WO2024098189A1 - 一种协效抗菌防霉剂及其制备方法 - Google Patents

一种协效抗菌防霉剂及其制备方法 Download PDF

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Publication number
WO2024098189A1
WO2024098189A1 PCT/CN2022/130293 CN2022130293W WO2024098189A1 WO 2024098189 A1 WO2024098189 A1 WO 2024098189A1 CN 2022130293 W CN2022130293 W CN 2022130293W WO 2024098189 A1 WO2024098189 A1 WO 2024098189A1
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shaped
fixed
assembly
antibacterial
groups
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PCT/CN2022/130293
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English (en)
French (fr)
Inventor
刘宇宸
孙洪
周泽雄
吴金航
晋新亮
于涛涛
罗军
李静静
郭舒宇
李婷婷
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浙江丰虹新材料股份有限公司
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Priority to PCT/CN2022/130293 priority Critical patent/WO2024098189A1/zh
Publication of WO2024098189A1 publication Critical patent/WO2024098189A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages

Definitions

  • the invention relates to a green and environmentally friendly new material, and in particular to a synergistic antibacterial and mildew-proof agent and a preparation method thereof.
  • Metal ions such as silver, copper and zinc attach to the cell wall membrane. Their strong adsorption force allows them to penetrate the cell wall and enter the bacterial cells.
  • the metal ions destroy the proteins in the bacterial cells and change their helical structure (the -NH2 , -SH and -COOH groups on the proteins can react with most heavy metal ions).
  • the proteins lose their activity, making the bacterial cells unable to divide and regenerate (the active center of the protein-enzyme is mainly composed of amino, hydroxyl, sulfhydryl and carboxyl groups, so most enzymes can be inhibited by heavy metal ions), thereby killing the bacteria.
  • the antibacterial agent carriers mainly include porous ion exchange materials such as zeolite, montmorillonite, silica, zirconium phosphate, etc., which improve the heat resistance, dissolution, migration and other problems of inorganic metal ion antibacterial agents.
  • the main shortcomings are poor dispersibility in polymer systems such as plastics, rubber and textiles, slow antibacterial effect, and inability to eliminate viruses as quickly as organic antibacterial agents.
  • the inhibitory effect on spore fungi and plum fungi is weak.
  • the mechanism of action of quaternary ammonium salt fungicides is mainly that positively charged cations adsorb negatively charged bacteria and aggregate on the cell wall, producing a chamber barrier effect, resulting in bacterial growth inhibition and death; at the same time, its hydrophobic group interacts with the hydrophilic group of bacteria, changes the permeability of the membrane, and then lyses, destroys the cell structure, and causes cell dissolution and death. It has high efficiency, low toxicity, is not easily affected by pH changes, has long-lasting bactericidal activity, has a strong stripping effect on the mucus layer, has stable chemical properties, good dispersion and corrosion inhibition, and has the characteristics of algaecide and flocculation. It is widely used internationally.
  • ordinary quaternary ammonium salts have low chemical activity and basically exist in a free state when used. They are relatively toxic and irritating. When used as an antibacterial agent on textiles, they are dissolution-type, easy to wash off, and easy to enrich on the human body surface. Long-term use is prone to cause lesions.
  • the first technical purpose of the present invention is to provide a synergistic antibacterial and antifungal agent that can effectively solve the dissolution and thermal stability problems of quaternary ammonium antibacterial agents.
  • the second technical purpose of the present invention is to provide a method for preparing a synergistic antibacterial and antifungal agent.
  • a synergistic antibacterial and antifungal agent the structure of which is:
  • Mn + is Ag, Cu, Zn metal ions loaded in the pores of zeolite, molecular sieve and clay, R1 is methyl or hydrogen, R2 is methyl, benzyl or alkane with 12 to 22 carbon chains, and R3 is alkane with 12 to 22 carbon chains.
  • the antibacterial and mildew-proof agent of the present invention effectively solves the dissolution and thermal stability problems of quaternary ammonium salt antibacterial agents and the dispersibility problems of inorganic antibacterial agents, and has a wider antibacterial spectrum than existing inorganic antibacterial agents and quaternary ammonium salt antibacterial agents.
  • the present invention effectively solves the thermal stability and dispersibility problems, mainly because zeolite has a complete crystal structure and is tightly combined with the loaded ions, thereby improving the original thermal stability. When dissolved in water, water molecules can surround the ions, so that the ions are no longer combined with the skeleton on the crystal, thereby improving the dispersibility.
  • a method for preparing a synergistic antibacterial and antifungal agent comprises the following preparation steps:
  • the surface of the carrier is modified by using an organic silicon quaternary ammonium salt containing an alkoxy group.
  • the alkoxy group reacts with the hydroxyl group on the surface of the carrier to form a Si-O bond, so that the quaternary ammonium salt is firmly bonded to the carrier.
  • the porous cationic ion exchange carrier containing surface hydroxyl groups is used to load silver, copper and zinc metal ions, specifically comprising: adding 200-30 parts by weight of silver nitrate or copper sulfate solution to 100 parts by weight of zeolite, dispersing at high speed, reacting at a temperature of 70-80° C., and reacting at normal pressure for 1.5-2.5 hours.
  • the use of a porous cationic ion exchange carrier containing surface hydroxyl groups to load silver, copper and zinc metal ions specifically includes: adding 250 parts by weight of silver nitrate or copper sulfate solution to 100 parts by weight of zeolite, reacting at a temperature of 75° C. and reacting at normal pressure for 2 hours.
  • the method of surface modification with alkoxy-containing organosilicon quaternary ammonium salt specifically comprises: adding 5-15 parts by weight of organic quaternary ammonium salt solution to 100 parts by weight of zeolite, dispersing at high speed, reacting at a temperature of 70-80° C., and reacting at normal pressure for 1.5-2.5 hours.
  • the method of surface modification with an alkoxy-containing organic silicon quaternary ammonium salt specifically comprises: adding 10 parts by weight of an organic quaternary ammonium salt solution to 100 parts by weight of zeolite, reacting at a reaction temperature of 75° C. and reacting at normal pressure for 2 hours.
  • the porous cationic ion exchange carrier containing surface hydroxyl groups is natural zeolite (Zeolite), synthetic silica-alumina molecular sieve (MOLECULAR SIEVE), montmorillonite (bentonite), attapulgite (also known as Palygorskite), and sepiolite.
  • Zeolite natural zeolite
  • MOLECULAR SIEVE synthetic silica-alumina molecular sieve
  • montmorillonite bentonite
  • attapulgite also known as Palygorskite
  • sepiolite sepiolite
  • the solid-liquid dispersion high-speed homogenizer used in the preparation steps (1) and (2) of the synergistic antibacterial and antifungal agent comprises:
  • a lifting mechanism wherein the lifting mechanism is a hydraulic cylinder
  • a rotary drive assembly wherein the rotary drive assembly is fixed on the top of the hydraulic cylinder, the hydraulic cylinder pushes the rotary drive assembly to perform lifting motion, and the rotary drive assembly includes a driving member, a belt, a driving wheel and a driven wheel, the driving member drives the driving wheel to rotate, the driving wheel drives the driven wheel to rotate through the belt, and the output shaft of the driven wheel is connected to the agitator output assembly, thereby driving the agitator output assembly to rotate;
  • a detachable stirring component wherein the detachable stirring component is connected and fixed to the stirrer output component, drives the stirrer output component to rotate and drives the detachable stirring component to rotate, so as to disperse and homogenize the solid-liquid mixture;
  • the flip material cylinder assembly comprises a material cylinder, and the detachable stirring assembly is inserted into or away from the material cylinder under the pushing action of the hydraulic cylinder.
  • the detachable stirring assembly is inserted into the material cylinder, it is used to mix the solid-liquid mixture in the material cylinder.
  • the existing high-speed homogenizer for solid-liquid dispersion has only a dispersion disc as the stirring component, and the dispersion disc is an integrated structure, which is not convenient to disassemble and clean.
  • the existing high-speed disperser cannot efficiently, quickly and evenly dissolve the solid and liquid into one, so that the material cannot effectively produce the comprehensive effects of liquid layer friction, impact tearing and turbulence in a narrow space.
  • the product stability still needs to be improved, and the dispersion efficiency is low.
  • the solid-liquid dispersion high-speed homogenizer of the present invention is composed of a lifting mechanism, a rotary drive component, a detachable stirring component and a flip material cylinder component.
  • the detachable stirring component is installed on the rotary drive component and is driven to rotate by the rotary drive component.
  • the material is fully dispersed during the rotation process.
  • the lifting mechanism drives the rotary drive component to rise and fall, thereby driving the detachable stirring component to rise and fall, and performs two movements of inserting into the inner side of the flip material cylinder component or moving away from the flip material cylinder component.
  • the positioning plug-in block is connected and fixed to the docking column by bolts and nuts running through the positioning plug-in block and the docking column, which facilitates the installation and disassembly of the detachable stirring assembly, and facilitates the disassembly and cleaning of the detachable stirring assembly.
  • the exterior of the detachable stirring assembly is designed as a frame-type turning material stirring, and the high shear dispersion of the middle dispersion disk enables the solid-liquid mixing of medium and high viscosity materials.
  • the flip material cylinder assembly is designed as a flippable structure, which is convenient for flipping, cleaning and cleaning after unloading; and has high dispersion efficiency, and the final prepared product has good stability.
  • the lifting mechanism also includes a vertical outer shell fixed on the outer side of the hydraulic cylinder, three groups of cross-shaped guide opening grooves arranged on the left side of the vertical outer shell, a docking assembly with a clamp on the outer side of the vertical outer shell and docked with a fixed ring on the outer side of the material cylinder, and a base fixed at the bottom of the vertical outer shell.
  • the horizontal cross-section of the vertical outer shell is a U-shape formed by a semicircle and a rectangle.
  • the docking assembly includes a limit plate limited on the left side of the vertical outer shell, a U-shaped hoop hooped on the outer side of the vertical outer shell and with both ends passing through the limit plate, three groups of cross-shaped plug blocks fixed on the right side of the limit plate and matched with the three groups of cross-shaped guide opening grooves to be plugged in, and a U-shaped groove plug block fixed on the left side of the limit plate, and the left side of the limit plate and the two ends of the U-shaped hoop are screwed with locking nuts that lock and fix the U-shaped hoop on the vertical outer shell;
  • the fixing ring After the insert block on the fixing ring is inserted into the notch in the U-shaped groove insert block, the fixing ring is fixed on the docking assembly by bolts penetrating through the insert block and the U-shaped groove insert block.
  • the rotary drive assembly also includes a transverse mounting box fixed at the end of the hydraulic cylinder piston rod, a truncated cone-shaped connecting seat arranged below the left end of the transverse mounting box and fixedly connected to the wheel axle of the driven wheel, a connecting rod fixedly arranged at the bottom of the truncated cone-shaped connecting seat, and a positioning plug-in block fixedly arranged at the bottom of the connecting rod.
  • the driving wheel is rotatably arranged at the right end inside the transverse mounting box, the driven wheel is rotatably arranged at the left end inside the transverse mounting box, the driving member is fixed at the bottom of the right end of the transverse mounting box, the driving member is a driving motor, and the connecting rod is rotatably connected to the cylinder head through a bearing.
  • the detachable stirring assembly includes a docking column with a slot, a stirring rod fixed under the docking column, two sets of dispersion plates symmetrically fixed on the outer side of the stirring rod, a sleeve limitedly sleeved on the outer side of the bottom end of the stirring rod and locked and fixed by a locking screw, two sets of inverted U-shaped mounting plates on the left and right sides of the sleeve, two side plates fixed on the outer side of the top ends of the two sets of inverted U-shaped mounting plates and cooperating with the inverted U-shaped mounting plates to form a frame-type stirring rod, two bottom scrapers screwed and fixed to the bottom of the inverted U-shaped mounting plates and used for scraping materials adhered to the bottom wall of the material cylinder, side scrapers screwed and fixed to the outer sides of the two side plates and used for scraping materials adhered to the side walls of the material cylinder, and two sets of fork-shaped stirring blades symmetrically
  • the flanges on the outside of the two side plates are screwed to the flanges on the docking plate on the outside of the top of the stirring rod through bolts, and a reinforcing plate connected to a sleeve is fixedly connected to the top of each group of inverted U-shaped mounting plates, and the sleeve is limited below the limiting ring on the outer side of the stirring rod;
  • the positioning plug-in block After the positioning plug-in block is inserted into the slot, the positioning plug-in block is connected and fixed to the docking column by bolts and nuts that penetrate through the positioning plug-in block and the docking column.
  • the flip material cylinder assembly includes a flip plate fixed at the bottom of the material cylinder and a pushing assembly for pushing the flip plate to flip, three groups of first convex blocks are arranged longitudinally on the left side of the bottom of the flip plate, three groups of second convex blocks are arranged at the bottom of the flip plate and on the right side of the three groups of first convex blocks, and longitudinal axes are fixed through the three groups of second convex blocks;
  • the pushing assembly includes two U-shaped fixing grooves symmetrically arranged front and back, two first rectangular grooves fixedly arranged at the left ends of the tops of the two U-shaped fixing grooves, three groups of bearing seats fixedly distributed on the tops of the two first rectangular grooves and arranged longitudinally, a rotating shaft rotatably connected to the three groups of bearing seats, an L-shaped fixing seat fixedly connected to the two first rectangular grooves, a motor fixedly arranged on the top of the L-shaped fixing seat, a worm gear reducer drivingly connected to the output shaft of the motor, and a lever arm connecting rod fixedly connected to the output shaft of the worm gear reducer;
  • the collar on the lever arm connecting rod is rotatably sleeved on the outer side of the longitudinal shaft, and the three groups of first convex blocks are fixedly sleeved on the outer side of the rotating shaft;
  • Support feet are fixed on both left and right ends of the two U-shaped fixing grooves
  • two square fixing plates are fixed on the outer sides of the two first convex blocks on the front and rear sides
  • guide blocks are fixed on the vertical plates at the bottom of the two square fixing plates
  • connecting blocks fixed on the outer sides of the left ends of the two U-shaped fixing grooves are fixedly connected with the two arc-shaped guide plates respectively
  • the guide blocks cooperate with the arc-shaped guide plates to limit and guide sliding
  • the arc-shaped guide plates are provided with arc-shaped guide through-hole grooves that match the guide blocks for guiding and interlacing sliding
  • the top of the flip plate is provided with a positioning piece that cooperates with the material cylinder for positioning and fixing
  • a second rectangular groove is also fixed on the top right end of the two U-shaped fixing grooves.
  • the present invention has the following beneficial effects:
  • the antibacterial and mildew-proof agent of the present invention effectively solves the dissolution and thermal stability problems of quaternary ammonium antibacterial agents and the dispersibility problems of inorganic antibacterial agents, and has a wider antibacterial spectrum than existing inorganic antibacterial agents and quaternary ammonium antibacterial agents.
  • the present invention effectively solves the thermal stability and dispersibility problems, mainly because zeolite has a complete crystal structure and is tightly combined with the loaded ions, thereby improving the original thermal stability. When dissolved in water, water molecules can surround the ions, so that the ions no longer bind to the skeleton on the crystal, thereby improving the dispersibility;
  • the solid-liquid dispersion high-speed homogenizer of the present invention can disperse and stir evenly, achieve an ideal material stirring effect, have good mixing effect, and have good homogenization effect.
  • the flip material cylinder assembly is designed as a flippable structure, which is convenient for flipping, cleaning and washing after unloading; thus, the dispersion efficiency is high and the final prepared product has good stability.
  • Fig. 1 is a schematic diagram of the structure of the present invention
  • FIG2 is an exploded view of FIG1 of the present invention
  • FIG3 is a schematic diagram of the structure of the hydraulic cylinder of the present invention.
  • FIG4 is a schematic structural diagram of a docking assembly according to the present invention.
  • FIG5 is a schematic structural diagram of a rotary drive assembly according to the present invention.
  • FIG. 6 is a schematic diagram of the structure of the rotary drive assembly of the present invention after the upper cylinder cover is disassembled.
  • FIG7 is a schematic structural diagram of a detachable stirring assembly according to the present invention.
  • FIG8 is a schematic structural diagram of the connection rod and the docking column of the present invention.
  • FIG9 is a schematic structural diagram of a tiltable material cylinder assembly of the present invention.
  • FIG10 is a schematic diagram of the structure of the flip plate of the present invention.
  • FIG11 is a schematic diagram of the structure of a push assembly of the present invention.
  • Example 12 is an analysis diagram of the anti-dissolution performance of the antibacterial and antifungal agent in Example 1;
  • FIG. 13 is an infrared spectrum analysis diagram of the antibacterial and antifungal agent of Example 2.
  • lifting mechanism 101. hydraulic cylinder; 102. vertical outer shell; 103. cross-shaped guide opening groove; 104. docking assembly; 105. limit plate; 106. U-shaped hoop; 107. cross-shaped plug block; 108. U-shaped slot plug block; 109. locking nut; 110. base; 2. rotary drive assembly; 201. driving member; 202. belt; 203. driving wheel; 204. driven wheel; 205. horizontal installation box; 206. truncated cone connecting seat; 207. connecting rod; 208. positioning plug block; 209. cylinder cover; 210; 3. detachable stirring assembly; 301. slot; 302. docking column; 303. stirring rod; 304. dispersion disk; 305.
  • 100 kg 1000 mesh zeolite was mixed with 300 kg deionized water, dispersed at high speed with a homogenizer for 1 hour, added with 250 kg 3M zinc nitrate solution, heated and stirred in a boiling water bath for 2 hours, cooled, filtered and washed, added with 10 kg 42% (dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution, stirred at 80°C for 2 hours, and spray dried and packaged.
  • the anti-dissolution performance analysis diagram of the product of this embodiment is shown in Figure 12. As can be seen from Figure 12, the product of this embodiment has good thermal stability and can withstand a high temperature of at least 160°C.
  • 150L of 0.03mol of silver acetate and 150L of 0.07mol of sodium glycinate aqueous solution were mixed and placed at room temperature for 30min, and stirred for 2 hours at 50°C jacket insulation with stirring speed of 60r/min.
  • 10kg 4A molecular sieve was mixed with 30kg of deionized water, dispersed at high speed for 1 hour with a homogenizer, and then added to the silver ammonia solution and stirred evenly, sealed, and stirred at 50°C overnight, cooled, filtered, and washed.
  • 1kg 42% (dimethyloctadecyl [3- (trimethoxysilyl) propyl] ammonium chloride solution was stirred at 80°C for 2 hours, and vacuum dried at 70°C, crushed and packaged.
  • 25kg of sodium montmorillonite with a blue absorption capacity of 38 was mixed with 300kg of deionized water, dispersed at high speed for 1 hour, stirred for 4 hours, added with 40kg of 3M copper sulfate solution, heated and stirred in a boiling water bath for 2h, cooled, filtered and washed, 3kg of 42% methylbenzyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution was stirred at 80°C for 2 hours, and spray dried and packaged.
  • the infrared spectrum analysis diagram of the antibacterial and antifungal agent of the product of this embodiment is shown in FIG13 .
  • 1039cm-1 in the infrared spectrum analysis is the characteristic peak of montmorillonite
  • 2923cm-1, 2853cm-1 and 1467cm-1 are the characteristic absorption peaks of long-chain fatty hydrocarbons in organosilicon quaternary ammonium salts
  • 625cm-1, 796cm-1 and 1250cm-1 are the characteristic peaks of organosilicon Si-C bond, indicating that organosilicon quaternary ammonium salts have reacted and combined with montmorillonite and have not been removed in the dehydration and washing process.
  • FIG1-11 A solid-liquid dispersion high-speed homogenizer used for high-speed dispersion is shown in FIG1-11, comprising a lifting mechanism 1, a rotary drive component 2, a detachable stirring component 3 and a flip material cylinder component 4.
  • the detachable stirring component 3 is installed on the rotary drive component 2 and driven to rotate by the rotary drive component 2.
  • the material is fully dispersed during the rotation process.
  • the lifting mechanism 1 pushes the rotary drive component 2 to rise and fall, thereby driving the detachable stirring component 3 to rise and fall, and performs two movements of inserting into the inner side of the flip material cylinder component 4 or moving away from the flip material cylinder component 4.
  • the lifting mechanism 1 is a hydraulic cylinder 101, and the lifting mechanism 1 also includes a vertical outer shell 102 fixed on the outer side of the hydraulic cylinder 101, three groups of cross-shaped guide opening grooves 103 arranged on the left side of the vertical outer shell 102, a docking assembly 104 that is clamped on the outer side of the vertical outer shell 102 and docked with the fixing ring 402 on the outer side of the material cylinder 401, and a base 110 fixed to the bottom of the vertical outer shell 102.
  • the horizontal section shape of the vertical outer shell 102 is a U-shape spliced by a semicircle and a rectangle;
  • the docking assembly 104 includes a limit plate 105 limited on the left side of the vertical outer shell 102, a U-shaped hoop 106 clamped on the outer side of the vertical outer shell 102 and with both ends penetrating the limit plate 105, three groups of cross-shaped plug blocks 107 fixed on the right side of the limit plate 105 and matched with the three groups of cross-shaped guide opening grooves 103 to be plugged in, and a U-shaped groove plug block 108 fixed on the left side of the limit plate 105.
  • the left side of the limit plate 105 and the two ends of the U-shaped hoop 106 are screwed with locking nuts 109 for locking and fixing the U-shaped hoop 106 on the vertical outer shell 102;
  • the fixing ring 402 is fixed to the docking assembly 104 by bolts penetrating through the insert block 403 and the U-shaped slot insert block 108 .
  • the docking assembly 104 is fixedly sleeved on the outer side of the vertical outer shell 102 through the cooperation of the U-shaped hoop 106 and the limiting plate 105, it is convenient to adjust the installation height of the docking assembly 104 according to different installation requirements, which is convenient to adjust and expands the scope of application;
  • the rotary drive assembly 2 is fixed on the top of the hydraulic cylinder 101.
  • the hydraulic cylinder 101 pushes the rotary drive assembly 2 to perform lifting motion.
  • the rotary drive assembly 2 includes a driving member 201, a belt 202, a driving wheel 203 and a driven wheel 204.
  • the driving member 201 drives the driving wheel 203 to rotate.
  • the driving wheel 203 drives the driven wheel 204 to rotate through the belt 202.
  • the output shaft of the driven wheel 204 is connected to the agitator output assembly, thereby driving the agitator output assembly to rotate.
  • the rotary drive assembly 2 also includes a transverse mounting box 205 fixed to the end of the piston rod of the hydraulic cylinder 101, a truncated cone-shaped connecting seat 206 disposed below the left end of the transverse mounting box 205 and fixedly connected to the axle of the driven wheel 204, a connecting rod 207 fixedly disposed at the bottom of the truncated cone-shaped connecting seat 206, and a positioning plug-in block 208 fixedly disposed at the bottom of the connecting rod 207.
  • the driving wheel 203 is rotatably disposed at the right end inside the transverse mounting box 205
  • the driven wheel 204 is rotatably disposed at the left end inside the transverse mounting box 205.
  • the driving member 201 is fixed at the bottom of the right end of the transverse mounting box 205.
  • the driving member is a driving motor, and the connecting rod 207 is rotatably connected to the cylinder cover 209 through a bearing.
  • the hydraulic cylinder 101 pushes the horizontal installation box 205 to rise and fall, thereby driving the connecting rod 207 and the cylinder cover 209 to rise and fall, so that the cylinder cover 209 can be conveniently connected to the material cylinder 401 or away from the material cylinder 401, and the connecting rod 207 is connected to the detachable stirring assembly 3;
  • the detachable stirring component 3 is connected and fixed to the stirrer output component, driving the stirrer output component to rotate and driving the detachable stirring component 3 to rotate, so as to disperse and homogenize the solid-liquid mixture;
  • the detachable stirring assembly 3 comprises a docking column 302 with a slot 301, a stirring rod 303 fixed below the docking column 302, two groups of dispersion plates 304 symmetrically fixed on the outer side of the stirring rod 303, a sleeve 311 limitedly sleeved on the outer side of the bottom end of the stirring rod 303 and locked and fixed by a locking screw 305, two groups of inverted U-shaped mounting plates 306 arranged on the left and right sides of the sleeve 311, two side plates 307 fixed on the outer side of the top ends of the two groups of inverted U-shaped mounting plates 306 and cooperating with the inverted U-shaped mounting plates 306 to form a frame-type stirring rod, two bottom scrapers 308 screwed and fixed to the bottom of the inverted U-shaped mounting plates 306 and used for scraping the material adhered to the bottom wall of the material cylinder 401, side scrapers 309 screwed and fixed to the outer sides of the two side plates 307 and used
  • the outer flanges of the two side panels 307 are screwed to the flanges on the docking plate 312 on the outer side of the top end of the stirring rod 303 through bolts.
  • the top of each set of inverted U-shaped mounting plates 306 is fixedly connected to a reinforcing plate 313 connected to a sleeve 311.
  • the sleeve 311 is limited below the limiting ring 314 on the outer side of the stirring rod 303. Since the flanges of the two side panels 307 are screwed to the flanges on the docking plate 312, the two side panels 307 and the two sets of inverted U-shaped mounting plates 306 can be easily disassembled separately to replace the scraper or clean the sticky coating.
  • the hydraulic cylinder 101 pushes the detachable stirring assembly 3 up and down, saving height space and convenient operation.
  • the exterior of the detachable stirring assembly 3 is designed as a frame-type material turning stirring, and the high shear dispersion of the middle dispersion plate 304 makes the solid-liquid mixing of medium and high viscosity materials, and with the fork-shaped stirring blade 310, the dispersion stirring can be uniform, achieving an ideal material stirring effect, good mixing effect, and good homogenization effect;
  • the positioning plug-in block 208 is connected and fixed to the docking post 302 by bolts and nuts penetrating through the positioning plug-in block 208 and the docking post 302 .
  • the positioning plug-in block 208 After the positioning plug-in block 208 is inserted into the slot 301 , it is fixed by a nut, which facilitates the installation and disassembly of the detachable stirring component 3 , and facilitates the disassembly and cleaning of the detachable stirring component 3 .
  • the tiltable material cylinder assembly 4 includes a material cylinder 401 .
  • the detachable stirring assembly 3 is inserted into or away from the material cylinder 401 under the pushing action of the hydraulic cylinder 101 .
  • the detachable stirring assembly 3 is inserted into the material cylinder 401 , it is used to mix the solid-liquid mixture in the material cylinder 401 .
  • the flip material cylinder assembly 4 includes a flip plate 404 fixed at the bottom of the material cylinder 401 and a pushing assembly 405 for pushing the flip plate 404 to flip.
  • Three groups of first convex blocks 406 are arranged longitudinally on the left side of the bottom of the flip plate 404.
  • Three groups of second convex blocks 407 are arranged at the bottom of the flip plate 404 and on the right side of the three groups of first convex blocks 406.
  • a longitudinal shaft 408 is fixed through the three groups of second convex blocks 407.
  • the pushing assembly 405 includes two U-shaped fixing grooves 410 symmetrically arranged front and back, two first rectangular grooves 411 fixedly arranged at the left ends of the tops of the two U-shaped fixing grooves 410, three groups of bearing seats 412 fixedly distributed on the tops of the two first rectangular grooves 411 and arranged longitudinally, a rotating shaft 413 rotatably connected to the three groups of bearing seats 412, an L-shaped fixing seat 414 fixedly connected to the two first rectangular grooves 411, a motor 415 fixedly arranged at the top of the L-shaped fixing seat 414, a worm gear reducer 416 drivingly connected to the output shaft of the motor 415, and a lever arm connecting rod 417 fixedly connected to the output shaft of the worm gear reducer 416;
  • the collar 419 on the lever arm connecting rod 417 is rotatably sleeved on the outer side of the longitudinal shaft 408, and the three groups of first convex blocks 406 are fixedly sleeved on the outer side of the rotating shaft 413;
  • Support feet 418 are fixedly provided at both ends of the left and right sides of the two U-shaped fixing grooves 410, and two square fixing plates 420 are fixedly provided on the outer sides of the two first convex blocks 406 on the front and rear sides respectively, and guide blocks 422 are fixedly provided on the vertical plates 421 at the bottom of the two square fixing plates 420, and the connecting blocks 423 fixedly provided on the outer sides of the left ends of the two U-shaped fixing grooves 410 are fixedly connected with the two arc-shaped guide plates 424 respectively, and the guide blocks 422 cooperate with the arc-shaped guide plates 424 to limit and guide sliding, and the arc-shaped guide through-hole grooves 425 that match the guide blocks 422 for guiding and interlacing sliding are provided on the arc-shaped guide plates 424, and a positioning piece that cooperates with the material cylinder for positioning and fixing is provided on the top of the flip plate 404, and a second rectangular groove 426 is also fixedly provided on the top right end of the two U-shaped fixing groove
  • the motor 415 drives the worm gear reducer 416 to push the arm connecting rod 417 to open and fold, so that the arm connecting rod 417 is connected to the longitudinal shaft 408 through the collar 419, which can push the longitudinal shaft 408 to lift up and flip the flip plate 404 or lay it flat.
  • the self-locking function can be achieved, and the flip plate 404 can be flipped and lifted smoothly.
  • the arm connecting rod 417 connects the longitudinal shaft 408 to form a labor-saving lever structure. After the material cylinder 401 is unloaded, it can be flipped for easy cleaning.
  • the flip plate 404 Compared with the hydraulic rod lifting, the flip plate 404 has better stability during the flipping process, and the material cylinder 401 has better stability during the flipping process. It is more convenient to flip, and no large vibration will be generated during the flipping process. It is more peaceful and stable.
  • 50 kg of 95% pure attapulgite was mixed with 300 kg of deionized water, dispersed at high speed for 1 hour, stirred for 4 hours, added with 20 kg of 3 M copper sulfate solution and 20 kg of 3 M zinc nitrate solution, heated in a boiling water bath with stirring for 2 hours, cooled, filtered and washed, 6 kg of 42% methyl dioctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride solution was stirred at 80°C for 2 hours, and spray dried and packaged.
  • 25 kg of 95% pure sepiolite was mixed with 300 kg of deionized water, dispersed at high speed with a homogenizer for 1 hour, added with 20 kg of 3 M zinc nitrate solution, heated and stirred in a boiling water bath for 2 hours, cooled, filtered and washed, added with 2 kg of 42% (dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution, stirred at 80°C for 2 hours, and spray dried and packaged.
  • 100kg 1000 mesh stilbene was mixed with 300kg deionized water, dispersed at high speed with a homogenizer for 1 hour, added with 250kg 3M zinc nitrate solution, heated and stirred in a boiling water bath for 2 hours, cooled, filtered and washed, 10kg 42% (dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution was stirred at 80°C for 2 hours, 10kg zinc oxide was added and stirred at 80°C for 1 hour, and then spray dried and packaged.
  • the coating was prepared using the formula in Table 3, and a blank coating was applied on a 50 mm x 50 mm blank control panel as a blank control panel.
  • the antibacterial properties were tested according to the antibacterial property determination method and antibacterial effect of antibacterial coatings (paint films) in GB/T21866-2008.
  • Antibacterial plastics that meet the 0 level can be reported as having strong antifungal effects; antibacterial plastics that meet the mold growth level of Level I can be reported as having antifungal effects)

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Abstract

一种协效抗菌防霉剂，其结构中包括金属离子M n+，M n+为Ag、Cu、Zn金属离子，负载在沸石、分子筛和粘土的孔道中；还包括连接R 1-R 3的季铵基团，其中R 1为甲基或氢，R 2为甲基、苄基或12至22个碳链的烷烃，R 3为12至22个碳链的烷烃。协效抗菌防霉剂制备方法包括以下制备步骤：采用含表面羟基的多孔阳离子离子交换载体负载银、铜和锌金属离子；用含有烷氧基的有机硅季铵盐对其进行表面改性，烷氧基与载体表面的羟基反应形成Si-O键，使季铵盐牢固地结合载载体上。协效抗菌防霉剂解决了季铵盐抗菌剂的溶出及热稳定性和无机抗菌剂的分散性问题，抗菌谱更广泛。

Description

一种协效抗菌防霉剂及其制备方法 技术领域
本发明涉及一种绿色环保新材，特别涉及一种协效抗菌防霉剂及其制备方法。
背景技术
银铜锌等金属离子附着在细胞壁膜上，强大的吸附力使其穿破细胞壁，进入细菌细胞内部，金属离子对细菌细胞内的蛋白质进行破坏，改变其螺旋结构(蛋白质上的-NH 2基，-SH基和-COOH基可与大部分的重金属离子反应)，蛋白质丧失了活性，导致细菌细胞无法进行***再生的能力(蛋白质-酶的活性中心主要是由氨基、羟基、巯基和羧基组成的，因而大部分的酶都可以被重金属离子抑制)，达到杀死细菌的效果。
银、铜、锌离子不稳定，容易溶出和迁移，造成健康和环境问题，并影响抗菌的持久性。目前市场上无机纳米抗菌剂主要采用载体加以改善，抗菌剂载体主要有沸石、蒙脱石、二氧化硅、磷酸锆等多孔离子交换材料，提高了无机金属离子抗菌剂的耐热、溶出、迁移等问题，目前存在的不足主要有在聚合物体系如塑料、橡胶及纺织上分散性较差，抑菌的迟效性，不能像有机抗菌剂那般迅速消灭病毒，对孢子菌、梅菌的抑制效果较弱。
季铵盐杀菌剂的作用机理主要是带正电荷的阳离子吸附带负电的细菌体并聚集在细胞壁上，产生室阻效应，导致细菌生长受抑而死亡；同时其疏水基与细菌的亲水基作用，改变膜的通透性，继而发生溶胞作用，破坏细胞结构，引起细胞的溶解和死亡。具有高效、低毒、不易受pH值变化的影响、持续时间长的杀菌活性，且对粘液层有较强的剥离作用、化学性能稳定、分散及缓蚀作用较好，还具有灭藻、絮凝等特点,在国际上使用广泛。但是，普通季铵盐化学活性较低，应用时基本以游离态存在，毒性相对较大，刺激性也强，将其作为抗菌剂应用在纺织品上是溶出型的，易洗脱，且易在人体表面富集，长期使用易产生病变。
发明内容
本发明的第一技术目的是提供一种能有效解决季铵盐抗菌剂的溶出及热稳定性协效抗菌防霉剂。
本发明的第二技术目的是提供一种协效抗菌防霉剂的制备方法。
本发明的第一技术目的是通过以下技术方案得以实现的：
一种协效抗菌防霉剂，其结构为：
Figure PCTCN2022130293-appb-000001
结构图中，M n+为Ag、Cu、Zn金属离子,负载在沸石、分子筛和粘土的孔道 中，R 1为甲基或氢，R 2为甲基、苄基或12至22个碳链的烷烃，R 3为12至22个碳链的烷烃。
本发明抗菌防霉剂有效地解决了季铵盐抗菌剂的溶出及热稳定性和无机抗菌剂的分散性问题，抗菌谱较现有的无机抗菌剂和季铵盐抗菌剂更广泛。本发明有效解决了热稳定性和分散性，主要是沸石有完整的晶体结构，而且与载入的离子紧密结合，提高原来了的热稳定性。当溶解在水中，水分子可以把离子包围，让离子不再跟晶体上的骨架结合，从而提高分散性。
本发明的第二技术目的是通过以下技术方案得以实现的：
一种协效抗菌防霉剂的制备方法，包括以下制备步骤：
(1)采用含表面羟基的多孔阳离子离子交换载体负载银、铜和锌金属离子；
(2)用含有烷氧基的有机硅季铵盐对其进行表面改性，烷氧基与载体表面的羟基反应形成Si-O键，使季铵盐牢固地结合载载体上。
作为优选，采用含表面羟基的多孔阳离子离子交换载体负载银、铜和锌金属离子具体包括：在100重量份的沸石中加入硝酸银或者硫酸铜溶液200-30重量份，高速分散，反应温度70-80℃，常压反应1.5-2.5个小时。
更优选地，采用含表面羟基的多孔阳离子离子交换载体负载银、铜和锌金属离子具体包括：在100重量份的沸石中加入硝酸银或者硫酸铜溶液250重量份，反应温度75℃，常压反应2个小时。
作为优选，用含有烷氧基的有机硅季铵盐对其进行表面改性的方法具体包括：在100重量份的沸石中加入有机季铵盐溶液5-15重量份，高速分散，反应温度70-80℃，常压反应1.5-2.5小时。
更优选地，用含有烷氧基的有机硅季铵盐对其进行表面改性的方法具体包括：在100重量份的沸石中加入有机季铵盐溶液10重量份，反应温度75℃，常压反应2小时。
作为优选，所述含表面羟基的多孔阳离子离子交换载体是天然沸石(Zeolite)、合成硅铝分子筛(MOLECULAR SIEVE)、蒙脱石(膨润土bentonite)、凹凸棒土(又称坡缕石Palygorskite)、海泡石。分子式为：
Figure PCTCN2022130293-appb-000002
作为优选，协效抗菌防霉剂的制备步骤(1)和步骤(2)高速分散使用的固液分散高速均化机，包括：
升降机构，所述升降机构为液压缸；
旋转驱动组件，所述旋转驱动组件固定在液压缸顶部，液压缸推动旋转驱动组件进行升降运动，且旋转驱动组件包括驱动件、皮带、主动轮以及从动轮，驱动件驱动主动轮转动，主动轮通过皮带带动从动轮转动，从动轮的输出轴与搅拌器输出组件相连接，从而带动搅拌器输出组件转动；
可拆式搅拌组件，所述可拆式搅拌组件与搅拌器输出组件连接固定，带动搅拌器输出组件转动带动可拆式搅拌组件转动，对固液混合物进行分散均化；
翻转式物料缸组件，所述翻转式物料缸组件包括物料缸，所述可拆式搅拌组件在液压缸的推动作用下***或远离物料缸，可拆式搅拌组件***物料缸内时用于拌匀物料缸内的固液混合物。
现有技术的固液分散高速均化机在使用过程中，由于搅拌组件只有分散盘，而且分散盘为一体结构，不方便拆卸清洗。而且现有的高速分散机不能够高效、快速、均匀地将固液溶解为一体，使物料在狭窄的空间中，不能有效的产生液层摩擦、撞击撕裂和湍流等综合作用，并且经过长时间的反复循环的分散剪切，产品稳定性仍然有待改进，分散效率低下。
本发明该固液分散高速均化机，由升降机构、旋转驱动组件、可拆式搅拌组件以及翻转式物料缸组件组成，拆式搅拌组件安装在旋转驱动组件上，并由旋转驱动组件带动旋转，在旋转的工程中将物料充分分散，升降机构推动旋转驱动组件升降，从而带动可拆式搅拌组件升降，进行***翻转式物料缸组件内侧或者远离翻转式物料缸组件的两种运动；
旋转驱动组件通过其上的定位插接块***可拆式搅拌组件的插槽后，通过贯穿于定位插接块和对接柱的螺栓螺母将定位插接块与对接柱连接固定，方便可拆式搅拌组件的安装和拆卸，方便对可拆式搅拌组件进行拆卸清洗，将可拆式搅拌组件的外部设计为框式翻料搅拌，中间分散盘的高剪切分散，使中高粘度物料的固液混和，搭配叉型搅拌叶片，分散搅拌能够均匀，达到理想的物料搅拌效果，混合效果好，均化效果好，翻转式物料缸组件设计为可翻转的结构，方便卸料后的翻转清理和清洗；并且分散效率高，最终制备的产品稳定性好。
作为本技术方案的进一步优化，所述升降机构还包括固定在液压缸外侧面的立式外壳体、设于立式外壳体左侧面的三组十字型导向开口槽、抱箍在立式外壳体外侧面且与物料缸外侧面的固定圈对接的对接组件以及固定设于立式外壳体底部的底座，所述立式外壳体的水平切面形状为半圆形与矩形拼接成的U形。
作为本技术方案的进一步优化，所述对接组件包括限位在立式外壳体左侧面的限位板、箍在立式外壳体外侧面且两端贯穿于限位板的U型箍、固定在限位板右侧面且与三组十字型导向开口槽相配合到相插接的三组十字形插块以及固定设于限位板左侧面的U型槽插块，限位板左侧面且位于U型箍的两端螺接有将U型箍锁紧固定在立式外壳体上的锁紧螺母；
所述固定圈上的插块***U型槽插块内的槽口内后，固定圈通过贯穿于插块和U型槽插块的螺栓固定在对接组件上。
作为本技术方案的进一步优化，所述旋转驱动组件还包括固定在液压缸活塞杆端部的横向安装箱、设于横向安装箱左端下方且与从动轮的轮轴固定连接的圆台形连接座、固定设于圆台形连接座底部的连接杆以及固定设于连接杆底部的定位插接块，所述主动轮转动设于横向安装箱内部右端，从动轮转动设于横向安装箱内部左端，驱动件固定在横向安装箱右端底部，驱动件为驱动电机，所述连接杆通过轴承与缸盖转动连接。
作为本技术方案的进一步优化，所述可拆式搅拌组件包括带有插槽的对接柱、固定在对接柱下方的搅拌杆、上下对称固定设于搅拌杆外侧面的两组分散盘、限位套接在搅拌杆底端外侧面且通过锁紧螺钉锁紧固定的套筒、设于套筒左右两侧的两组倒U形安装板、固定在两组倒U形安装板顶端外侧且与倒U形安装板配合形成框式搅拌杆的两根侧板、螺接固定在倒U形安装板底部且用于刮物料缸底壁粘覆的物料的两个底刮板、螺接固定在两根侧板外侧面且用于刮物料缸侧壁粘覆的物料的侧刮板以及两组前后对称且与侧板固定连接的叉型搅拌叶片；
两根侧板外侧的翻边通过螺栓与搅拌杆顶端外侧的对接板上的翻边螺接连接，每组所述倒U形安装板顶部固定连接有与套筒连接的加强板，所述套筒限位在搅拌杆外侧面的限位圈的下方；
所述定位插接块***插槽后，通过贯穿于定位插接块和对接柱的螺栓螺母将定位插接块与对接柱连接固定。
作为本技术方案的进一步优化，所述翻转式物料缸组件包括固定在物料缸底部的翻转板以及推动翻转板翻转的推动组件，所述翻转板的底部左侧纵向排列设有三组第一凸字型块，所述翻转板的底部且位于三组第一凸字型块右侧设有三组第二凸字型块，三组第二凸字型块上贯穿固定有纵向轴；
所述推动组件包括前后对称设置的两个U型固定槽、固定设于两个U型固定槽顶部左端的两个第一矩形槽、固定分布在两个第一矩形槽顶部且纵向设置的三组轴承座、与三组轴承座转动连接的转轴、与两个第一矩形槽固定连接的L型固定座、固定设于L型固定座顶部的电机、与电机的输出轴传动连接的蜗轮蜗杆减速机以及与蜗轮蜗杆减速机的输出轴固定连接的力臂连杆；
所述力臂连杆上的套环转动套接在纵向轴的外侧面，三组第一凸字型块固定套接在转轴的外侧面；
两个所述U型固定槽的左右两端均固定设有支撑脚，前后两侧的两个所述第一凸字型块外侧面分别固定设有两个方形固定板，两个方形固定板底部的立板上固定设有导向块，两个U型固定槽左端外侧固定设置的连接块分别与两个弧形导向板固定连接，所述导向块与弧形导向板相配合限位导向滑动，所述弧形导向板上设有与导向块相配导向穿插滑动的弧形导向通孔槽，所述翻转板的顶部设有与物料缸相配合定位固定的定位件，两个所述U型固定槽的顶部右端还固定设有第二矩形槽。
综上所述，本发明具有以下有益效果：
1、本发明抗菌防霉剂有效地解决了季铵盐抗菌剂的溶出及热稳定性和无机抗菌剂的分散性问题，抗菌谱较现有的无机抗菌剂和季铵盐抗菌剂更广泛。本发明有效解决了热稳定性和分散性，主要是沸石有完整的晶体结构，而且与载入的离子紧密结合，提高原来了的热稳定性。当溶解在水中，水分子可以把离子包围，让离子不再跟晶体上的骨架结合，从而提高分散性；
2、本发明固液分散高速均化机，分散搅拌能够均匀，达到理想的物料搅拌效果，混合效果好，均化效果好，翻转式物料缸组件设计为可翻转的结构，方便卸料后的翻转清理和清洗；从而分散效率高，最终制备的产品稳定性好。
附图说明
图1为本发明的结构示意图；
图2为本发明图1的分解图；
图3为本发明液压缸的结构示意图；
图4为本发明对接组件的结构示意图；
图5为本发明旋转驱动组件的结构示意图；
图6为本发明旋转驱动组件上缸盖拆卸后的结构示意图。
图7为本发明可拆式搅拌组件的结构示意图；
图8为本发明连接杆与对接柱对接的结构示意图；
图9为本发明翻转式物料缸组件的结构示意图；
图10为本发明翻转板的结构示意图；
图11为本发明推动组件的结构示意图；
图12是实施例1抗菌防霉剂抗溶出性能分析图；
图13是实施例2抗菌防霉剂红外光谱分析图。
图中：1、升降机构；101、液压缸；102、立式外壳体；103、十字型导向开口槽；104、对接组件；105、限位板；106、U型箍；107、十字形插块；108、U型槽插块；109、锁紧螺母；110、底座；2、旋转驱动组件；201、驱动件；202、皮带；203、主动轮；204、从动轮；205、横向安装箱；206、圆台形连接座；207、连接杆；208、定位插接块；209、缸盖；210、；3、可拆式搅拌组件；301、插槽；302、对接柱；303、搅拌杆；304、分散盘；305、锁紧螺钉；306、倒U形安装板；307、侧板；308、底刮板；309、侧刮板；310、叉型搅拌叶片；311、套筒；312、对接板；313、加强板；314、限位圈；4、翻转式物料缸组件；401、物料缸；402、固定圈；403、插块；404、翻转板；405、推动组件；406、第一凸字型块；407、第二凸字型块；408、纵向轴；410、U型固定槽；411、第一矩形槽；412、轴承座；413、转轴；414、L型固定座；415、电机；416、蜗轮蜗杆减速机；417、力臂连杆；418、支撑脚；419、套环；420、方形固定板；421、立板；422、导向块；423、连接块；424、弧形导向板；425、弧形导向通孔槽；426、第二矩形槽。
具体实施方式
实施例1
100kg 1000目辉沸石与300kg去离子水混合，用均化器高速分散1小时，加入250kg 3M硝酸锌溶液，沸水浴加热搅拌2h，冷却过滤洗涤，10kg42％的(二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵溶液80℃搅拌2小时，喷雾干燥包装。
本实施例产品的抗溶出性能分析图见图12。从图12中可以看出，本实施例产品热稳定性好，至少可以耐160℃的高温。
实施例2
0.03mol的醋酸银150L与0.07mol的甘氨酸钠水溶液150L，混匀室温放置30min，50℃夹套保温搅拌2小时，搅拌速度60r/min。10kg 4A分子筛与30kg去离子水混合，用均化器高速分散1小时，然后加入到银氨溶液中搅拌均匀，密封，50℃保温继续搅拌过夜，冷却过滤洗涤，1kg42％的(二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵溶液80℃搅拌2小时，70℃低温真空干燥粉碎包装。
实施例3
25kg吸蓝量38的钠基蒙脱石与300kg去离子水混合，高速分散1小时，搅拌4小时，加入40kg 3M硫酸铜溶液，沸水浴加热搅拌2h，冷却过滤洗涤，3kg42％的甲基苄基十八烷基[3-(三甲氧基硅基)丙基]氯化铵溶液80℃搅拌2小时， 喷雾干燥包装。
本实施例产品的抗菌防霉剂红外光谱分析图见图13。
其中，红外光谱分析中1039cm-1为蒙脱石特征峰，2923cm-1、2853cm-1和1467cm-1为有机硅季铵盐中长链脂肪烃的特征吸收峰，625cm-1、796cm-1和1250cm-1为有机硅Si-C健特征峰，表明有机硅季铵盐已与蒙脱石反应结合，未在脱水洗涤工艺中脱除。
高速分散使用的一种固液分散高速均化机如图1-11所示，包括升降机构1、旋转驱动组件2、可拆式搅拌组件3以及翻转式物料缸组件4，可拆式搅拌组件3安装在旋转驱动组件2上，并由旋转驱动组件2带动旋转，在旋转的工程中将物料充分分散，升降机构1推动旋转驱动组件2升降，从而带动可拆式搅拌组件3升降，进行***翻转式物料缸组件4内侧或者远离翻转式物料缸组件4的两种运动；
升降机构1为液压缸101，升降机构1还包括固定在液压缸101外侧面的立式外壳体102、设于立式外壳体102左侧面的三组十字型导向开口槽103、抱箍在立式外壳体102外侧面且与物料缸401外侧面的固定圈402对接的对接组件104以及固定设于立式外壳体102底部的底座110，立式外壳体102的水平切面形状为半圆形与矩形拼接成的U形；
对接组件104包括限位在立式外壳体102左侧面的限位板105、箍在立式外壳体102外侧面且两端贯穿于限位板105的U型箍106、固定在限位板105右侧面且与三组十字型导向开口槽103相配合到相插接的三组十字形插块107以及固定设于限位板105左侧面的U型槽插块108，限位板105左侧面且位于U型箍106的两端螺接有将U型箍106锁紧固定在立式外壳体102上的锁紧螺母109；
固定圈402上的插块403***U型槽插块108内的槽口内后，固定圈402通过贯穿于插块403和U型槽插块108的螺栓固定在对接组件104上。
由于对接组件104通过U型箍106与限位板105的配合固定套接在立式外壳体102外侧面，方便根据不同安装需求，进行对接组件104安装高度的调整，调整方便，扩大适用范围；
旋转驱动组件2固定在液压缸101顶部，液压缸101推动旋转驱动组件2进行升降运动，且旋转驱动组件2包括驱动件201、皮带202、主动轮203以及从动轮204，驱动件201驱动主动轮203转动，主动轮203通过皮带202带动从动轮204转动，从动轮204的输出轴与搅拌器输出组件相连接，从而带动搅拌器输出组件转动；
旋转驱动组件2还包括固定在液压缸101活塞杆端部的横向安装箱205、设于横向安装箱205左端下方且与从动轮204的轮轴固定连接的圆台形连接座206、固定设于圆台形连接座206底部的连接杆207以及固定设于连接杆207底部的定位插接块208，主动轮203转动设于横向安装箱205内部右端，从动轮204转动设于横向安装箱205内部左端，驱动件201固定在横向安装箱205右端底部，驱动件为驱动电机，连接杆207通过轴承与缸盖209转动连接。
液压缸101推动横向安装箱205升降，从而带动连接杆207和缸盖209升降，方便缸盖209盖接在物料缸401上或者远离物料缸401，连接杆207与可拆式搅拌组件3连接；
可拆式搅拌组件3与搅拌器输出组件连接固定，带动搅拌器输出组件转动带动可拆式搅拌组件3转动，对固液混合物进行分散均化；
可拆式搅拌组件3包括带有插槽301的对接柱302、固定在对接柱302下方 的搅拌杆303、上下对称固定设于搅拌杆303外侧面的两组分散盘304、限位套接在搅拌杆303底端外侧面且通过锁紧螺钉305锁紧固定的套筒311、设于套筒311左右两侧的两组倒U形安装板306、固定在两组倒U形安装板306顶端外侧且与倒U形安装板306配合形成框式搅拌杆的两根侧板307、螺接固定在倒U形安装板306底部且用于刮物料缸401底壁粘覆的物料的两个底刮板308、螺接固定在两根侧板307外侧面且用于刮物料缸401侧壁粘覆的物料的侧刮板309以及两组前后对称且与侧板307固定连接的叉型搅拌叶片310；
两根侧板307外侧的翻边通过螺栓与搅拌杆303顶端外侧的对接板312上的翻边螺接连接，每组倒U形安装板306顶部固定连接有与套筒311连接的加强板313，套筒311限位在搅拌杆303外侧面的限位圈314的下方，由于两根侧板307的翻边与对接板312上的翻边螺接连接，方便两根侧板307以及两组倒U形安装板306单独拆卸，进行更换刮板或者清理粘覆物。
液压缸101推动可拆式搅拌组件3升降，节省高度空间，操作方便。将可拆式搅拌组件3的外部设计为框式翻料搅拌，中间分散盘304的高剪切分散，使中高粘度物料的固液混和，搭配叉型搅拌叶片310，分散搅拌能够均匀，达到理想的物料搅拌效果，混合效果好，均化效果好；
定位插接块208***插槽301后，通过贯穿于定位插接块208和对接柱302的螺栓螺母将定位插接块208与对接柱302连接固定。
定位插接块208***插槽301后通过螺母固定，方便可拆式搅拌组件3的安装和拆卸，方便对可拆式搅拌组件3进行拆卸清洗。
翻转式物料缸组件4包括物料缸401，可拆式搅拌组件3在液压缸101的推动作用下***或远离物料缸401，可拆式搅拌组件3***物料缸401内时用于拌匀物料缸401内的固液混合物。
翻转式物料缸组件4包括固定在物料缸401底部的翻转板404以及推动翻转板404翻转的推动组件405，翻转板404的底部左侧纵向排列设有三组第一凸字型块406，翻转板404的底部且位于三组第一凸字型块406右侧设有三组第二凸字型块407，三组第二凸字型块407上贯穿固定有纵向轴408；
推动组件405包括前后对称设置的两个U型固定槽410、固定设于两个U型固定槽410顶部左端的两个第一矩形槽411、固定分布在两个第一矩形槽411顶部且纵向设置的三组轴承座412、与三组轴承座412转动连接的转轴413、与两个第一矩形槽411固定连接的L型固定座414、固定设于L型固定座414顶部的电机415、与电机415的输出轴传动连接的蜗轮蜗杆减速机416以及与蜗轮蜗杆减速机416的输出轴固定连接的力臂连杆417；
力臂连杆417上的套环419转动套接在纵向轴408的外侧面，三组第一凸字型块406固定套接在转轴413的外侧面；
两个U型固定槽410的左右两端均固定设有支撑脚418，前后两侧的两个第一凸字型块406外侧面分别固定设有两个方形固定板420，两个方形固定板420底部的立板421上固定设有导向块422，两个U型固定槽410左端外侧固定设置的连接块423分别与两个弧形导向板424固定连接，导向块422与弧形导向板424相配合限位导向滑动，弧形导向板424上设有与导向块422相配导向穿插滑动的弧形导向通孔槽425，翻转板404的顶部设有与物料缸相配合定位固定的定位件，两个U型固定槽410的顶部右端还固定设有第二矩形槽426。
电机415带动蜗轮蜗杆减速机416从而推动力臂连杆417进行张开宇收折，使得力臂连杆417通过套环419与纵向轴408连接，能够推动顶起纵向轴408， 将翻转板404顶起翻转或者放平，在电机415以及蜗轮蜗杆减速机416的作用下，可以达到自锁的功能，平稳的将翻转板404翻转顶起，力臂连杆417连接纵向轴408为省力的杠杆结构，在物料缸401卸料结束后，能够翻转，方便清洗，相比于液压杆顶起，翻转板404翻转过程中的平稳性能更好，物料缸401翻转过程中稳定性更好，翻转更方便，不会在翻转过程中产生大震动，更加平和稳定。
实施例4
50kg纯度95％的凹凸棒土与300kg去离子水混合，高速分散1小时，搅拌4小时，加入20kg 3M硫酸铜溶液和20kg 3M硝酸锌溶液，沸水浴加热搅拌2h，冷却过滤洗涤，6kg 42％的甲基双十八烷基[3-(三甲氧基硅基)丙基]氯化铵溶液80℃搅拌2小时，喷雾干燥包装。
实施例5
25kg纯度95％的海泡石与300kg去离子水混合，用均化器高速分散1小时，加入20kg 3M硝酸锌溶液，沸水浴加热搅拌2h，冷却过滤洗涤，2kg 42％的(二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵溶液80℃搅拌2小时，喷雾干燥包装。
实施例6
100kg 1000目辉沸石与300kg去离子水混合，用均化器高速分散1小时，加入250kg 3M硝酸锌溶液，沸水浴加热搅拌2h，冷却过滤洗涤，10kg42％的(二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵溶液80℃搅拌2小时，加入10kg氧化锌80℃继续搅拌1h，喷雾干燥包装。
对照例
100kg 1000目辉沸石与300kg去离子水混合，用均化器高速分散1小时，加入250kg 3M硝酸锌溶液，沸水浴加热搅拌2h，冷却过滤洗涤，喷雾干燥包装。粉体抗菌评价试验
以纯度98-99％，粒径不大于100nm的二氧化硅为对照样，用GB/T 21510-2008附录A方法测试实施例样品的抗菌性能。
表1对大肠杆菌的抗菌效果
Figure PCTCN2022130293-appb-000003
Figure PCTCN2022130293-appb-000004
表2对金黄色葡萄球菌的抗菌效果
Figure PCTCN2022130293-appb-000005
在抗菌涂料中的应用评价
采用表3配方配制涂料，以空白配方涂料涂布50mmx50mm为空白对照样板，按GB/T21866-2008抗菌涂料(漆膜)抗菌性测定方法和抗菌效果测试抗菌性能。
表3抗菌涂料评价配方
Figure PCTCN2022130293-appb-000006
Figure PCTCN2022130293-appb-000007
表4抗菌涂料涂膜抗菌效果
Figure PCTCN2022130293-appb-000008
在抗菌塑料中的应用评价
对照和实施例样品3份，线性低密度聚乙烯47份,碳酸钙50份经熔融注塑制得50mmx50mmx5mm的试块，按QB/T 2591-2003抗菌塑料抗菌性能试验方法和抗菌效果测试。
表5聚乙烯塑料抗菌性能
Figure PCTCN2022130293-appb-000009
(符合0级的抗菌塑料可以报告有强抗霉菌作用；长霉等级符合I级的抗菌塑料可以报告有抗霉菌作用)
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。

Claims (10)

  1. 一种协效抗菌防霉剂，其特征在于结构为：
    Figure PCTCN2022130293-appb-100001
    结构图中，M n+为Ag、Cu、Zn金属离子,负载在沸石、分子筛和粘土的孔道中，R 1为甲基或氢，R 2为甲基、苄基或12至22个碳链的烷烃，R 3为12至22个碳链的烷烃。
  2. 一种如权利要求1所述的协效抗菌防霉剂的制备方法，其特征在于包括以下制备步骤：
    (1)采用含表面羟基的多孔阳离子离子交换载体负载银、铜和锌金属离子；
    (2)用含有烷氧基的有机硅季铵盐对其进行表面改性，烷氧基与载体表面的羟基反应形成Si-O键，使季铵盐牢固地结合载载体上。
  3. 一种如权利要求2所述的协效抗菌防霉剂的制备方法，其特征在于：采用含表面羟基的多孔阳离子离子交换载体负载银、铜和锌金属离子具体包括：在100重量份的沸石中加入硝酸银或者硫酸铜溶液200-30重量份，高速分散，反应温度70-80℃，常压反应1.5-2.5个小时。
  4. 一种如权利要求3所述的协效抗菌防霉剂的制备方法，其特征在于：用含有烷氧基的有机硅季铵盐对其进行表面改性的方法具体包括：在100重量份的沸石中加入有机季铵盐溶液5-15重量份，高速分散，反应温度70-80℃，常压反应1.5-2.5小时。
  5. 一种如权利要求4所述的协效抗菌防霉剂的制备方法，其特征在于：所述含表面羟基的多孔阳离子离子交换载体是天然沸石(Zeolite)、合成硅铝分子筛(MOLECULAR SIEVE)、蒙脱石(膨润土bentonite)、凹凸棒土(又称坡缕石Palygorskite)、海泡石。分子式为：
    Figure PCTCN2022130293-appb-100002
    Figure PCTCN2022130293-appb-100003
  6. 一种如权利要求2-5任一项所述的协效抗菌防霉剂的制备方法，其特征在于：协效抗菌防霉剂的制备步骤(1)和步骤(2)高速分散使用的固液分散高速均化机，包括：
    升降机构(1)，所述升降机构(1)为液压缸(101)；
    旋转驱动组件(2)，所述旋转驱动组件(2)固定在液压缸(101)顶部，液压缸(101)推动旋转驱动组件(2)进行升降运动，且旋转驱动组件(2)包括驱动件(201)、皮带(202)、主动轮(203)以及从动轮(204)，驱动件(201)驱动主动轮(203)转动，主动轮(203)通过皮带(202)带动从动轮(204)转动，从动轮(204)的输出轴与搅拌器输出组件相连接，从而带动搅拌器输出组件转动；
    可拆式搅拌组件(3)，所述可拆式搅拌组件(3)与搅拌器输出组件连接固定，带动搅拌器输出组件转动带动可拆式搅拌组件(3)转动，对固液混合物进行分散均化；
    翻转式物料缸组件(4)，所述翻转式物料缸组件(4)包括物料缸(401)，所述可拆式搅拌组件(3)在液压缸(101)的推动作用下***或远离物料缸(401)，可拆式搅拌组件(3)***物料缸(401)内时用于拌匀物料缸(401)内的固液混合物。
  7. 一种如权利要求6所述的协效抗菌防霉剂的制备方法，其特征在于：所述对接组件(104)包括限位在立式外壳体(102)左侧面的限位板(105)、箍在立式外壳体(102)外侧面且两端贯穿于限位板(105)的U型箍(106)、固定在限位板(105)右侧面且与三组十字型导向开口槽(103)相配合到相插接的三组十字形插块(107)以及固定设于限位板(105)左侧面的U型槽插块(108)，限位板(105)左侧面且位于U型箍(106)的两端螺接有将U型箍(106)锁紧固定在立式外壳体(102)上的锁紧螺母(109)；
    所述固定圈(402)上的插块(403)***U型槽插块(108)内的槽口内后，固定圈(402)通过贯穿于插块(403)和U型槽插块(108)的螺栓固定在对接组件(104)上。
  8. 一种如权利要求7所述的协效抗菌防霉剂的制备方法，其特征在于：所述旋转驱动组件(2)还包括固定在液压缸(101)活塞杆端部的横向安装箱(205)、设于横向安装箱(205)左端下方且与从动轮(204)的轮轴固定连接的圆台形连接座(206)、固定设于圆台形连接座(206)底部的连接杆(207)以及固定设于连接杆(207)底部的定位插接块(208)，所述主动轮(203)转动设于横向安装箱(205)内部右端，从动轮(204)转动设于横向安装箱(205)内部左端，驱动件(201)固定在横向安装箱(205)右端底部，驱动件为驱动电机，所述连接杆(207)通过轴承与缸盖(209)转动连接。
  9. 一种如权利要求8所述的协效抗菌防霉剂的制备方法，其特征在于：所 述可拆式搅拌组件(3)包括带有插槽(301)的对接柱(302)、固定在对接柱(302)下方的搅拌杆(303)、上下对称固定设于搅拌杆(303)外侧面的两组分散盘(304)、限位套接在搅拌杆(303)底端外侧面且通过锁紧螺钉(305)锁紧固定的套筒(311)、设于套筒(311)左右两侧的两组倒U形安装板(306)、固定在两组倒U形安装板(306)顶端外侧且与倒U形安装板(306)配合形成框式搅拌杆的两根侧板(307)、螺接固定在倒U形安装板(306)底部且用于刮物料缸(401)底壁粘覆的物料的两个底刮板(308)、螺接固定在两根侧板(307)外侧面且用于刮物料缸(401)侧壁粘覆的物料的侧刮板(309)以及两组前后对称且与侧板(307)固定连接的叉型搅拌叶片(310)；
    两根侧板(307)外侧的翻边通过螺栓与搅拌杆(303)顶端外侧的对接板(312)上的翻边螺接连接，每组所述倒U形安装板(306)顶部固定连接有与套筒(311)连接的加强板(313)，所述套筒(311)限位在搅拌杆(303)外侧面的限位圈(314)的下方；
    所述定位插接块(208)***插槽(301)后，通过贯穿于定位插接块(208)和对接柱(302)的螺栓螺母将定位插接块(208)与对接柱(302)连接固定。
  10. 一种如权利要求9所述的协效抗菌防霉剂的制备方法，其特征在于：所述翻转式物料缸组件(4)包括固定在物料缸(401)底部的翻转板(404)以及推动翻转板(404)翻转的推动组件(405)，所述翻转板(404)的底部左侧纵向排列设有三组第一凸字型块(406)，所述翻转板(404)的底部且位于三组第一凸字型块(406)右侧设有三组第二凸字型块(407)，三组第二凸字型块(407)上贯穿固定有纵向轴(408)；
    所述推动组件(405)包括前后对称设置的两个U型固定槽(410)、固定设于两个U型固定槽(410)顶部左端的两个第一矩形槽(411)、固定分布在两个第一矩形槽(411)顶部且纵向设置的三组轴承座(412)、与三组轴承座(412)转动连接的转轴(413)、与两个第一矩形槽(411)固定连接的L型固定座(414)、固定设于L型固定座(414)顶部的电机(415)、与电机(415)的输出轴传动连接的蜗轮蜗杆减速机(416)以及与蜗轮蜗杆减速机(416)的输出轴固定连接的力臂连杆(417)；
    所述力臂连杆(417)上的套环(419)转动套接在纵向轴(408)的外侧面，三组第一凸字型块(406)固定套接在转轴(413)的外侧面；
    两个所述U型固定槽(410)的左右两端均固定设有支撑脚(418)，前后两侧的两个所述第一凸字型块(406)外侧面分别固定设有两个方形固定板(420)，两个方形固定板(420)底部的立板(421)上固定设有导向块(422)，两个U型固定槽(410)左端外侧固定设置的连接块(423)分别与两个弧形导向板(424)固定连接，所述导向块(422)与弧形导向板(424)相配合限位导向滑动，所述弧形导向板(424)上设有与导向块(422)相配导向穿插滑动的弧形导向通孔槽(425)，所述翻转板(404)的顶部设有与法兰(2)相配合定位固定的定位件，两个所述U型固定槽(410)的顶部右端还固定设有第二矩形槽(426)。
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