CN104530308B - Method for preparing antibacterial agent emulsion - Google Patents
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- CN104530308B CN104530308B CN201410808754.XA CN201410808754A CN104530308B CN 104530308 B CN104530308 B CN 104530308B CN 201410808754 A CN201410808754 A CN 201410808754A CN 104530308 B CN104530308 B CN 104530308B
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Abstract
The invention relates to a method for preparing antibacterial agent emulsion. The method comprises the following steps: adding deionized water and an emulsifier into a polymerization reaction kettle, dropwise adding a mixing monomer at 55 DEG C, and emulsifying for 0.5 hour; dissolving an initiator in the deionized water; adding 1/3 volume of initiator aqueous solution at 65-70 DEG C, and reacting for 1 hour in a heat preservation manner; dropwise adding the residual initiator aqueous solution and a silane coupling agent into the reaction kettle, after dropwise adding for 1-3 hours, further reacting at 75-78 DEG C for 1 hour, and cooling to 50 DEG C; dropwise adding silver nitrate aqueous solution into step (4), stirring uniformly, and regulating the pH value to neutral via ammonia water. By adopting the method provided by the invention, the defects of an organic antibacterial agent in the prior art of poor thermal stability and easiness for migrating to a product surface to drop are overcome, and the problems of dispersion, migration and slow release of a silver-carrying antibacterial agent in a medium are avoided.
Description
Technical field
The present invention relates to a kind of preparation method of emulsion, especially a kind of preparation method of antibacterial agent emulsion, belongs to high score
Sub- Material Field.
Technical background
Chemosynthesis organic antibacterial agent mainly includes quaternary ammonium salts, pyridines, halogen, biguanideses, alcohols, phenols, aldehyde
Class, organic acid, ethers, peroxide and organic metal copolymer etc., its antimicrobial long-acting is higher, is currently anti-
One focus of microbial inoculum research, its antibacterial mechanisms is mainly by surface contact and antibacterial and the surface of cell membrane anion of mycete
Combine, or with sulfenyl reaction, the synthesis system of protein and cell membrane is destroyed, so as to suppress the growth of antibacterial and mycete and numerous
Grow.At present, organic antibacterial agent has been widely used in the fields such as weaving, health care, health care of food, building decoration.But it is organic
The shortcomings of antibacterial has poor stability, poor chemical stability, poor heat resistance, limits its application in article of manufacture.
The antibacterial ability having using silver metal itself, by methods such as physical absorption or ion exchanges, by silver metal
(or its ion) is fixed on different carriers prepared different types of antibacterial and is referred to as silver-series antibacterial agent.According to the difference of carrier,
It is broadly divided into：1. zeolite antibacterial agent：Zeolite is the aluminum silicate that a class has the very alkali of macrocation exchange capacity or alkaline-earth metal
Salt mineral, by exchanging Ag+It is attached in its structure and zeolite antibacterial agent is obtained, 2. bentonite bactericidal agent：Bentonite is one
The layer structure inorganic mineral with good monovalent cation switching performance is planted, cation exchange can be passed through by Ag+Introduce interlayer
Prepared bentonite bactericidal agent, 3. silica gel antibacterial：Silica gel has very big specific surface area, by adsorbable complex, and can utilize
Sol-gel method forms SiO on its surface2Layer and the antibacterial with heat stability and Durability of antimicrobial effect is obtained, 4. phosphoric acid is answered
Salt antibacterial：It is obtained using the method for porous devitrified glass.But there is scattering problem in medium in general carrying silver antimicrobials, and
And silver ion also has migration and slow release in carrier, these problems are mainly the absorption property and dispersive property of carrier and make
Into.
If copolymer will be formed on organic antibacterial agent monomer, phenylpropyl alcohol monomer copolymerizable and polymer molecular chain, can avoid
The thermally-stabilised difference of organic antibacterial agent, the defect for easily migrating to product surface and coming off；Silver ion by with polymer molecular chain on
Amino complexation and be fixedly combined in polymer, then can overcome carrying silver antimicrobials scattering problem present in medium, migration
And slow release problem.Additionally, organic antibacterial agent, inorganic antiseptic are combined, antibacterial light spectrality, the effectiveness of antibacterial can be strengthened.
The content of the invention
It is an object of the invention to provide a kind of preparation method of antibacterial agent emulsion, a kind of by organic antibacterial agent monomer, phenylpropyl alcohol
Generate the preparation method of antibacterial after monomer copolymerization with silver ion complexation again, can effectively overcome the thermally-stabilised difference of organic antibacterial agent, easily
Migrate to product surface and the defect that comes off and avoid carrying silver antimicrobials from disperseing present in medium, migrate and slow release is asked
Topic.
For achieving the above object, present invention employs technical scheme below：
A kind of preparation method of antibacterial agent emulsion, comprises the steps (each component raw material is in parts by weight)：
(1), in polymerization reaction kettle add 620～835 parts deionized water and 12～21 parts of emulsifying agents, 600～800
Rev/min mixing speed under stirring be allowed to dilution dispersion, be warming up to 55 DEG C, then Deca by 72～174 parts of soft monomers, 40～
The mixed liquor that 76 parts of hard monomers, 42～64 parts of antibacterial monomers are mixed to form, after completion of dropping, low whipping speed is 300～400
Continue to stir 0.5 hour in the state of rev/min, obtain emulsion；
(2), 1～3 part of initiator is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 65～70 DEG C, adds the initiator solution of 1/3 volume, insulation reaction
1 hour；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 8～13 parts of silane couplers, 1～3 hour
After completion of dropping, then 75～78 DEG C are warming up to, continuation reaction 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred
Uniformly, pH value is adjusted to neutrality with ammonia, obtains antibacterial agent emulsion.
Described soft monomer is included in butyl acrylate, n-octyl, ethyl acrylate, Behenyl acrylate
It is at least one.
Described hard monomer includes at least one in methyl methacrylate, butyl methacrylate, styrene.
The initiator is the one kind in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
The silane coupler be N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-
γ-aminopropyltrimethoxysilane, γ-methacryloxypropyl trimethoxy silane.
Described antibacterial monomer including N- (4- gives a tongue-lashing pyridine) give a tongue-lashing thiamine hydrochloride, 4-vinylpridine nitrate, N- n-octadecane-
At least one in 4- stibazole bromides.
Described emulsifying agent is by hexadecanol Polyethylene oxide ether dimethyl-octa alkyl ammomium chloride, trimethylene base [(palmitamide third
Base dimethyl/stearamide propyl-dimethyl) chlorine bromine ammonium], dodecyl polyoxyethylene/polyoxypropylene base octadecyl bromide
Change ammonium compounding to form.
The antibacterial that the inventive method is prepared with organic antibacterial agent monomer, phenylpropyl alcohol monomer copolymerization polymer and silver ion complexation
Emulsion, combines the advantage of organic antibacterial agent, inorganic antiseptic, and antibacterial activity is good, also with spies such as wide spectrum, efficient, hypotoxicities
Point.The present invention overcomes the thermally-stabilised difference of organic antibacterial agent in prior art, the defect for easily migrating to product surface and coming off
And avoid carrying silver antimicrobials and disperse present in medium, migrate and slow release problem；Emulsifying agent in the present invention is quaternary ammonium
Salt, is effectively antibacterial, can strengthen the antibacterial effect of product emulsion；Additionally, the inventive method is easy to operate, simply may be used
OK, it is easy to promote.
Specific embodiment
Below by specific embodiment, the invention will be further described：
Embodiment 1：
A kind of preparation method of antibacterial agent emulsion, comprises the steps (each component raw material is in parts by weight)：
(1), in polymerization reaction kettle add 620 parts deionized water and 12 parts of emulsifying agents, in 600 revs/min of stirring
Stirring under speed is allowed to dilution dispersion, is warming up to 55 DEG C, and then Deca is by 72 parts of soft monomers, 40 parts of hard monomers, 42 parts of antibacterial lists
The mixed liquor that body is mixed to form, after completion of dropping, low whipping speed is stirred 0.5 hour for continuation in the state of 300 revs/min,
Obtain emulsion；
(2), 1 part of initiator ammonium persulfate is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 65 DEG C, adds the initiator solution of 1/3 volume, insulation reaction 1 is little
When；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 8 parts of silane couplers, 1 hour completion of dropping
Afterwards, then it is warming up to 75 DEG C, continues to react 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred
Uniformly, pH value is adjusted to neutrality with ammonia, obtains antibacterial agent emulsion.
Wherein, soft monomer is 31 parts of butyl acrylate, 18 parts of n-octyl, 14 parts of ethyl acrylate, acrylic acid two
19 parts of diester；Hard monomer is 12 parts of methyl methacrylate, 10 parts of butyl methacrylate, 18 parts of styrene；Silane coupler
For N- β-(aminoethyl)-γ -3 parts of aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl trimethoxy silicon
3 parts of alkane, 2 parts of γ-methacryloxypropyl trimethoxy silane；Antibacterial monomer is N- (4- pyridines) pyridine hydrochloride 15
Part, 15 parts of 4-vinylpridine nitrate, 13 parts of N- n-octadecane -4- stibazoles bromide；Emulsifying agent is by 4 parts of hexadecanol
Polyethylene oxide ether dimethyl-octa alkyl ammomium chloride, 5 parts of trimethylene base [(palmitamide propyl-dimethyls/stearamide dimethylamine
Base) chlorine bromine ammonium], 3 parts of dodecyl polyoxyethylene/polyoxypropylene base octadecyl bromination ammoniums compounding forms.
Embodiment 2：
A kind of preparation method of antibacterial agent emulsion, comprises the steps (each component raw material is in parts by weight)：
(1), in polymerization reaction kettle add 663 parts deionized water and 14 parts of emulsifying agents, in 650 revs/min of stirring
Stirring under speed is allowed to dilution dispersion, is warming up to 55 DEG C, and then Deca is by 98 parts of soft monomers, 52 parts of hard monomers, 47 parts of antibacterial lists
The mixed liquor that body is mixed to form, after completion of dropping, low whipping speed is stirred 0.5 hour for continuation in the state of 350 revs/min,
Obtain emulsion；
(2), 1.5 parts of initiator potassium persulfate is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 66 DEG C, adds the initiator solution of 1/3 volume, insulation reaction 1 is little
When；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 9 parts of silane couplers, drip within 1.5 hours
Bi Hou, then 76 DEG C are warming up to, continuation reaction 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred
Uniformly, pH value is adjusted to neutrality with ammonia, obtains antibacterial agent emulsion.
Wherein, soft monomer is 42 parts of butyl acrylate, 25 parts of n-octyl, 19 parts of ethyl acrylate, acrylic acid two
Ten 12 parts of diester；Hard monomer is 17 parts of methyl methacrylate, 14 parts of butyl methacrylate, 21 parts of styrene；It is silane coupled
Agent is N- β-(aminoethyl)-γ -3 parts of aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl trimethoxy
3 parts of silane, 3 parts of γ-methacryloxypropyl trimethoxy silane；Antibacterial monomer is N- (4- pyridines) pyridine hydrochloride 17
Part, 19 parts of 4-vinylpridine nitrate, 9 parts of N- n-octadecane -4- stibazoles bromide；Emulsifying agent is by 5 parts of hexadecanol
Polyethylene oxide ether dimethyl-octa alkyl ammomium chloride, 4 parts of trimethylene base [(palmitamide propyl-dimethyls/stearamide dimethylamine
Base) chlorine bromine ammonium], 5 parts of dodecyl polyoxyethylene/polyoxypropylene base octadecyl bromination ammoniums compounding forms.
Embodiment 3：
A kind of preparation method of antibacterial agent emulsion, comprises the steps (each component raw material is in parts by weight)：
(1), in polymerization reaction kettle add 718 parts deionized water and 17 parts of emulsifying agents, in 700 revs/min of stirring
Stirring under speed is allowed to dilution dispersion, is warming up to 55 DEG C, and then Deca is by 123 parts of soft monomers, 63 parts of hard monomers, 53 parts of antibacterial lists
The mixed liquor that body is mixed to form, after completion of dropping, low whipping speed is stirred 0.5 hour for continuation in the state of 300 revs/min,
Obtain emulsion；
(2), 2 parts of initiator is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 68 DEG C, adds the initiator solution of 1/3 volume, insulation reaction 1 is little
When；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 10 parts of silane couplers, drip within 2 hours
Bi Hou, then 77 DEG C are warming up to, continuation reaction 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred
Uniformly, pH value is adjusted to neutrality with ammonia, obtains antibacterial agent emulsion.
Wherein, soft monomer is 59 parts of butyl acrylate, 31 parts of n-octyl, 27 parts of ethyl acrylate, acrylic acid two
16 parts of diester；Hard monomer is 23 parts of methyl methacrylate, 12 parts of butyl methacrylate, 28 parts of styrene；Silane coupler
For N- β-(aminoethyl)-γ -3 parts of aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl trimethoxy silicon
4 parts of alkane, 3 parts of γ-methacryloxypropyl trimethoxy silane；Antibacterial monomer is N- (4- pyridines) pyridine hydrochloride 19
Part, 21 parts of 4-vinylpridine nitrate, 13 parts of N- n-octadecane -4- stibazoles bromide；Emulsifying agent is by 7 parts of hexadecanol
Polyethylene oxide ether dimethyl-octa alkyl ammomium chloride, 7 parts of trimethylene base [(palmitamide propyl-dimethyls/stearamide dimethylamine
Base) chlorine bromine ammonium], 3 parts of dodecyl polyoxyethylene/polyoxypropylene base octadecyl bromination ammoniums compounding forms.
Embodiment 4：
A kind of preparation method of antibacterial agent emulsion, comprises the steps (each component raw material is in parts by weight)：
(1), in polymerization reaction kettle add 784 parts deionized water and 19 parts of emulsifying agents, in 750 revs/min of stirring
Stirring under speed is allowed to dilution dispersion, is warming up to 55 DEG C, and then Deca is by 149 parts of soft monomers, 68 parts of hard monomers, 59 parts of antibacterial lists
The mixed liquor that body is mixed to form, after completion of dropping, low whipping speed is stirred 0.5 hour for continuation in the state of 400 revs/min,
Obtain emulsion；
(2), 2.5 parts of initiator is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 69 DEG C, adds the initiator solution of 1/3 volume, insulation reaction 1 is little
When；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 11 parts of silane couplers, 2.5 hours Deca
After finishing, then 76 DEG C are warming up to, continuation reaction 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred
Uniformly, pH value is adjusted to neutrality with ammonia, obtains antibacterial agent emulsion.
Wherein, soft monomer is 73 parts of butyl acrylate, 45 parts of n-octyl, 31 parts of ethyl acrylate；Hard monomer is
29 parts of methyl methacrylate, 6 parts of butyl methacrylate, 24 parts of styrene；Silane coupler be N- β-(aminoethyl)-γ-
4 parts of aminopropyltriethoxy dimethoxysilane, N- β -3 parts of (aminoethyl)-γ-aminopropyltrimethoxysilane, γ-methacryl
4 parts of epoxide propyl trimethoxy silicane；Antibacterial monomer is 29 parts of N- (4- pyridines) pyridine hydrochloride, 4-vinylpridine nitrate
30 parts；Emulsifying agent is by 7 parts of hexadecanol Polyethylene oxide ether dimethyl-octa alkyl ammomium chlorides, 6 parts of trimethylene base [(palmitamide propyl group
Dimethyl/stearamide propyl-dimethyl) chlorine bromine ammonium], 6 parts of dodecyl polyoxyethylene/polyoxypropylene base octadecyl bromides
Change ammonium compounding to form.
Embodiment 5：
A kind of preparation method of antibacterial agent emulsion, comprises the steps (each component raw material is in parts by weight)：
(1), in polymerization reaction kettle add 835 parts deionized water and 21 parts of emulsifying agents, in 800 revs/min of stirring
Stirring under speed is allowed to dilution dispersion, is warming up to 55 DEG C, and then Deca is by 174 parts of soft monomers, 76 parts of hard monomers, 64 parts of antibacterial lists
The mixed liquor that body is mixed to form, after completion of dropping, low whipping speed is stirred 0.5 hour for continuation in the state of 350 revs/min,
Obtain emulsion；
(2), 3 parts of initiator is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 70 DEG C, adds the initiator solution of 1/3 volume, insulation reaction 1 is little
When；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 13 parts of silane couplers, drip within 3 hours
Bi Hou, then 78 DEG C are warming up to, continuation reaction 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred
Uniformly, pH value is adjusted to neutrality with ammonia, obtains antibacterial agent emulsion.
Wherein, soft monomer is 88 parts of butyl acrylate, 57 parts of n-octyl, 18 parts of ethyl acrylate, acrylic acid two
Ten 11 parts of diester；Hard monomer is 34 parts of methyl methacrylate, 30 parts of styrene；Silane coupler be N- β-(aminoethyl)-γ-
5 parts of aminopropyltriethoxy dimethoxysilane, N- β -3 parts of (aminoethyl)-γ-aminopropyltrimethoxysilane, γ-methacryl
5 parts of epoxide propyl trimethoxy silicane；Antibacterial monomer is 26 parts of N- (4- pyridines) pyridine hydrochloride, 4-vinylpridine nitrate
21 parts, 17 parts of N- n-octadecane -4- stibazoles bromide；Emulsifying agent is by 6 parts of hexadecanol Polyethylene oxide ether dimethyl-octas
Alkyl ammomium chloride, 7 parts of trimethylene bases [(palmitamide propyl-dimethyl/stearamide propyl-dimethyl) chlorine bromine ammonium], 8 part ten
Dialkyl group polyoxyethylene/polyoxypropylene base octadecyl bromination ammonium compounding is formed.
Antibacterial agent emulsion made by above-described embodiment is used to arrange textile poplin cloth (40 × 40/110 × 90) fabric, and is adopted
With the standards of AATCC 100, antibacterial effect is evaluated.Antibacterial finishing process is：Pad antiseptic solution (pick-up rate 80%, 30 DEG C) → baking
Dry (100 DEG C).
The antibacterial agent emulsion anti-microbial property of table 1
As seen from table, the excellent antibacterial performance of antibacterial agent emulsion of the present invention.
Claims (6)
1. a kind of preparation method of antibacterial agent emulsion, it is characterised in that comprise the steps, each component raw material is in parts by weight：
(1), in polymerization reaction kettle add 620～835 parts deionized water and 12～21 parts of emulsifying agents, 600～800 turns/
Minute mixing speed under stirring be allowed to dilution dispersion, be warming up to 55 DEG C, then Deca by 72～174 parts of soft monomers, 40～76
The mixed liquor that part hard monomer, 42～64 parts of antibacterial monomers are mixed to form, after completion of dropping, low whipping speed is 300～400 turns/
Continue to stir 0.5 hour in the state of minute, obtain emulsion；
(2), 1～3 part of initiator is stand-by with 30 parts of deionized water dissolving；
(3), the temperature of polymerization reaction kettle is risen to into 65～70 DEG C, adds the initiator solution of 1/3 volume, insulation reaction 1 is little
When；
(4), to the remaining initiator solution of Deca in polymerization reaction kettle and 8～13 parts of silane couplers, 1～3 hour Deca
After finishing, then 75～78 DEG C are warming up to, continuation reaction 1 hour；Then 50 DEG C are cooled to；
(5), the silver nitrate aqueous solution that 2 parts of silver nitrate and 100 parts of distilled water are configured to is added in step (4), is stirred,
PH value is adjusted to neutrality with ammonia, antibacterial agent emulsion is obtained；
Described antibacterial monomer includes N- (4- pyridines) pyridine hydrochloride, 4-vinylpridine nitrate, N- n-octadecane -4- benzene
At least one in vinylpyridine bromide.
2. a kind of preparation method of antibacterial agent emulsion as claimed in claim 1, it is characterised in that：Described soft monomer includes third
At least one in olefin(e) acid butyl ester, n-octyl, ethyl acrylate, Behenyl acrylate.
3. a kind of preparation method of antibacterial agent emulsion as claimed in claim 1, it is characterised in that：Described hard monomer includes first
At least one in base acrylic acid methyl ester., butyl methacrylate, styrene.
4. a kind of preparation method of antibacterial agent emulsion as claimed in claim 1, it is characterised in that：The initiator is persulfuric acid
One kind in ammonium, potassium peroxydisulfate, sodium peroxydisulfate.
5. a kind of preparation method of antibacterial agent emulsion as claimed in claim 1, it is characterised in that：The silane coupler is N-
β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-first
Base acryloxypropyl trimethoxy silane.
6. a kind of preparation method of antibacterial agent emulsion as claimed in claim 1, it is characterised in that：Described emulsifying agent is by 16
Polyoxyethylenated alcohol base dimethyl-octa alkyl ammomium chloride, trimethylene base [(palmitamide propyl-dimethyl/stearamide dimethylamine
Base) chlorine bromine ammonium], dodecyl polyoxyethylene/polyoxypropylene base octadecyl bromination ammonium compounding form.
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| CN106259445A (en) * | 2015-05-26 | 2017-01-04 | 东莞市昊天化工有限公司 | A kind of fine silver antibacterial |
| CN105111725B (en) * | 2015-09-23 | 2017-08-25 | 福建越特新材料科技有限公司 | A kind of antimicrobial form anion flexible polyurethane foams and preparation method thereof |
| WO2017058708A1 (en) * | 2015-09-30 | 2017-04-06 | Dow Global Technologies Llc | Method of preparing an antimicrobial composition |
| CN107619535A (en) * | 2016-07-15 | 2018-01-23 | 汉达精密电子(昆山)有限公司 | Antibacterial polypropylene material and its products formed |
| CN107236084A (en) * | 2017-05-27 | 2017-10-10 | 南通成山高分子材料有限公司 | A kind of high-molecular anti-bacteria material |
| CN108263037A (en) * | 2018-02-07 | 2018-07-10 | 枣庄市超钱塑业有限公司 | A kind of kraft compounded chemical industry bag and preparation method thereof |
| CN108948250B (en) * | 2018-06-14 | 2021-08-31 | 广州大学 | Antibacterial polymer emulsion and preparation method and application thereof |
| CN110343197B (en) * | 2019-06-24 | 2020-11-06 | 浙江大学 | Preparation method and antibacterial application of polymer type quaternary ammonium salt photocatalyst |
| CN112175600B (en) * | 2020-08-31 | 2022-07-01 | 西南石油大学 | Novel foam stabilizer and preparation method thereof |
| CN114539840A (en) * | 2022-02-25 | 2022-05-27 | 珠海市金团化学品有限公司 | Nano composite antibacterial emulsion and preparation method and application thereof |
| CN115746619B (en) * | 2022-12-09 | 2023-08-25 | 广东英科集团股份有限公司 | Antibacterial water-based ink and preparation method thereof |
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| CN101189971A (en) * | 2006-11-20 | 2008-06-04 | 北京崇高纳米科技有限公司 | Inorganic/organic nano composite antibacterial agent and its fabric product application |
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