CN106797955A - Antifouling algicide of environment-protection nano and preparation method thereof - Google Patents
Antifouling algicide of environment-protection nano and preparation method thereof Download PDFInfo
- Publication number
- CN106797955A CN106797955A CN201710025195.9A CN201710025195A CN106797955A CN 106797955 A CN106797955 A CN 106797955A CN 201710025195 A CN201710025195 A CN 201710025195A CN 106797955 A CN106797955 A CN 106797955A
- Authority
- CN
- China
- Prior art keywords
- antifouling
- environment
- water
- algicide
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
- A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Abstract
The embodiment of the invention discloses antifouling algicide of a kind of environment-protection nano and preparation method thereof, the antifouling algicide of environment-protection nano is mixed by the raw material of following mass fractions：The ketone 10%~20% of 5%~10%, 4,54 isothiazoline of dichloro N octyl groups of water nano silver dispersions slurry 3, the ketone 5%~10% of 2 octyl group, 4 isothiazoline 3, benzimidazole 5%~10%, emulsifying agent 3~5%, antifreezing agent 5%~8%, bleeding agent 1%~3%, amine neutralizer 1%~3%, thickener 1%~3%, solubilized stabilizer 5%~10%, synergetic effect additive 5%~10%, ethanol 5%~8%, deionized water 20%~30%.The antifouling algicide of environment-protection nano of the present invention and preparation method thereof low cost of manufacture, toxicity is low, to water source and Environmental security the features such as, it is significant to energy saving, environmental protection, the harmonious relationships for creating man and nature.
Description
Technical field
The present embodiments relate to function fine chemicals field of material technology, specifically one kind being capable of extensive use
In industrial circle, degradable antifouling algicide of environment-protection nano and preparation method thereof.
Background technology
For many years, marine biofouling problem annoyings exploitation and application of the mankind to ocean always, prevents and treats marine organisms
Being stained also turns into global problem and study hotspot.The underwater sailing bodys such as ship, warship, submarine are submerged in the seawater, no for a long time
Only corroded by seawater, marine organisms are also easily adhered on its surface, be stained by ocean attachment.On the one hand it increase hull
Deadweight and frictional resistance, increase fuel consumption, there is data surface, and fouling organism can cause fuel consumption to be increased up to 40%, very
To possible 50%；On the other hand Ship's corrosion can be accelerated, shortens the service life of hull.The attachment of fouling organism also results in ocean
Instrument signal distortion, performance reduction even instrument failure；Block the seawater pipeline on instrument facility；Cause the anaerobism of metal rotten
Erosion, increased maintenance number of times and the time of ship, reduce ship in boat rate etc..
With the development of marine technology, the ship pollution prevention of China is heavy antisepsis, multi-functional, nuisanceless, long to high-performance
The directions such as life-span are developed.The antifouling of marine facility is depended primarily on based on generation to biological poisonous surface, allows the biology cannot
Perch.Common toxin of the use containing tin for preventing fouling organism from adhering to is copper and its compound, exist antifouling approach it is single,
Static antifouling property is poor, the antifouling phase imitates the key problems such as short, broad spectrum activity is poor, is not enough to expel or kills attempt to be attached to hull
Fouling organism, and cannot be degraded in natural environment, the heavy damage marine eco-environment causes the interior accumulation of organism in food chain
Property, therefore, the antifouling products of New-type long-acting wide spectrum are developed, break foreign technology monopolization extremely urgent.
Meanwhile, with the growing tension and the pay attention to day by day to microorganism problem in water system of water resource, develop new anti-
Dirty algicide especially will continuously have the area of certain history as highly important task using identical bactericide, lack and close
The guidance of the use experience of reason and specialty, use environment resistance problems have been in becoming of growing in intensity.How to overcome or delay and be micro-
The generation and development of biomolecule resistant, while with the Acceptable life for extending bactericide, reduce environment and water source cause dirt
Dye, it has also become all trades and professions bactericide uses middle faced great difficult problem.
Economize on resources, energy-saving and emission-reduction, ecological, environmental protective, low-carbon circular economy be economic development basic model, as water is provided
The growing tension in source and the pay attention to day by day to microorganism problem in water system, developing new, high-efficiency industrial bactericide will turn into
Highly important task.Recently as the increasingly strict of environmental requirement, national requirements development environment friendly is new antifouling except algae
Sterilized formulation, formulation towards water baseization, environmental protection, ultramicronising, without dust and controlled release in terms of develop, environmentally friendly noresidue formulation also will
As antifouling except one of the direction of algae bactericide Technology effort development.
On the premise of reliability that product is used and security is ensured, exploitation compounded is combined antifouling except algae bactericide
Agent, on the basis of the existing antifouling bactericide except algae, strengthens antifouling except the theoretical research of algae sterilization mechanism, and emphasis is to pharmacy effect
Mechanism and collaboration efficiency are studied, and defect and deficiency that single medicament exists in use can be made up, while having
Technology for producing low cost, bactericidal effect are good, have no toxic side effect, noresidue is free from environmental pollution and water source, and this point is to promoting
Promote the antifouling technology shifts except algae bactericide industry to upgrade, reach the progress of industrial circle production capacity upgrading, there is important meaning
Justice, ring environment-protection nano is antifouling to have good development prospect except algae bactericide.
At present, yet there are some shortcomings in traditional antifouling algicide, such as relatively costly, contain VOC, aromatic hydrocarbons, a huge sum of money
The harmful poisonous volatile substances such as category, serious to environment and pollution of waterhead, the antifouling approach of formulation of some kinds is single, static antifouling
Poor performance, antifouling phase imitate short, broad spectrum activity is poor, physical property is not ideal enough etc..
The content of the invention
Embodiment of the present invention technical problem to be solved is, there is provided a kind of antifouling algicide of environment-protection nano, Ke Yishi
The superposition of existing bioactivity, increases that its is antifouling except algae anti-microbial property, and degradability is good, and ring is not polluted in inanimate object accumulation, noresidue
Border and water source, safe operation, stability are strong.
Further technical problem to be solved is the embodiment of the present invention, there is provided a kind of antifouling algicide of environment-protection nano
Preparation method, its preparation process is simple, it is easy to implement, energy is efficient, it is antifouling except algae anti-microbial property is strong to prepare to energy-conservation, degradable
Property it is good, inanimate object accumulation, noresidue is free from environmental pollution and water source, the antifouling algicide of the strong environment-protection nano of safe operation, stability.
In order to solve the above technical problems, the embodiment of the present invention provides following technical scheme first：A kind of environment-protection nano is antifouling
Algicide, its raw material is by following into being grouped into terms of mass fraction：Water nano silver dispersions slurry 5%~10%, 4,
The chloro- N- octyl groups -4- isothiazolines -3- ketone 10%~20% of 5- bis-, 2- octyl group -4- isothiazoline -3- ketone 5%~10%, benzo
Imidazoles 5%~10%, emulsifying agent 3%~5%, antifreezing agent 5%~8%, bleeding agent 1%~3%, amine neutralizer 1%~3%,
Thickener 1%~3%, solubilized stabilizer 5%~10%, synergetic effect additive 5%~10%, ethanol 5%~8%, deionized water
20%~30%.
Further, the water nano silver dispersions slurry be from particle diameter 30~70nm Nano Silver obtained in it is solid
Containing the water-borne dispersions slurry for 20~40%.
Further, the chloro- N- octyl groups -4- isothiazolines -3- ketone of 4, the 5- bis- is for solid containing being 100%, boiling point is 300~
332.921 DEG C, molten point is 42.2~42.8 DEG C of pure medicament.
Further, the 2- octyl groups -4- isothiazoline -3- ketone is solid content 100%, and boiling point is 115~120 DEG C, phase
Than the pure medicament that the relative density of the water in 20 DEG C is 1.01~1.05.
Further, the benzimidazole is that solid content is 100%, and boiling point is between 340 DEG C~360 DEG C, molten point is 170
~180 DEG C of pure medicament.
Further, the emulsifying agent is glycerin polyoxyethylene ether fatty ester, dodecyl benzene sulfonate, polyethylene mistake
At least one in water sorbierite, polyethylene glycol hard fatty acid ester, alkyl polyoxyethylene, polyphosphazene polymer phosphate；It is described antifreeze
Agent is at least one in glycerine, isopropanol or urea；The bleeding agent is organosilicon aerosol-OT salt, fat
At least one in fat alcohol polyoxyalkyl ether, AEO；The amine neutralizer is diethanol amine, dodecyl
At least one in amine, monoethanolamine；The thickener is at least one in polyvinyl alcohol, bentonite or cellulose ether；It is described
Solubilized stabilizer is in AEO, APES, APG or N-2 methyl glucamines
At least one；The synergetic effect additive is Sensiva SC50,1,2- pentanediols, 1,2- decanediols, phenmethylol or benzene oxygen
At least one or mixture of ethanol；The relative density when ethanol is with 4 DEG C of water as object of reference is 0.789, and boiling point is
78.5 DEG C, the industrial absolute alcohol of -114.1 DEG C of fusing point；The dispersant is polyvinyl alcohol, neopelex, six inclined
At least one in sodium phosphate；The deionized water is to remove deimpurity running water.
On the other hand, the embodiment of the present invention also provides the preparation side of the antifouling algicide of environment-protection nano described in as above any one
Method, comprises the following steps：
Based on the mass fraction of formula, the chloro- N- octyl groups -4- isothiazolines -3- ketone of 4,5- bis-, the different thiophenes of 2- octyl groups -4- are sequentially added
Oxazoline -3- ketone, benzimidazole, addition account for the deionized water of the total consumption 15%~30% of ionized water, stir, and open at a high speed
Mixer, under the rotating speed of 2000~3000rmp, dispersion 20~35 minutes, are subsequently adding and account for the total consumption 60% of emulsifying agent at a high speed
Emulsifying agent, high-speed stirred pre-emulsification, prepare pre-emulsification mixed liquor it is standby；
Add remaining emulsifying agent, deionized water in reaction vessel, intensification is heated to 75~90 DEG C, keep isothermal reaction to anti-
When answering system without backflow, be cooled to 45~50 DEG C, start to be added dropwise successively water nano silver dispersions slurry, antifreezing agent, bleeding agent,
Solubilized stabilizer, synergetic effect additive, ethanol, the speed in 10~20 drop/minutes are dripped off after finishing, and control temperature at 45~50 DEG C,
After insulation 0.5~1 hour, less than 35~40 DEG C are cooled to, then call in amine neutralizer regulation pH to 7~9, thickening is then added dropwise
Agent, the speed in 10~20 drop/minutes is dripped off and keeps reaction temperature at 40~57 DEG C after finishing, and isothermal reaction 2~5 hours stops
Heating, cooling down, that is, the antifouling algicide of environment-protection nano stablized.
Further, the preparation process of the water nano silver dispersions slurry is：Sequentially add deionized water, dispersant
Stir, aluminium powder is then slowly added to while stirring, first stirring mixes 15min after powder is added, then is disperseed with ultrasonic wave
15min, finally stirs 15min, after mixed liquor is formed the uniform and suspension of good dispersion, opens grinder, is circulated
Grinding, milling time is about 11~15hr, obtains solid content for 20~40%, median is silver-colored in 30~70nm water nanos
Dispersion.
Further, the reaction vessel be with condenser, Dropping feeder, agitator, thermometer four-hole boiling flask.
After adopting the above technical scheme, the present invention at least has the advantages that：Environment-protection nano of the present invention is antifouling except algae
Agent and preparation method thereof low cost of manufacture, toxicity is low, to water source and Environmental security the features such as, to energy saving, environmental protection, wound
Make children significant with natural harmonious relationships.It is embodied in the following aspects：
1. the antifouling algicide of environment-protection nano of the invention, with water as matrix, water resource is enriched, especially preparation method process is simple,
Packaging, storage and convenient transportation, so that industrialization cost is reduced, beneficial to industrialized production；Based on aqueous emulsifying formulation product, system
Organic solvent is not used during standby, without flash-point problem, is not burnt and is not exploded, production is stored and uses safety.
2. the antifouling algicide of environment-protection nano of the invention, environmental pollution is small, environmentally harmful without formaldehyde, VOC etc.
Volatile matter, while not using traditional bacteriostatic agent to contain the metal ion compounds such as organo-arsenic, the organotin of huge poison, and can be quickly
By hydrolysis, light degradation and biodegradable decomposition, cumulative effect will not be produced, it is very safe to water source and environment.
3. the antifouling algicide of environment-protection nano of the invention, employs Nano Silver, and Nano Silver is ground based on nanometer technology
The novel antibacterial product of system, takes full advantage of the physicochemical characteristics of Nano Silver stabilization, in the side such as electricity, optics and catalysis
The excellent specific property in face.Due to the quantum effect of Nano Silver, small-size effect and with great specific surface area, thus with tradition
The incomparable antibacterial effect of inorganic antiseptic, the potent disinfecting and sterilizing functions that making silver has have been even more qualitative leap, and
Safe, effect is a kind of with long-lasting and weatherability antibacterial new material persistently.
4. the antifouling algicide of environment-protection nano of the invention, using multiple pharmaceutical agent combinations technology, on the basis of monomer bactericide
On, especially the combination solution after Water-borne modification preparation technique, makes full use of the complementary advantage of storeroom, it is possible to achieve effective part is lived
Property superposition, strengthen the antifouling mechanism except algae while, increase its antibacterial anticorrosive mildewproof performance, widen its application field, make an addition to
In coating, the water system of industrial circle, initial bacteria containing amount in water system product can be rapidly reduced, effectively solve and inhibit water system
Unite a large amount of harmful microorganisms, bacterium, fungi and algae reproduction, it is slow with high-efficiency broad spectrum while irreversibly suppressing its growth
That releases is antifouling except algae bactericidal performance, prevents and delay the generation and development of water system microbial resistance, antifouling to extend
Except the Acceptable life of algae bactericide, noresidue is free from environmental pollution and water source, and effect is lasting.
5. the antifouling algicide of environment-protection nano of the invention, good penetrability, emphasis enters to pharmacy effect mechanism and collaboration efficiency
Row research, makes up defect and deficiency that single medicament exists in use.Making an addition to when be discharged into water system in environment
Wait, can rapidly penetrate into sediment and decompose, active ingredient Omnibearing Infiltration matrix catch microorganism, with by disconnecting carefully
The key of bacterium and algae protein matter and play killing action, promptly can irreversibly suppress after being contacted with microorganism its growth, from
And causing the death of microbial cell, sheaf space bactericidal property being capable of effectively anti-water-stopping system on distinctive slow bactericide-release
It is putrid and deteriorated and between circulation aquatic products storage period, suppress microorganism, the breeding of bacterium, effectively kill bacterium, mould, fungi
Performance is much higher by other like products.
In sum, compared with traditional bacteriostatic agent, the antifouling algicide of environment-protection nano is based on water to the antifouling algicide of environment-protection nano
Combination solution after property preparation technique, makes full use of the complementary advantage of storeroom, free from extraneous odour, inanimate object characteristic of concentration, with
In environment can quickly by hydrolysis, light degradation and it is biodegradable decompose, noresidue is free from environmental pollution and water source, under high light and high temperature
Stabilization, and it is antifouling except algae restraining and sterilizing bacteria anti-mold effect is lasting, reach the restraining and sterilizing bacteria anti-mold effect of preferable high-efficiency broad spectrum.This
Point promotes the technology shifts upgrading for promoting industrial circle water system industry, reaches the progress of industrial circle industry production capacity upgrading, right
Energy saving, environmental protection, the harmonious relationships of creation man and nature are significant.
Specific embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combine, the application is described in further detail with reference to specific embodiment.
The embodiment of the present invention provides a kind of environment-protection nano antifouling algicide first, and its raw material is by below in terms of mass fraction
It is each into being grouped into：
Water nano silver dispersions slurry 5%~10%；
4,5- bis- chloro- N- octyl groups -4- isothiazoline -3- ketone 10%~20%；
2- octyl group -4- isothiazoline -3- ketone 5%~10%；
Benzimidazole 5%~10%；
Emulsifying agent 3~5%；
Antifreezing agent 5%~8%；
Bleeding agent 1%~3%；
Amine neutralizer 1%~3%；
Thickener 1%~3%；
Solubilized stabilizer 5%~10%；
Synergetic effect additive 5%~10%；
Ethanol 5%~8%；And
Deionized water 20%~30%.
In the specific implementation, the water nano silver dispersions slurry is obtained from the Nano Silver that particle diameter is 30~70nm
The solid water-borne dispersions slurry containing for 20~40%.
In one embodiment, the chloro- N- octyl groups -4- isothiazolines -3- ketone of 4, the 5- bis-, from solid containing being 100%, boils
Point between 300~332.921 DEG C, molten point（Refer to that material dissolves the temperature for liquid by solid-state under field conditions (factors)）For 42.2~
42.8 DEG C of active compound agent, the chloro- N- octyl groups -4- isothiazolines -3- ketone of 4,5- bis- that this contains admittedly is without organotin, Organic Chromium, arsenic etc.
Noxious material and heavy metal, when being discharged into environment, can rapidly penetrate into sediment and decompose, thus in marine organisms
Will not accumulate.The chloro- N- octyl groups -4- isothiazolines -3- ketone of 4,5- bis- especially after Water-borne modification preparation technique, cooperates with other groups
Point, it is possible to achieve the superposition of bioactivity, increase its anti-microbial property, widen its application field.To mould, fungi, heterotroph, algae
Class plant, marine fouling organism etc. to be had suppress well and killing action, after being contacted with harmful microorganism, can be thin by disconnecting
The key of bacterium and algae protein matter irreversibly suppresses its growth and plays killing action, so as to cause the death of microbial cell, therefore
The suppression with long-acting, broad-spectrum and killing action to common mould, bacterium, fungi, algae etc..
In one embodiment, the 2- octyl groups -4- isothiazoline -3- ketone is solid content 100%, and boiling point is 115~120
DEG C, the relative density of the water compared to 20 DEG C is 1.01~1.05 pure medicament.2- octyl groups -4- after Water-borne modification preparation technique is different
Thiazoline -3- ketone, VOC free, inanimate object characteristic of concentration, in the environment can natural degradation be innocuous substance, water source and environment are not caused
Pollution.Physics is reached with chlorine, corrosion inhibiter, dirt dispersion agent and most of anion, cation and nonionic surfactant etc.
Dissolve each other, it is long-term using not developing immunity to drugs in water system, have remarkable result to biological sludge stripping, collaboration other components can
Suppress the microorganisms such as mould, bacterium, fungi and mould simultaneously, effectively divide in the case where concentration is very low, still can effectively press down
The growth of bacterium, fungi and algae in cooling water processed, the medicament is when being diluted under concentration, it is possible to achieve biology is living
The superposition of property, increases its anti-microbial property, widens its application field, and this is that other medicaments are incomparable.
In one embodiment, the benzimidazole, from solid containing being 100%, boiling point is between 340 DEG C~360 DEG C, molten
Point is the active compound agent between 170~180 DEG C, benzimidazole collaboration other components, it is possible to achieve the superposition of bioactivity, with height
The remarkable antimycotic antiseptic effect of effect, the comprehensive catch microorganism of active ingredient rapidly suppresses mould, bacterium, fungi and mould etc.
The erosion and growth of microorganism, promptly can irreversibly suppress its growth after contact.Water can quickly be passed through in natural environment
Solution, light degradation and biodegradable decomposition, high light and high temperatures, permeability are strong, fungus-resistant broad-spectrum high efficacy outstanding feature.
In one embodiment, the emulsifying agent is glycerin polyoxyethylene ether fatty ester, dodecyl benzene sulfonate, gathers
At least one in ethene anhydrous sorbitol, polyethylene glycol hard fatty acid ester, alkyl polyoxyethylene, polyphosphazene polymer phosphate.
In one embodiment, the antifreezing agent is at least one in glycerine, isopropanol or urea.
In one embodiment, the bleeding agent is organosilicon aerosol-OT salt, poly alkyl alcohol oxyalkyl
At least one in ether, AEO.
In one embodiment, the amine neutralizer is at least one in diethanol amine, lauryl amine, monoethanolamine.
In one embodiment, the thickener is at least one in polyvinyl alcohol, bentonite or cellulose ether.
In one embodiment, the solubilized stabilizer is AEO, APES, alkyl
At least one in glucosides or N-2 methyl glucamines.
In one embodiment, the synergetic effect additive be Sensiva SC50,1,2- pentanediols, 1,2- decanediols,
At least one or mixture of phenmethylol or Phenoxyethanol.
In one embodiment, the relative density when ethanol is with 4 DEG C of water as object of reference is 0.789, and boiling point is
78.5 DEG C, the industrial absolute alcohol of -114.1 DEG C of fusing point.
In one embodiment, the deionized water is to remove deimpurity running water.
The present invention also provides the formula such as following table of several specific implementations, and the percentage in table is mass percent：
On the other hand, the embodiment of the present invention additionally provides a kind of preparation method of the antifouling algicide of above-mentioned environment-protection nano, its step
It is as follows：
Based on the mass fraction of formula, the chloro- N- octyl groups -4- isothiazolines -3- ketone of 4,5- bis-, the different thiophenes of 2- octyl groups -4- are sequentially added
Oxazoline -3- ketone, benzimidazole, addition account for the deionized water of the total consumption 15%~30% of ionized water, stir, and open at a high speed
Mixer, under the rotating speed of 2000~3000rmp, dispersion 20~35 minutes, are subsequently adding and account for the total consumption 60% of emulsifying agent at a high speed
Emulsifying agent, high-speed stirred pre-emulsification, prepare pre-emulsification mixed liquor it is standby；
Add remaining emulsifying agent, deionized water in reaction vessel, intensification is heated to 75~90 DEG C, keep isothermal reaction to anti-
When answering system without backflow, 45~50 DEG C are cooled to, start that water nano silver dispersions, antifreezing agent, bleeding agent, solubilising are added dropwise successively
Stabilizer, synergetic effect additive, ethanol, the speed in 10~20 drop/minutes are dripped off after finishing, and control temperature is incubated at 45~50 DEG C
After 0.5~1 hour, less than 35~40 DEG C are cooled to, then call in amine neutralizer regulation pH to 7~9, thickening is then added dropwise successively
Agent, the speed in 10~20 drop/minutes is dripped off and keeps reaction temperature at 40~57 DEG C after finishing, and isothermal reaction 2~5 hours stops
Heating, cooling down, that is, the antifouling algicide of environment-protection nano stablized.
The water nano silver dispersions slurry will in advance be obtained according to following preparation technology：Sequentially add deionized water,
Dispersant stirs, and is then slowly added to aluminium powder while stirring, powder add after first stirring mixing 15min, then with ultrasound
Wavelength-division dissipates 15min, finally stirs 15min, after mixed liquor is formed the uniform and suspension of good dispersion, opens grinder, enters
Row circular grinding, milling time is about 11~15hr, obtains solid content for 20~40%, median is aqueous in 30~70nm
Nanometer silver dispersions.Nano Silver is the novel antibacterial product developed based on nanometer technology, with the physico of stabilization
Characteristic is learned, there is very excellent characteristic at aspects such as electricity, optics and catalysis.Due to quantum effect, small-size effect and tool
There is a great specific surface area, thus with the incomparable antibacterial effect of traditional inorganic antiseptic, make that silver has potent disappears
Malicious sterilizing function has been even more qualitative leap, and safe, effect is persistently, is a kind of with long-lasting and weatherability antibacterial
Material.
When implementing, the reaction vessel can be with condenser, Dropping feeder, agitator, four mouthfuls of thermometer burnings
Bottle.
The antifouling algicide of environment-protection nano of the invention has the advantages that：
1. environmental protection, VOC content is less than 50g/L, far below HJ2537-2014《The aqueous painting of environmental labelling product technical requirements
Material》It is required that 80g/L, meet national green building requirements.
2. antifouling algae removal efficiency is protruded, to the algae in aqueous systems, marine fouling organism, mould, fungi, heterotrophism
Bacterium etc. to be had suppress well and killing action.Under product standard state, meet IMO's《The world harmful Housing system of control ship
Pact》（AFS pacts）、《Ballast tank of ship protective coating performance standard》（PSPC）, European Union《Bactericide product guide》（BPD）
With the requirement of the regulation such as REACH；Meet SN/T3122-2012《Inorganic antibacterial material Anti-microbial Performance Tests method》、GBT
30706-2014《Photocatalysis antibacterial material and product anti-microbial property test method and evaluation under radiation of visible light》、JIS Z
2911-1992《Fungus resistance test method》、JIS Z 2801-2000《Antibiotic plastic Anti-microbial Performance Tests method and antibacterial are imitated
Really》、ASTM G21-96（2002）《Synthetic polymeric material is mould proof（Resistance to fungi）Performance test standard》、SN/T 2399-2010《It is anti-
Bacterium Evaluation of metallic materials method》Etc. domestic and international antibacterial standard.
3. have wide range of applications, the antifouling algicide of environment-protection nano of the invention, using nanometer and formulation complex configuration technology,
The superposition of bioactivity can be realized, increase its it is antifouling except algae anti-microbial property, widen its application field, in making an addition to coating, can
To allow organic matter during film prevents water system to gather, microbial film is formed, and reduces microalgae, fungi, the attachment of animals and plants；Directly
Make an addition in the water of industrial circle, can rapidly reduce initial bacteria containing amount in water system product, effectively solve and inhibit water system
A large amount of harmful microorganism, bacterium, fungi and algae reproductions, extremely strong can efficiently control or kill the harmful micro- life in water system
Thing, bacterium, fungi and algae, good with degradability while irreversibly suppressing its growth, inanimate object accumulation, noresidue are not
Pollution environment and water source, safe operation, stability are strong, and bacteriostasis property is notable.
4. environmentally friendly, the antifouling algicide of environment-protection nano of the invention can quickly by hydrolysis, light in natural environment
Degraded and it is biodegradable decompose, noresidue, inanimate object characteristic of concentration, in the environment can natural degradation be innocuous substance, do not cause water
Source and environmental pollution.With chlorine, corrosion inhibiter, dirt dispersion agent and most of anion, cation and nonionic surfactant etc.
Dissolving each other for physics is reached, long-term use is not developed immunity to drugs in water system.
5. the antifouling algicide of environment-protection nano of the invention, with water as matrix, water resource is enriched, especially preparation method technique letter
It is single, packaging, storage and convenient transportation, so that industrialization cost is reduced, beneficial to industrialized production.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand, can these embodiments be carried out with various equivalent changes without departing from the principles and spirit of the present invention
Change, change, replace and modification, the scope of the present invention is limited by appended claims and its equivalency range.
Claims (9)
1. the antifouling algicide of a kind of environment-protection nano, it is characterised in that its raw material is by following into being grouped into terms of mass fraction：
The chloro- N- octyl groups -4- isothiazolines -3- ketone 10%~20%, 2- of water nano silver dispersions slurry 5%~10%, 4,5- bis- is pungent
Base -4- isothiazoline -3- ketone 5%~10%, benzimidazole 5%~10%, emulsifying agent 3%~5%, antifreezing agent 5%~8%,
Bleeding agent 1%~3%, amine neutralizer 1%~3%, thickener 1%~3%, solubilized stabilizer 5%~10%, synergetic effect additive
5%~10%, ethanol 5%~8%, deionized water 20%~30%.
2. the antifouling algicide of environment-protection nano as claimed in claim 1, it is characterised in that the water nano silver dispersions slurry
Be be from particle diameter 30~70nm Nano Silver obtained in the solid water-borne dispersions slurry containing for 20~40%.
3. the antifouling algicide of environment-protection nano as claimed in claim 1, it is characterised in that the chloro- N- octyl groups -4- of 4, the 5- bis- are different
For solid containing being 100%, boiling point is 300~332.921 DEG C to thiazoline -3- ketone, and molten point is 42.2~42.8 DEG C of pure medicament.
4. the antifouling algicide of environment-protection nano as claimed in claim 1, it is characterised in that the 2- octyl groups -4- isothiazolines -3-
Ketone is solid content 100%, and boiling point is 115~120 DEG C, and the relative density of the water compared to 20 DEG C is 1.01~1.05 pure medicine
Agent.
5. the antifouling algicide of environment-protection nano as claimed in claim 1, it is characterised in that the benzimidazole is for solid content
100%, boiling point is between 340 DEG C~360 DEG C, molten point is 170~180 DEG C of pure medicament.
6. the antifouling algicide of environment-protection nano as claimed in claim 1, it is characterised in that the emulsifying agent is glycerin polyoxyethylene
Ether fatty acid ester, dodecyl benzene sulfonate, polyethylene sorbitan alcohol, polyethylene glycol hard fatty acid ester, alkyl polyoxyethylene,
At least one in polyphosphazene polymer phosphate；The antifreezing agent is at least one in glycerine, isopropanol or urea；It is described to ooze
Saturating agent is at least in organosilicon aerosol-OT salt, fatty alcohol polyoxyalkyl ether, AEO
Kind；The amine neutralizer is at least one in diethanol amine, lauryl amine, monoethanolamine；The thickener be polyvinyl alcohol,
At least one in bentonite or cellulose ether；The solubilized stabilizer is AEO, alkylphenol-polyethenoxy
At least one in ether, APG or N-2 methyl glucamines；The synergetic effect additive be Sensiva SC50,1,
At least one or mixture of 2- pentanediols, 1,2- decanediols, phenmethylol or Phenoxyethanol；The ethanol is with 4 DEG C of water
Relative density during for object of reference is 0.789, and boiling point is 78.5 DEG C, the industrial absolute alcohol of -114.1 DEG C of fusing point；It is described go from
Sub- water is to remove deimpurity running water.
7. the preparation method of the antifouling algicide of environment-protection nano as any one of claim 1~6, it is characterised in that bag
Include following steps：
Based on the mass fraction of formula, the chloro- N- octyl groups -4- isothiazolines -3- ketone of 4,5- bis-, the different thiophenes of 2- octyl groups -4- are sequentially added
Oxazoline -3- ketone, benzimidazole, addition account for the deionized water of the total consumption 15%~30% of ionized water, stir, and open at a high speed
Mixer, under the rotating speed of 2000~3000rmp, dispersion 20~35 minutes, are subsequently adding and account for the total consumption 60% of emulsifying agent at a high speed
Emulsifying agent, high-speed stirred pre-emulsification, prepare pre-emulsification mixed liquor it is standby；
Add remaining emulsifying agent, deionized water in reaction vessel, intensification is heated to 75~90 DEG C, keep isothermal reaction to anti-
When answering system without backflow, be cooled to 45~50 DEG C, start to be added dropwise successively water nano silver dispersions slurry, antifreezing agent, bleeding agent,
Solubilized stabilizer, synergetic effect additive, ethanol, the speed in 10~20 drop/minutes are dripped off after finishing, and control temperature at 45~50 DEG C,
After insulation 0.5~1 hour, less than 35~40 DEG C are cooled to, then call in amine neutralizer regulation pH to 7~9, thickening is then added dropwise
Agent, the speed in 10~20 drop/minutes is dripped off and keeps reaction temperature at 40~57 DEG C after finishing, and isothermal reaction 2~5 hours stops
Heating, cooling down, that is, the antifouling algicide of environment-protection nano stablized.
8. the preparation method of the antifouling algicide of environment-protection nano as claimed in claim 7, it is characterised in that the water nano silver
The preparation process of dispersion slurry is：Sequentially add deionized water, dispersant to stir, silver is then slowly added to while stirring
Powder, first stirring mixes 15min after powder is added, then disperses 15min with ultrasonic wave, finally stirs 15min, forms mixed liquor
After the uniform and suspension of good dispersion, grinder is opened, be circulated grinding, milling time is about 11~15hr, is obtained
Solid content is 20~40%, median in 30~70nm water nano silver dispersions.
9. the preparation method of the antifouling algicide of environment-protection nano as claimed in claim 7, it is characterised in that the reaction vessel is
With condenser, Dropping feeder, agitator, thermometer four-hole boiling flask.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710025195.9A CN106797955A (en) | 2017-01-13 | 2017-01-13 | Antifouling algicide of environment-protection nano and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710025195.9A CN106797955A (en) | 2017-01-13 | 2017-01-13 | Antifouling algicide of environment-protection nano and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106797955A true CN106797955A (en) | 2017-06-06 |
Family
ID=58984312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710025195.9A Pending CN106797955A (en) | 2017-01-13 | 2017-01-13 | Antifouling algicide of environment-protection nano and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106797955A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108308194A (en) * | 2018-04-20 | 2018-07-24 | 东莞市顶盛环保科技有限公司 | A kind of composite multifunction fungicide |
| CN109293807A (en) * | 2018-08-28 | 2019-02-01 | 汕头市炜星工艺实业有限公司 | A kind of long acting antibiotic moldproof polyethylene alcohol and the preparation method and application thereof |
| CN110946149A (en) * | 2019-12-09 | 2020-04-03 | 王映镝 | Bactericidal and algae-killing synergistic composition for paint, coating, water body and wood and application thereof |
| CN111286273A (en) * | 2020-02-12 | 2020-06-16 | 石家庄市油漆厂 | Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof |
| CN111528222A (en) * | 2020-04-27 | 2020-08-14 | 博富科技股份有限公司 | Nano zinc oxide antibacterial and antiviral spray and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277025A (en) * | 2011-07-21 | 2011-12-14 | 上海海事大学 | Sea antifouling coating |
| CN102304303A (en) * | 2011-08-04 | 2012-01-04 | 上海海事大学 | High-dispersibility controlled-release silver composite anti-fouling agent and preparation method thereof |
| CN102939973A (en) * | 2012-11-21 | 2013-02-27 | 安徽省电力科学研究院 | Compound type sterilizing algaecide and application thereof |
| CN104621143A (en) * | 2015-01-30 | 2015-05-20 | 无锡昊瑜节能环保设备有限公司 | Compounding method of algae removal bactericide |
-
2017
- 2017-01-13 CN CN201710025195.9A patent/CN106797955A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277025A (en) * | 2011-07-21 | 2011-12-14 | 上海海事大学 | Sea antifouling coating |
| CN102304303A (en) * | 2011-08-04 | 2012-01-04 | 上海海事大学 | High-dispersibility controlled-release silver composite anti-fouling agent and preparation method thereof |
| CN102939973A (en) * | 2012-11-21 | 2013-02-27 | 安徽省电力科学研究院 | Compound type sterilizing algaecide and application thereof |
| CN104621143A (en) * | 2015-01-30 | 2015-05-20 | 无锡昊瑜节能环保设备有限公司 | Compounding method of algae removal bactericide |
Non-Patent Citations (1)
| Title |
|---|
| 陈复: "《水处理技术及药剂大全》", 31 October 2000, 中国石化出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108308194A (en) * | 2018-04-20 | 2018-07-24 | 东莞市顶盛环保科技有限公司 | A kind of composite multifunction fungicide |
| CN109293807A (en) * | 2018-08-28 | 2019-02-01 | 汕头市炜星工艺实业有限公司 | A kind of long acting antibiotic moldproof polyethylene alcohol and the preparation method and application thereof |
| CN110946149A (en) * | 2019-12-09 | 2020-04-03 | 王映镝 | Bactericidal and algae-killing synergistic composition for paint, coating, water body and wood and application thereof |
| CN111286273A (en) * | 2020-02-12 | 2020-06-16 | 石家庄市油漆厂 | Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof |
| CN111528222A (en) * | 2020-04-27 | 2020-08-14 | 博富科技股份有限公司 | Nano zinc oxide antibacterial and antiviral spray and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106797955A (en) | Antifouling algicide of environment-protection nano and preparation method thereof | |
| US20140030306A1 (en) | Methods and compositions for remediating microbial induced corrosion and environmental damage, and for improving wastewater treatment processes | |
| CN106396037B (en) | Peracetic acid/hydrogen peroxide and peroxide reducing agent are used to handle drilling fluid, fracturing fluid, recirculation water and the purposes for discharging water | |
| Peller et al. | TiO2 as a photocatalyst for control of the aquatic invasive alga, Cladophora, under natural and artificial light | |
| CN102300944B (en) | Marine organism anti-fouling paint and preparing method and use thereof | |
| JP2003528967A (en) | Antifouling paint composition comprising rosin and enzyme | |
| CN111286273A (en) | Novel long-acting broad-spectrum antibacterial multifunctional water-based building coating and preparation method thereof | |
| Alum et al. | Cement-based biocide coatings for controlling algal growth in water distribution canals | |
| Yadav et al. | Nanobioremediation: A sustainable approach towards the degradation of sodium dodecyl sulfate in the environment and simulated conditions | |
| CN104365668B (en) | Environment-friendly long-life is combined anti-fouling material | |
| KR101254723B1 (en) | Environmental-friendly antifouling paint composition comprising zinc undecylenate | |
| CN105238579A (en) | Computer electronic display screen cleaning agent and preparation method thereof | |
| Soliman et al. | Antifouling and antibacterial activities of marine bioactive compounds extracted from some red sea cucumber | |
| Rao | Biofouling in industrial water systems | |
| Kochina et al. | Biocorrosion, biofouling, and advanced methods of controlling them | |
| CN103805371A (en) | Scavenging agent for sludge on surfaces of aquatic plants in aquaculture pond | |
| Cappitelli et al. | New environmentally friendly approaches against biodeterioration of outdoor cultural heritage | |
| Abi Nassif et al. | Development of alginate hydrogels active against adhesion of microalgae | |
| KR101701092B1 (en) | Red tide removal materials | |
| KR20010067384A (en) | 5-carboxanilido-haloalkylthiazoles as antimicrobial and marine antifouling agent | |
| Zhao et al. | Antifouling based on biocides: From toxic to green | |
| Lang et al. | Self-Immolative Polythiophene for sunlight inactivation of harmful cyanobacteria | |
| KR20060103311A (en) | Composition to eliminate red tide | |
| KR101890801B1 (en) | The mixture for the removal of green algae | |
| CN101654594B (en) | Dimethyl silicone polymer marine antifouling paint containing sodium benzoate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170606 |
|
| RJ01 | Rejection of invention patent application after publication |