42％
2.83％
2.47％
>315μm
5.36％
4.86％
4.75％
5.53％
>150μm
79.61％
81.33％
80.67％
80.92％
>105μm
10.25％
9.56％
9.95％
8.84％
>45μm
1.72％
1.60％
1.58％
1.97％
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.