CN117603544A - Antibacterial and mildew-proof modified plastic and preparation method thereof - Google Patents
Antibacterial and mildew-proof modified plastic and preparation method thereof Download PDFInfo
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- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000011787 zinc oxide Substances 0.000 claims abstract description 78
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 54
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 54
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003607 modifier Substances 0.000 claims abstract description 28
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 22
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims abstract description 11
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 11
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 11
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002347 injection Methods 0.000 claims abstract description 9
- 239000007924 injection Substances 0.000 claims abstract description 9
- NMILVDSXWZZAKX-UHFFFAOYSA-N 1h-imidazole;silicon Chemical compound [Si].C1=CNC=N1 NMILVDSXWZZAKX-UHFFFAOYSA-N 0.000 claims abstract 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
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- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- SNYNNFDVNITLRQ-UHFFFAOYSA-N 2,2,4,4,6,6,8-heptamethyl-1,3,5,7,2,4,6,8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 SNYNNFDVNITLRQ-UHFFFAOYSA-N 0.000 claims description 15
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 6
- WSPOQKCOERDWJQ-UHFFFAOYSA-N 2-methyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 WSPOQKCOERDWJQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses an antibacterial mildew-proof modified plastic and a preparation method thereof, and relates to the technical field of high polymer materials. In the preparation of the antibacterial mildew-proof modified plastic, 2-amino ethanol, paraformaldehyde and dimethyl phosphite are reacted to prepare a modifier, polyvinyl chloride is reacted with the modifier, and then the modified polyvinyl chloride is prepared by hydrochloric acid aqueous solution treatment; methyl cyclotetrasiloxane and N-vinyl imidazole react and then react with 1-bromo-N-dodecane to prepare organosilicon imidazole salt; the nano zinc oxide is sequentially reacted with allyl triethoxysilane, pentamethyl disiloxane and organic silicon imidazole salt to prepare modified nano zinc oxide, and the modified polyvinyl chloride and the modified nano zinc oxide are mixed, extruded and injection molded to prepare the antibacterial mildew-proof modified plastic. The antibacterial mildew-proof modified plastic prepared by the invention has good antibacterial mildew-proof performance, tensile performance and flame retardant performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antibacterial and mildew-proof modified plastic and a preparation method thereof.
Background
In daily life, people can contact various plastic products such as garbage bags, plastic garbage cans, food packaging bags and other kitchen and sanitary tools. Under the general condition, bacteria are easily adhered to the surface of the plastic product, and bacterial infection can be caused in the using process. Therefore, the application range of the antibacterial plastic in daily life of people is wider and wider. Such as plastic articles that are often exposed to water in toilets, kitchens, etc., or are often in a relatively humid environment. In addition, household appliances, such as refrigerators, washing machines, etc., which are necessary in daily life, are often in a humid and water-contacting environment during normal use. Under these environmental conditions, bacteria, fungi and other microorganisms are greatly bred, so that people contacted with the bacteria, fungi and other microorganisms are at risk of bacterial and fungal infection, and the health and safety of the people are threatened. In addition, the use of antimicrobial plastic articles in the field of food packaging, such as food packaging plastic bags or plastic films, is also important.
Nowadays, people have extremely high attention in health and safety, medical treatment and health and the like, and the people are promoted to have higher and stricter standards and demands on products such as plastic dishes, preservative films, medical appliances, disposable medical consumables and the like which are in direct contact or indirect contact in use. There are more and more cases of bacterial infection of wounds of patients during or after operation and cases of oral intake caused by bacteria, fungi and other microorganisms growing on plastic dishes and plastic preservative films. Therefore, the plastic with good antibacterial effect is developed, and has great market prospect.
Disclosure of Invention
The invention aims to provide antibacterial and mildew-proof modified plastic and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
an antibacterial and mildew-proof modified plastic is prepared by mixing, extruding and injection molding modified polyvinyl chloride and modified nano zinc oxide.
As optimization, the modified polyvinyl chloride is prepared by reacting 2-aminoethanol, paraformaldehyde and dimethyl phosphite to prepare a modifier and reacting the polyvinyl chloride with the modifier.
As optimization, the modified nano zinc oxide is prepared by sequentially reacting nano zinc oxide with allyl triethoxysilane, pentamethyl disiloxane and organosilicon imidazole salt.
Preferably, the organosilicon imidazole salt is prepared by reacting heptamethyl cyclotetrasiloxane with N-vinyl imidazole and then reacting with 1-bromo-N-dodecane.
The preparation method of the antibacterial mildew-proof modified plastic comprises the following preparation steps:
(1) Uniformly mixing heptamethyl cyclotetrasiloxane, chloroplatinic acid and N-hexane according to the mass ratio of (0.01-0.02) (8-10), adding N-vinylimidazole with the same molar weight as that of the heptamethyl cyclotetrasiloxane, stirring and refluxing for 4-6 hours at 70-80 ℃ and 500-800 r/min, standing for 2-3 hours at 20-30 ℃, mixing and washing for 3-5 times by pure water and N-hexane with the same volume as that of the pure water, standing for layering after each washing, removing the water phase, and drying for 6-8 hours at 30-40 ℃ and 1-2 kPa to obtain the organosilicon imidazole; uniformly mixing organosilicon imidazole and 1-bromo-n-dodecane according to a molar ratio of 1:1, and stirring at a temperature of 5-10 ℃ and a speed of 200-300 r/min for reacting for 40-48 hours to obtain organosilicon imidazole salt;
(2) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1 (6-8) (0.01-0.02) to prepare a pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1 (3-4) (10-12), stirring and reacting for 1-2 hours at 20-30 ℃ at 200-300 r/min, centrifugally separating, washing for 3-5 times by absolute ethyl alcohol, drying for 6-8 hours at 60-70 ℃, placing in a pentamethyl disiloxane mixed solution with the mass of 8-10 times of nano zinc oxide, stirring and refluxing for 3-4 hours at 70-80 ℃ at 300-500 r/min in a nitrogen atmosphere, centrifugally separating, washing for 3-5 times by absolute ethyl alcohol, and drying for 6-8 hours at 60-70 ℃ to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, organosilicon imidazole salt and N, N-dimethylformamide according to the mass ratio of 1:1 (4-6), dropwise adding a trifluoromethane sulfonic acid aqueous solution with the mass fraction of 10-12% which is 1.6-2 times of the mass of the pretreated nano zinc oxide at a constant speed within 15-20 min under the stirring condition of 300-500 r/min at the temperature of 70-80 ℃, continuously stirring for reacting for 60-80 min after the dropwise adding, centrifugally separating, washing 3-5 times by pure water and absolute ethyl alcohol respectively, and drying for 6-8 h at the temperature of 60-70 ℃ under the pressure of 10-50 Pa to obtain modified nano zinc oxide;
(3) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 8-10 and tetrahydrofuran according to the mass ratio of (8-10) of 1:2, stirring for 20-30 min at the temperature of 65-70 ℃ at 300-500 r/min, continuously stirring, adding dimethyl phosphite with the molar weight of 2 times that of 2-aminoethanol at a constant speed within 10-15 min, continuously stirring for reacting for 8-10 h after the addition is finished, and drying for 6-8 h at the temperature of 40-50 ℃ at 100-500 Pa to obtain a modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to the mass ratio of 1:1 (0.3-0.4) (25-30), stirring at 30-40 ℃ for reaction for 10-12 h at 300-500 r/min, drying at 30-40 ℃ for 10-12 h at 10-50 Pa, then placing in a hydrochloric acid aqueous solution with the mass fraction of 3-5% and the mass fraction of 6-8 times of the polyvinyl chloride, stirring at 30-40 ℃ for 6-8 min at 300-500 r/min, filtering, washing with pure water for 3-5 times, and drying at 30-40 ℃ for 10-50 Pa for 10-12 h to obtain modified polyvinyl chloride;
(4) Weighing 80-100 parts of modified polyvinyl chloride according to parts by weight, placing 10-15 parts of modified nano zinc oxide in a double screw extruder for mixing extrusion, wherein the temperature of three areas of the double screw extruder is 180-185 ℃, 185-190 ℃, the screw speed of 190-195 ℃ is 44-48 r/min, injecting the extruded mixture into a die at 200-210 ℃ and the injection pressure of 7-7.5 MPa by an injection molding machine, standing for 20-24 h at 90-100 ℃, and naturally cooling to room temperature to obtain the antibacterial and mildew-proof modified plastic.
As an optimization, the reaction process of the organosilicon imidazole in the step (1) is as follows:
；
the reaction process of the organosilicon imidazole salt is as follows:
。
as an optimization, the reaction process of the modifier in the step (3) is as follows:
。
as optimization, the reaction process of the polyvinyl chloride and the modifier in the step (3) is as follows:
。
and (3) optimally, the model of the polyvinyl chloride in the step (3) is S-1000.
As an optimization, the antibacterial and mildew-proof modified plastic can be added with related polyvinyl chloride auxiliary agents according to the requirement in the step (4).
Compared with the prior art, the invention has the following beneficial effects:
when the antibacterial mildew-proof modified plastic is prepared, polyvinyl chloride and a modifier react, and then the modified polyvinyl chloride is prepared by hydrochloric acid aqueous solution treatment; the antibacterial and mildew-proof modified plastic is prepared by mixing, extruding and injection molding modified polyvinyl chloride and modified nano zinc oxide.
Firstly, methyl cyclotetrasiloxane and N-vinyl imidazole react and then react with 1-bromo-N-dodecane to prepare organosilicon imidazole salt, nano zinc oxide reacts with allyl triethoxysilane, pentamethyl disiloxane and organosilicon imidazole salt in sequence to prepare modified nano zinc oxide, a polysiloxane long chain is generated on the surface of the modified nano zinc oxide, the modified nano zinc oxide has good compatibility with modified polyvinyl chloride, the dispersibility of the nano zinc oxide is improved, the nano zinc oxide has certain antibacterial property, and the nano zinc oxide is also a reinforcing agent and a filling agent, so that the antibacterial mildew resistance and the tensile strength are improved, and meanwhile, the generated polysiloxane long chain can improve the flame retardant effect; the organosilicon imidazole salt makes polysiloxane long chain on the surface of the modified nano zinc oxide contain a large number of imidazole salt structures, the imidazole salt structure with positive charge attracts negatively charged bacterial cell walls under the action of electrostatic force, and fat-soluble long chain penetrates into the bacterial cell walls and cell membranes to crack and kill the bacteria, so that the antibacterial effect is further improved.
Secondly, 2-aminoethanol, paraformaldehyde and dimethyl phosphite react to prepare a modifier, the modifier is used for modifying polyvinyl chloride, a branched chain formed on the polyvinyl chloride contains a phosphate structure, and phosphorus has the effect of promoting the formation of a carbon layer, so that the flame retardance is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method provided by the present invention is described in detail by the following examples for more clarity of illustration.
The comparative examples below used a nano zinc oxide model ZnO-0020, available from Zhejiang submicron nanotechnology Co., ltd; the polyvinyl chloride model is S-1000, and is purchased from the Oletum Trogopterori.
Example 1
The preparation method of the antibacterial and mildew-proof modified plastic mainly comprises the following preparation steps:
(1) Uniformly mixing heptamethyl cyclotetrasiloxane, chloroplatinic acid and N-hexane according to the mass ratio of 1 (0.01) (8), adding N-vinylimidazole with the same molar weight as that of the heptamethyl cyclotetrasiloxane, stirring and refluxing for 6 hours at 70 ℃ and 500r/min, standing for 3 hours at 20 ℃ under 1kPa, mixing and washing for 3 times with pure water and N-hexane with the same volume as that of the pure water, standing for layering after each washing, removing the water phase, and drying for 8 hours at 30 ℃ under 1kPa to prepare the organosilicon imidazole; uniformly mixing organosilicon imidazole and 1-bromo-n-dodecane according to a molar ratio of 1:1, and stirring and reacting at 5 ℃ and 200r/min for 48 hours to obtain organosilicon imidazole salt;
(2) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:6:0.01 to prepare pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1:3:10, stirring at 20 ℃ for reaction for 2 hours at 200r/min, centrifugally separating, washing with absolute ethyl alcohol for 3 times, drying at 60 ℃ for 8 hours, placing in pentamethyl disiloxane mixed solution with the mass of 8 times of nano zinc oxide, stirring and refluxing at 70 ℃ for 4 hours at 300r/min in a nitrogen atmosphere, centrifugally separating, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 8 hours to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, organosilicon imidazole salt and N, N-dimethylformamide according to a mass ratio of 1:1:4, dropwise adding a 10% aqueous solution of trifluoromethane sulfonic acid with a mass fraction of 1.6 times that of the pretreated nano zinc oxide at a uniform speed within 15min under the stirring condition of 300r/min at 70 ℃, continuously stirring for reacting for 80min after the dropwise adding is finished, centrifugally separating, washing 3 times by pure water and absolute ethyl alcohol respectively, and drying for 8h at 10Pa at 60 ℃ to obtain modified nano zinc oxide;
(3) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 8 and tetrahydrofuran according to the mass ratio of 1:2:8, stirring for 30min at 65 ℃ and 300r/min, continuously stirring, adding dimethyl phosphite with the 2-aminoethanol molar quantity being 2 times at a constant speed within 10min, continuously stirring for reaction for 10h after the addition is finished, and drying for 8h at 40 ℃ and 100Pa to obtain a modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to a mass ratio of 1:1:0.3:25, stirring at 30 ℃ for reaction for 12 hours under 300r/min, drying at 30 ℃ under 10Pa for 12 hours, placing in a hydrochloric acid aqueous solution with mass fraction of 3% and 6 times of the mass of the polyvinyl chloride, stirring at 30 ℃ for 8 minutes under 300r/min, filtering, washing with pure water for 3 times, and drying at 30 ℃ under 10Pa for 12 hours to obtain modified polyvinyl chloride;
(4) Weighing 80 parts of modified polyvinyl chloride and 10 parts of modified nano zinc oxide according to parts by weight, putting the 80 parts of modified nano zinc oxide into a double-screw extruder for mixing and extrusion, wherein the temperature of three areas of the double-screw extruder is respectively 180 ℃, 185 ℃, 190 ℃ and the screw speed is 44r/min, injecting the extruded mixture into a die by an injection molding machine at 200 ℃ and the injection pressure of 7MPa, standing the die at 90 ℃ for 24 hours, and naturally cooling the die to room temperature to obtain the antibacterial mildew-proof modified plastic.
Example 2
The preparation method of the antibacterial and mildew-proof modified plastic mainly comprises the following preparation steps:
(1) Uniformly mixing heptamethyl cyclotetrasiloxane, chloroplatinic acid and N-hexane according to the mass ratio of 1:0.015:9, adding N-vinylimidazole with the same molar weight as that of the heptamethyl cyclotetrasiloxane, stirring and refluxing for 5 hours at 75 ℃ and 650r/min, standing for 2.5 hours at 25 ℃, mixing and washing for 4 times by pure water and N-hexane with the same volume as that of the pure water, standing and layering after each washing, removing the water phase, and drying for 7 hours at 35 ℃ and 1.5kPa to obtain the organosilicon imidazole; uniformly mixing organosilicon imidazole and 1-bromo-n-dodecane according to a molar ratio of 1:1, and stirring at 8 ℃ and 250r/min for reaction for 44 hours to prepare organosilicon imidazole salt;
(2) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:7:0.015 to prepare a pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1:3.5:11, stirring at 25 ℃ for reaction for 1.5 hours at 250r/min, centrifugally separating, washing with absolute ethyl alcohol for 4 times, drying at 65 ℃ for 7 hours, placing in pentamethyl disiloxane mixed solution with the mass of 9 times of nano zinc oxide, stirring at 75 ℃ for reflux for 3.5 hours at 400r/min in nitrogen atmosphere, centrifugally separating, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ for 7 hours to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, organosilicon imidazole salt and N, N-dimethylformamide according to a mass ratio of 1:1:5, dropwise adding a trifluoromethane sulfonic acid aqueous solution with a mass fraction of 11% which is 1.8 times that of the pretreated nano zinc oxide at a uniform speed within 18min under the stirring condition of 400r/min at the temperature of 75 ℃, continuously stirring for reacting for 70min after the dropwise adding is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying for 7h at the pressure of 30Pa at the temperature of 65 ℃ to obtain modified nano zinc oxide;
(3) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 9 and tetrahydrofuran according to the mass ratio of 1:2:9, stirring at 68 ℃ for 25min at 400r/min, continuously stirring, adding dimethyl phosphite with the 2-aminoethanol molar quantity being 2 times at a constant speed within 12min, continuously stirring for reacting for 9h after the addition is finished, and drying at 45 ℃ for 7h at 300Pa to obtain a modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to a mass ratio of 1:1:0.35:28, stirring at 35 ℃ for reaction at 400r/min for 11h, drying at 35 ℃ for 11h under 30Pa, placing in a hydrochloric acid aqueous solution with mass fraction of 4% and 7 times that of the polyvinyl chloride, stirring at 35 ℃ for 7min at 400r/min, filtering, washing with pure water, filtering for 4 times, and drying at 35 ℃ for 11h under 30Pa to obtain modified polyvinyl chloride;
(4) 90 parts of modified polyvinyl chloride and 12 parts of modified nano zinc oxide are weighed according to parts by weight, and are placed in a double-screw extruder for mixed extrusion, the temperature of three areas of the double-screw extruder is 182 ℃ and 187 ℃ respectively, the screw speed is 46r/min at 192 ℃, after extrusion, the three areas are injected into a die through an injection molding machine at 205 ℃ and the injection pressure is 7.2MPa, and the mixture is kept stand at 95 ℃ for 22 hours and naturally cooled to room temperature, so that the antibacterial mildew-proof modified plastic is prepared.
Example 3
The preparation method of the antibacterial and mildew-proof modified plastic mainly comprises the following preparation steps:
(1) Uniformly mixing heptamethyl cyclotetrasiloxane, chloroplatinic acid and N-hexane according to the mass ratio of 1:0.02:10, adding N-vinylimidazole with the same molar weight as that of the heptamethyl cyclotetrasiloxane, stirring and refluxing for 4 hours at 80 ℃ and 800r/min, standing for 2 hours at 30 ℃, mixing and washing for 5 times by pure water and N-hexane with the same volume as that of the pure water, standing for layering after each washing, removing a water phase, and drying for 6 hours at 40 ℃ and 2kPa to prepare the organosilicon imidazole; uniformly mixing organosilicon imidazole and 1-bromo-n-dodecane according to a molar ratio of 1:1, and stirring at 10 ℃ and 300r/min for reaction for 40 hours to prepare organosilicon imidazole salt;
(2) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:8:0.02 to prepare a pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1:4:12, stirring at 30 ℃ for reaction for 1h at 300r/min, centrifugally separating, washing with absolute ethyl alcohol for 5 times, drying at 70 ℃ for 6h, placing in pentamethyl disiloxane mixed solution with the mass of 10 times of nano zinc oxide, stirring and refluxing at 80 ℃ for 3h at 500r/min in a nitrogen atmosphere, centrifugally separating, washing with absolute ethyl alcohol for 5 times, and drying at 70 ℃ for 6h to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, organosilicon imidazole salt and N, N-dimethylformamide according to a mass ratio of 1:1:6, dropwise adding a trifluoromethane sulfonic acid aqueous solution with a mass fraction of 12% which is 2 times that of the pretreated nano zinc oxide at a uniform speed within 20min under the stirring condition of 500r/min at 80 ℃, continuously stirring for reacting for 60min after the dropwise adding is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 5 times respectively, and drying for 6h at 50Pa at 70 ℃ to obtain modified nano zinc oxide;
(3) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 10 and tetrahydrofuran according to the mass ratio of 1:2:10, stirring for 20min at 70 ℃ and 500r/min, continuously stirring, adding dimethyl phosphite with the 2-aminoethanol molar quantity being 2 times at a constant speed within 15min, continuously stirring and reacting for 8h after the addition is finished, and drying for 6h at 50 ℃ and 500Pa to obtain the modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to a mass ratio of 1:1:0.4:30, stirring at 40 ℃ for reaction for 10 hours at 500r/min, drying at 40 ℃ for 10 hours under 50Pa, placing in a hydrochloric acid aqueous solution with mass fraction of 5% and 8 times of the mass of the polyvinyl chloride, stirring at 40 ℃ for 6 minutes at 500r/min, filtering, washing with pure water, filtering for 5 times, and drying at 40 ℃ under 50Pa for 10 hours to obtain modified polyvinyl chloride;
(4) 100 parts of modified polyvinyl chloride and 15 parts of modified nano zinc oxide are weighed according to parts by weight, and are placed in a double-screw extruder for mixed extrusion, the temperature of three areas of the double-screw extruder is 185 ℃ and 190 ℃ respectively, the screw speed is 48r/min, the extruded materials are injected into a die by an injection molding machine at 210 ℃ and the injection pressure is 7.5MPa, and the materials are kept stand at 100 ℃ for 20 hours and naturally cooled to room temperature, so that the antibacterial mildew-proof modified plastic is prepared.
Comparative example 1
The preparation method of the antibacterial and mildew-proof modified plastic mainly comprises the following preparation steps:
(1) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:7:0.015 to prepare a pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1:3.5:11, stirring at 25 ℃ for reaction for 1.5 hours at 250r/min, centrifugally separating, washing with absolute ethyl alcohol for 4 times, drying at 65 ℃ for 7 hours, placing in pentamethyl disiloxane mixed solution with the mass of 9 times of nano zinc oxide, stirring at 75 ℃ for reflux for 3.5 hours at 400r/min in nitrogen atmosphere, centrifugally separating, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ for 7 hours to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, octamethyl cyclotetrasiloxane and N, N-dimethylformamide according to a mass ratio of 1:1:5, dropwise adding a trifluoromethane sulfonic acid aqueous solution with a mass fraction of 11% which is 1.8 times that of the pretreated nano zinc oxide at a uniform speed within 18min under the stirring condition of 400r/min at the temperature of 75 ℃, continuing stirring for reacting for 70min after the dropwise adding, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying for 7h at the pressure of 30Pa at the temperature of 65 ℃ to obtain modified nano zinc oxide;
(2) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 9 and tetrahydrofuran according to the mass ratio of 1:2:9, stirring at 68 ℃ for 25min at 400r/min, continuously stirring, adding dimethyl phosphite with the 2-aminoethanol molar quantity being 2 times at a constant speed within 12min, continuously stirring for reacting for 9h after the addition is finished, and drying at 45 ℃ for 7h at 300Pa to obtain a modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to a mass ratio of 1:1:0.35:28, stirring at 35 ℃ for reaction at 400r/min for 11h, drying at 35 ℃ for 11h under 30Pa, placing in a hydrochloric acid aqueous solution with mass fraction of 4% and 7 times that of the polyvinyl chloride, stirring at 35 ℃ for 7min at 400r/min, filtering, washing with pure water, filtering for 4 times, and drying at 35 ℃ for 11h under 30Pa to obtain modified polyvinyl chloride;
(3) 90 parts of modified polyvinyl chloride and 12 parts of modified nano zinc oxide are weighed according to parts by weight, and are placed in a double-screw extruder for mixed extrusion, the temperature of three areas of the double-screw extruder is 182 ℃ and 187 ℃ respectively, the screw speed is 46r/min at 192 ℃, after extrusion, the three areas are injected into a die through an injection molding machine at 205 ℃ and the injection pressure is 7.2MPa, and the mixture is kept stand at 95 ℃ for 22 hours and naturally cooled to room temperature, so that the antibacterial mildew-proof modified plastic is prepared.
Comparative example 2
The preparation method of the antibacterial and mildew-proof modified plastic mainly comprises the following preparation steps:
(1) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 9 and tetrahydrofuran according to the mass ratio of 1:2:9, stirring at 68 ℃ for 25min at 400r/min, continuously stirring, adding dimethyl phosphite with the 2-aminoethanol molar quantity being 2 times at a constant speed within 12min, continuously stirring for reacting for 9h after the addition is finished, and drying at 45 ℃ for 7h at 300Pa to obtain a modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to a mass ratio of 1:1:0.35:28, stirring at 35 ℃ for reaction at 400r/min for 11h, drying at 35 ℃ for 11h under 30Pa, placing in a hydrochloric acid aqueous solution with mass fraction of 4% and 7 times that of the polyvinyl chloride, stirring at 35 ℃ for 7min at 400r/min, filtering, washing with pure water, filtering for 4 times, and drying at 35 ℃ for 11h under 30Pa to obtain modified polyvinyl chloride;
(2) Weighing 90 parts of modified polyvinyl chloride and 12 parts of nano zinc oxide according to parts by weight, putting the 90 parts of modified polyvinyl chloride and the 12 parts of nano zinc oxide into a double-screw extruder for mixing and extrusion, wherein the temperature of three areas of the double-screw extruder is 182 ℃ and 187 ℃ respectively, the screw speed is 46r/min at 192 ℃, injecting the extruded materials into a die at 205 ℃ and the injection pressure of 7.2MPa through an injection molding machine, standing the die at 95 ℃ for 22 hours, and naturally cooling the die to room temperature to obtain the antibacterial mildew-proof modified plastic.
Comparative example 3
The preparation method of the antibacterial and mildew-proof modified plastic mainly comprises the following preparation steps:
(1) Uniformly mixing heptamethyl cyclotetrasiloxane, chloroplatinic acid and N-hexane according to the mass ratio of 1:0.015:9, adding N-vinylimidazole with the same molar weight as that of the heptamethyl cyclotetrasiloxane, stirring and refluxing for 5 hours at 75 ℃ and 650r/min, standing for 2.5 hours at 25 ℃, mixing and washing for 4 times by pure water and N-hexane with the same volume as that of the pure water, standing and layering after each washing, removing the water phase, and drying for 7 hours at 35 ℃ and 1.5kPa to obtain the organosilicon imidazole; uniformly mixing organosilicon imidazole and 1-bromo-n-dodecane according to a molar ratio of 1:1, and stirring at 8 ℃ and 250r/min for reaction for 44 hours to prepare organosilicon imidazole salt;
(2) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:7:0.015 to prepare a pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1:3.5:11, stirring at 25 ℃ for reaction for 1.5 hours at 250r/min, centrifugally separating, washing with absolute ethyl alcohol for 4 times, drying at 65 ℃ for 7 hours, placing in pentamethyl disiloxane mixed solution with the mass of 9 times of nano zinc oxide, stirring at 75 ℃ for reflux for 3.5 hours at 400r/min in nitrogen atmosphere, centrifugally separating, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ for 7 hours to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, organosilicon imidazole salt and N, N-dimethylformamide according to a mass ratio of 1:1:5, dropwise adding a trifluoromethane sulfonic acid aqueous solution with a mass fraction of 11% which is 1.8 times that of the pretreated nano zinc oxide at a uniform speed within 18min under the stirring condition of 400r/min at the temperature of 75 ℃, continuously stirring for reacting for 70min after the dropwise adding is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying for 7h at the pressure of 30Pa at the temperature of 65 ℃ to obtain modified nano zinc oxide;
(3) 90 parts of polyvinyl chloride and 12 parts of modified nano zinc oxide are weighed according to parts by weight, and are placed in a double-screw extruder for mixed extrusion, the temperature of three areas of the double-screw extruder is 182 ℃ and 187 ℃ respectively, the screw speed is 46r/min at 192 ℃, after extrusion, the mixture is injected into a die by an injection molding machine at 205 ℃ and the injection pressure is 7.2MPa, and the mixture is stood at 95 ℃ for 22 hours and naturally cooled to room temperature, so that the antibacterial mildew-proof modified plastic is prepared.
Test examples
Test of antibacterial and mildew-proof properties, tensile properties and flame retardant properties
The antibacterial and mildew-proof performance test method comprises the following steps: the inhibition rate against E.coli was tested according to GB/T27934 standard.
The tensile property testing method comprises the following steps: tensile strength was measured according to GB/T1040 standard.
The flame retardant performance test method comprises the following steps: limiting oxygen index was tested according to GB/T2406.2 standard. The results are shown in Table 1.
As can be seen from the comparison of experimental data of examples 1-3 and comparative examples 1-3 in Table 1, the antibacterial and mildew-proof modified plastic prepared by the invention has good antibacterial and mildew-proof properties, tensile properties and flame retardant properties.
As can be found by comparing the data of examples 1-3 and comparative example 1, the E.coli inhibition rate and tensile strength of examples 1-3 are high, which shows that the organosilicon imidazole salt is prepared by reacting heptamethyl cyclotetrasiloxane and N-vinyl imidazole and then reacting 1-bromo-N-dodecane, so that the surface of the subsequently prepared modified zinc oxide contains a large amount of imidazole salt structures, the imidazole salt structures with positive charges attract negatively charged bacterial cell walls under the action of electrostatic force, and fat-soluble long chains penetrate the bacterial cell walls and cell membranes to crack and kill the bacteria, thereby improving the antibacterial effect; and the positively charged imidazolium salt structure can be combined with negatively charged phosphate ions in the subsequent process to form a cross-linked network structure, so that the modified nano zinc oxide forms a stress node, and the tensile property is improved.
The comparison of the data of the comparative example 1 and the data of the comparative example 2 shows that the escherichia coli inhibition rate, the tensile strength and the limiting oxygen index of the comparative example 1 are high, the modification of the nano zinc oxide is proved, a polysiloxane long chain is generated on the surface of the nano zinc oxide, the nano zinc oxide has good compatibility with modified polyvinyl chloride, the dispersibility of the nano zinc oxide is improved, the nano zinc oxide has certain antibacterial property, the nano zinc oxide is also a reinforcing agent and a filling agent, the antibacterial mildew-proof property and the tensile strength are improved, and meanwhile, the generated polysiloxane long chain can improve the flame retardant effect.
As can be seen from the comparison of the data of examples 1-3 and comparative example 3, examples 1-3 have high tensile strength and limiting oxygen index, which indicates that the polyvinyl chloride is modified by the modifier, the branched chain formed on the polyvinyl chloride contains a phosphate structure, and the phosphorus element has the effect of promoting the formation of a carbon layer, so that the flame retardance is improved, and the phosphate structure is hydrolyzed into phosphate anions through the treatment of hydrochloric acid aqueous solution, so that the phosphate can be combined with the positively charged imidazolium salt structure on the modified nano zinc oxide through static electricity to form a crosslinked network structure, and the tensile property is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (6)
1. The antibacterial mildew-proof modified plastic is characterized by being formed by mixing and extruding modified polyvinyl chloride and modified nano zinc oxide, and injection molding;
the modified polyvinyl chloride is prepared by reacting 2-aminoethanol, paraformaldehyde and dimethyl phosphite to prepare a modifier and reacting the polyvinyl chloride with the modifier;
the modified nano zinc oxide is prepared by sequentially reacting nano zinc oxide with allyl triethoxysilane, pentamethyl disiloxane and organic silicon imidazole salt;
the organosilicon imidazole salt is prepared by reacting heptamethyl cyclotetrasiloxane and N-vinyl imidazole and then reacting with 1-bromo-N-dodecane.
2. The preparation method of the antibacterial and mildew-proof modified plastic is characterized by comprising the following preparation steps:
(1) Uniformly mixing heptamethyl cyclotetrasiloxane, chloroplatinic acid and N-hexane according to the mass ratio of (0.01-0.02) (8-10), adding N-vinylimidazole with the same molar weight as that of the heptamethyl cyclotetrasiloxane, stirring and refluxing for 4-6 hours at 70-80 ℃ and 500-800 r/min, standing for 2-3 hours at 20-30 ℃, mixing and washing for 3-5 times by pure water and N-hexane with the same volume as that of the pure water, standing for layering after each washing, removing the water phase, and drying for 6-8 hours at 30-40 ℃ and 1-2 kPa to obtain the organosilicon imidazole; uniformly mixing organosilicon imidazole and 1-bromo-n-dodecane according to a molar ratio of 1:1, and stirring at a temperature of 5-10 ℃ and a speed of 200-300 r/min for reacting for 40-48 hours to obtain organosilicon imidazole salt;
(2) Uniformly mixing pentamethyldisiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1 (6-8) (0.01-0.02) to prepare a pentamethyldisiloxane mixed solution; uniformly mixing nano zinc oxide, allyl triethoxysilane, ammonia water with the mass fraction of 20% and absolute ethyl alcohol according to the mass ratio of 1:1 (3-4) (10-12), stirring and reacting for 1-2 hours at 20-30 ℃ at 200-300 r/min, centrifugally separating, washing for 3-5 times by absolute ethyl alcohol, drying for 6-8 hours at 60-70 ℃, placing in a pentamethyl disiloxane mixed solution with the mass of 8-10 times of nano zinc oxide, stirring and refluxing for 3-4 hours at 70-80 ℃ at 300-500 r/min in a nitrogen atmosphere, centrifugally separating, washing for 3-5 times by absolute ethyl alcohol, and drying for 6-8 hours at 60-70 ℃ to obtain pretreated nano zinc oxide; uniformly mixing pretreated nano zinc oxide, organosilicon imidazole salt and N, N-dimethylformamide according to the mass ratio of 1:1 (4-6), dropwise adding a trifluoromethane sulfonic acid aqueous solution with the mass fraction of 10-12% which is 1.6-2 times of the mass of the pretreated nano zinc oxide at a constant speed within 15-20 min under the stirring condition of 300-500 r/min at the temperature of 70-80 ℃, continuously stirring for reacting for 60-80 min after the dropwise adding, centrifugally separating, washing 3-5 times by pure water and absolute ethyl alcohol respectively, and drying for 6-8 h at the temperature of 60-70 ℃ under the pressure of 10-50 Pa to obtain modified nano zinc oxide;
(3) Uniformly mixing 2-aminoethanol, paraformaldehyde with the polymerization degree of 8-10 and tetrahydrofuran according to the mass ratio of (8-10) of 1:2, stirring for 20-30 min at the temperature of 65-70 ℃ at 300-500 r/min, continuously stirring, adding dimethyl phosphite with the molar weight of 2 times that of 2-aminoethanol at a constant speed within 10-15 min, continuously stirring for reacting for 8-10 h after the addition is finished, and drying for 6-8 h at the temperature of 40-50 ℃ at 100-500 Pa to obtain a modifier; uniformly mixing polyvinyl chloride, a modifier, 2,4, 6-trimethylpyridine and tetrahydrofuran according to the mass ratio of 1:1 (0.3-0.4) (25-30), stirring at 30-40 ℃ for reaction for 10-12 h at 300-500 r/min, drying at 30-40 ℃ for 10-12 h at 10-50 Pa, then placing in a hydrochloric acid aqueous solution with the mass fraction of 3-5% and the mass fraction of 6-8 times of the polyvinyl chloride, stirring at 30-40 ℃ for 6-8 min at 300-500 r/min, filtering, washing with pure water for 3-5 times, and drying at 30-40 ℃ for 10-50 Pa for 10-12 h to obtain modified polyvinyl chloride;
(4) Weighing 80-100 parts of modified polyvinyl chloride according to parts by weight, placing 10-15 parts of modified nano zinc oxide in a double screw extruder for mixing extrusion, wherein the temperature of three areas of the double screw extruder is 180-185 ℃, 185-190 ℃, the screw speed of 190-195 ℃ is 44-48 r/min, injecting the extruded mixture into a die at 200-210 ℃ and the injection pressure of 7-7.5 MPa by an injection molding machine, standing for 20-24 h at 90-100 ℃, and naturally cooling to room temperature to obtain the antibacterial and mildew-proof modified plastic.
3. The method for preparing the antibacterial and mildew-proof modified plastic according to claim 2, wherein the reaction process of the organosilicon imidazole in the step (1) is as follows:
；
the reaction process of the organosilicon imidazole salt is as follows:
。
4. the method for preparing the antibacterial and mildew-proof modified plastic according to claim 2, wherein the reaction process of the modifier in the step (3) is as follows:
。
5. the method for preparing the antibacterial and mildew-proof modified plastic according to claim 2, wherein the reaction process of the polyvinyl chloride and the modifier in the step (3) is as follows:
。
6. the method for preparing the antibacterial and mildew-proof modified plastic according to claim 2, wherein the polyvinyl chloride in the step (3) is of a model number of S-1000.
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| CN102391403A (en) * | 2011-09-06 | 2012-03-28 | 中国科学技术大学苏州研究院 | Flame-retardant polymer containing phosphorus and nitrogen and preparation method thereof |
| CN111423696A (en) * | 2020-04-20 | 2020-07-17 | 同曦集团有限公司 | Antibacterial and antiviral toilet lid and preparation method thereof |
| CN115044045A (en) * | 2022-06-24 | 2022-09-13 | 上海睿思畅科技发展有限公司 | Silicon-containing ionic liquid flame retardant and preparation method thereof |
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| CN102391403A (en) * | 2011-09-06 | 2012-03-28 | 中国科学技术大学苏州研究院 | Flame-retardant polymer containing phosphorus and nitrogen and preparation method thereof |
| CN111423696A (en) * | 2020-04-20 | 2020-07-17 | 同曦集团有限公司 | Antibacterial and antiviral toilet lid and preparation method thereof |
| CN115044045A (en) * | 2022-06-24 | 2022-09-13 | 上海睿思畅科技发展有限公司 | Silicon-containing ionic liquid flame retardant and preparation method thereof |
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