CN106929934B - A kind of preparation method of composite Nano algicide-antifoulant - Google Patents
A kind of preparation method of composite Nano algicide-antifoulant Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000002519 antifouling agent Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 24
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 22
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 239000011858 nanopowder Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 7
- 239000004033 plastic Substances 0.000 claims abstract description 7
- 229920000098 polyolefin Polymers 0.000 claims abstract description 7
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052927 chalcanthite Inorganic materials 0.000 claims abstract description 6
- 230000006855 networking Effects 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 241000195493 Cryptophyta Species 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 230000008602 contraction Effects 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 231100001231 less toxic Toxicity 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- BQPJQBVGOAZYNB-UHFFFAOYSA-N hydrazine;hydrate Chemical compound O.NN.NN BQPJQBVGOAZYNB-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- -1 Sodium alkyl benzene Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000206602 Eukaryota Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003653 coastal water Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000009364 mariculture Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- 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
- A01N59/20—Copper
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of preparation methods of composite Nano algicide-antifoulant, are doing dispersing agent using polyethylene glycol (PEG), hydrazine hydrate (hydrazine) does reducing agent and CuSO4·5H2O reaction generates Cu2O precipitating, is centrifuged, washs to obtain the Cu of 10~15nm2O suspension；Then the suspension is made into surfactant with neopelex, evenly spreads to Cu2+In solution, the pH value of solution is controlled, NaHB is used4Reducing agent is made, reaction generates Cu/Cu2O composite nanoparticle is added organic diatomite, stirs in the suspension formed after being centrifuged, washing, then is centrifuged, is dried in vacuo to obtain Cu/Cu2O composite nano powder；The anti-algae agent of novel antifouling is made by certain mass proportion with waterglass again in the powder.It adds it in polyolefins plastic masterbatch, fusing post-tensioning works out networking, obtain the mesh sheet with antifouling anti-algae performance at filament.Plunged into the commercial sea experiments have shown that, antifouling life had the characteristics that less toxic, efficient, free of contamination at 6 months or more, and safety and environmental protection is easy to industrialized production.
Description
Technical field:
The present invention relates to a kind of method for preparing composite Nano algicide-antifoulant by chemosynthesis reaction, products obtained therefrom quilts
Among the antifouling anti-algae cable of mariculture industry, belong to technical field of nano material.
Background technique:
Marine aquaculture industry, such as coastal waters cage culture, wire net cultivation, due to marine organisms (algae and mollusk
Class) attachment to cultivation netting gear, especially June to September high temperature season high-incidence season for being ocean unicellular lower eukaryote, a large amount of biologies are to netting gear
Attachment, affect the normal growth of cultivation object, yield and quality is all difficult to work together for still greater successes in.External such as Japan, South Korea, the U.S.
Fishery developed country is directed to the research and development that culturing net has antifouling anti-algae project very early, achieves some achievements.Such as early stage
Anti-halobios adhersion technology be to be made an addition in netting gear material using organic metal class (such as organotin, Organic leadP), for antifouling anti-
Algae.But since heavy metal ion causes serious pollution to paralic environment, use inorganic elements instead in recent years.But Japan's test net cage
Tested in Jiangsu Qidong East China Sea region, the marine organisms high-incidence season 6,7, in August, one and a half months is seriously attached to biology
(chrysanthemum algae, barnacle etc.).
Currently, the serial nano CuO antibacterial agent that a company of the U.S. releases has had commercial practicability.This particle size range
It is easily added in plastics, synthetic fibers and coating in 20~50 nanometers of CuO, is mainly used for protective paint, anti-fouling paint and different coating
Additive.
Domestic last century the nineties middle and later periods and the beginning of this century, several fishing net anti-fouling agents or antifouling are successively succeeded in developing
Coating can be evenly coated at netting gear surface, formed " barrier ", i.e. the antifouling method of coating, can effectively prevent biological attachment (" Shandong
Fishery ", the 1997, the 6th phase).But the third month that these anti-fouling agents or antifouling paint are tested in marine linked network, has part sea
Foreign biological attachment, anti-fouling effect are less desirable；And netting gear need to be dipped into the anti-fouling agent or antifouling paint, then take out and dry in the air
It is dry to use, it is not only troublesome, also add the labor intensity of fisherman.
Summary of the invention:
A kind of items for greatly improving product are provided it is an object of the invention to overcome the shortcomings of above-mentioned prior art
Energy and use scope, antifouling life is long, and antifouling anti-algae effect is good, and less toxic, efficient, pollution-free, safety and environmental protection is easy to industrialize
The preparation method of the composite Nano algicide-antifoulant of production.
The purpose of the present invention can be obtained by following measure: a kind of preparation method of composite Nano algicide-antifoulant,
It is characterized in that it includes the following steps:
(1) CuSO is weighed4·5H2O is added in deionized water, agitating and heating, and Cu is made after dissolution2+Solution；Then it is added
Dissolution is sufficiently stirred in polyethylene glycol, 40% hydrazine hydrate solution is added dropwise in the case where constantly stirring, and gradually by solution
50 DEG C~70 DEG C are heated to, continues to stir at least 30 minutes to fully reacting；By reaction product deionized water centrifuge washing 3
Time, the Cu that 10~15nm is made is concentrated2O suspension；The polyethylene glycol and CuSO4·5H2The mol ratio of O is 0.01
~0.1:1；N in 40% hydrazine hydrate solution2H4·H2O and CuSO4·5H2The molar ratio of O is 1~2:1；
(2) CuSO is weighed again4·5H2O is added in deionized water, and Cu is made after agitating and heating dissolution2+Solution；It is added 12
Sodium alkyl benzene sulfonate stirring and dissolving, then by Cu made from step (1)2O suspension is added thereto, and is stirred evenly；Described 12
Sodium alkyl benzene sulfonate and CuSO4·5H2O、Cu2The mol ratio of O suspension is 0.01~0.2:2:1；
(3) taking concentration is 6% NaOH solution, and NaHB is added4NaHB is made in stirring and dissolving4It is molten to adjust control for alkaline solution
The pH value of liquid is 10~12, and solution made from above-mentioned steps (2) is added slowly thereto under constant stirring, is stirred for reaction 10
Minute to fully reacting, forms Cu/Cu2O composite nanoparticle is centrifuged, washs 2-3 obtained Cu/Cu after2O composite nano-granule
Sub- slurry, at this time by the quality proportioning of 1:1 in Cu/Cu2Organic diatomite is added in O composite nanoparticle slurry, is sufficiently stirred
20min absorbs Adsorption of Cu/Cu2O composite nanoparticle, forms complex therewith；It is centrifuged again, is dried in vacuo to obtain Cu/Cu2O is multiple
Close nano-powder；The NaHB4With the CuSO of step (2)4·5H2The molar ratio of O is 1~2:1；
(4) Cu/Cu made from above-mentioned steps (3) is weighed2Waterglass is added in O composite nano powder, mixes well, is made anti-
Dirty anti-algae agent, is added in polyolefins plastic masterbatch, and high temperature melting pulls into filament, works out networking to get good to having
The mesh sheet of antifouling anti-algae performance；The waterglass and Cu/Cu2The quality proportioning of O composite nano powder is 0.01~0.2:1.
In order to further realize the purpose of the present invention, polyethylene glycol and CuSO in the step (1)4·5H2O's rubs
Your proportion is 0.05:1；N in 40% hydrazine hydrate solution2H4·H2O and CuSO4·5H2The molar ratio of O is 1.5:1.
In order to further realize the purpose of the present invention, neopelex and CuSO in the step (2)4·
5H2O、Cu2The mol ratio of O suspension is 0.1:2:1.
NaHB in order to further realize the purpose of the present invention, in the step (3)4With the CuSO of step (2)4·5H2O
Molar ratio be 1.5:1.
In order to further realize the purpose of the present invention, waterglass and Cu/Cu in the step (4)2O composite nano powder
Quality proportioning be 0.1:1.
The present invention can produce following good effect compared with the prior art: nanotechnology is applied to antifouling anti-algae by the present invention
In the preparation of product, especially in the preparation of inorganic algicide-antifoulant, by the superfine powder for preparing inorganic algicide-antifoulant
End can greatly improve the properties and use scope of product.The present invention does dispersing agent using polyethylene glycol (PEG),
Compared with using other dispersing agents, it is formed by Cu2O nano particle is evenly distributed, and stability is more preferable.The present invention provides one kind
Manufactured Cu/Cu2O composite nano powder is main antifouling anti-algae main body, compound to activate promotor and control sustained release agent, is developed
New and effective algicide-antifoulant is gone out.It can relatively easily be added in cable made by polyolefin based materials, have received
Good antifouling anti-algae effect.The present invention plunged into the commercial sea experiments have shown that, antifouling life at 6 months or more, have low toxicity, efficiently,
Free of contamination feature, safety and environmental protection are easy to industrialized production.
Specific embodiment: detailed description is had a fling to specific embodiment party of the invention below:
A kind of embodiment 1: preparation method of composite Nano algicide-antifoulant, it is characterised in that it includes the following steps:
(1) CuSO of 50g is weighed4·5H2O is added in the deionized water of 1000mL, agitating and heating, is made after dissolution
The Cu of 0.2mol/L2+Solution；Then polyethylene glycol (PEO) is added, dissolution is sufficiently stirred, add dropwise in the case where constantly stirring
Enter hydrazine hydrate (40%) solution 12.5mL, and solution is gradually heated to 60 DEG C, continues to stir at least 30 minutes to fully reacting；
By reaction product with deionized water centrifuge washing 3 times, the Cu that 12nm is made is concentrated2O suspension；The polyethylene glycol of the step
With CuSO4·5H2The mol ratio of O is 0.05:1.
(2) CuSO of 50g is weighed again4·5H2O is added in the deionized water of 500mL, is made after agitating and heating dissolution
The Cu of 0.4mol/L2+Solution；Neopelex stirring and dissolving is added, then by Cu made from step (1)2O suspension adds
Enter wherein, stirs evenly, the neopelex and CuSO4·5H2O、Cu2The mol ratio of O suspension is 0.1:
2:1。
(3) taking concentration is 6% NaOH solution 1000mL, and 11.3gNaHB is added4NaHB is made in stirring and dissolving4Alkalinity is molten
Liquid, adjust control solution pH value be 10~12,30 DEG C of reaction temperature or so, by solution made from above-mentioned steps (2) continuous
It is added slowly thereto under stirring, is stirred for reaction 10 minutes to fully reacting, forms Cu/Cu2O composite nanoparticle, be centrifuged,
Cu/Cu is made after washing 3 times2O composite nanoparticle slurry, at this time by the quality proportioning of 1:1 in Cu/Cu2O composite nanoparticle
Organic diatomite is added in slurry, is sufficiently stirred 20 minutes, absorbs Adsorption of Cu/Cu2O composite nanoparticle is formed compound therewith
Body；It is centrifuged again, is dried in vacuo to obtain Cu/Cu2O composite nano powder.
(4) Cu/Cu made from 30g above-mentioned steps (3) is weighed23g waterglass is added in O composite nano powder, mixes well,
Algicide-antifoulant is made；It is added it in polyolefins plastic masterbatch again, high temperature melting pulls into filament, works out networking, i.e.,
Obtain the mesh sheet with good antifouling anti-algae performance.
A kind of embodiment 2: preparation method of composite Nano algicide-antifoulant, it is characterised in that it includes the following steps:
(1) CuSO of 250g is weighed4·5H2O is added in the deionized water of 5000mL, agitating and heating, is made after dissolution
The Cu of 0.2mol/L2+Solution；Then polyethylene glycol (PEO) is added, dissolution is sufficiently stirred, add dropwise in the case where constantly stirring
Enter hydrazine hydrate (40%) solution 94mL, and solution is gradually heated to 50 DEG C, continues to stir at least 30 minutes to fully reacting；It will
The Cu that 10nm is made is concentrated with deionized water centrifuge washing 3 times in reaction product2O suspension；The polyethylene glycol
(PEO) and CuSO4·5H2The mol ratio of O is 0.01:1.
(2) CuSO of 250g is weighed again4·5H2O is added in the deionized water of 2500mL, is made after agitating and heating dissolution
The Cu of 0.4mol/L2+Solution；Neopelex stirring and dissolving is added, then by Cu made from step (1)2O suspension adds
Enter wherein, stirs evenly, the neopelex and CuSO4·5H2O、Cu2The mol ratio of O suspension is 0.01:
2:1；
(3) taking concentration is 6% NaOH solution 5000mL, and 37.8gNaHB is added4NaHB is made in stirring and dissolving4Alkalinity is molten
Liquid, adjust control solution pH value be 10~12,30 DEG C of reaction temperature or so, by solution made from above-mentioned steps (2) continuous
It is added slowly thereto under stirring, is stirred for reaction 10 minutes to fully reacting, forms Cu/Cu2O composite nanoparticle, be centrifuged,
Cu/Cu is made after washing 2 times2O composite nanoparticle slurry, at this time by the quality proportioning of 1:1 in Cu/Cu2O composite nanoparticle
Organic diatomite is added in slurry, is sufficiently stirred 20 minutes, absorbs Adsorption of Cu/Cu2O composite nanoparticle is formed compound therewith
Body；It is centrifuged again, is dried in vacuo to obtain Cu/Cu2O composite nano powder.
(4) Cu/Cu made from 300g above-mentioned steps (3) is weighed23g waterglass is added in O composite nano powder, mixes well,
Algicide-antifoulant is made；It is added it in polyolefins plastic masterbatch again, high temperature melting pulls into filament, works out networking, i.e.,
Obtain the mesh sheet with good antifouling anti-algae performance.
A kind of embodiment 3: preparation method of composite Nano algicide-antifoulant, it is characterised in that it includes the following steps:
(1) CuSO of 500g is weighed4·5H2O is added in the deionized water of 10L, agitating and heating, and 0.2mol/ is made after dissolution
The Cu of L2+Solution；Then polyethylene glycol (PEO) is added, dissolution is sufficiently stirred, hydration is added dropwise in the case where constantly stirring
Hydrazine (40%) solution 250mL, and solution is gradually heated to 70 DEG C, continue to stir at least 30 minutes to fully reacting；Reaction is produced
The Cu that 15nm is made is concentrated with deionized water centrifuge washing 3 times in object2O suspension；The polyethylene glycol (PEO) with
CuSO4·5H2The mol ratio of O is 0.1:1.
(2) CuSO of 500g is weighed again4·5H2O is added in the deionized water of 5000mL, is made after agitating and heating dissolution
The Cu of 0.4mol/L2+Solution；Neopelex stirring and dissolving is added, then by Cu made from step (1)2O suspension adds
Enter wherein, stirs evenly, the neopelex and CuSO4·5H2O、Cu2The mol ratio of O suspension is 0.2:
2:1；
(3) taking concentration is 6% 10 L of NaOH solution, and 151.2gNaHB is added4NaHB is made in stirring and dissolving4Alkaline solution,
The pH value for adjusting control solution is 10~12,30 DEG C of reaction temperature or so, solution made from above-mentioned steps (2) is being stirred continuously
Under be added slowly thereto, be stirred for reaction 10 minutes to fully reacting, form Cu/Cu2O composite nanoparticle is centrifuged, is washed
Cu/Cu is made after 3 times2O composite nanoparticle slurry, at this time by the quality proportioning of 1:1 in Cu/Cu2O composite nanoparticle slurry
It is interior that organic diatomite is added, it is sufficiently stirred 20 minutes, absorbs Adsorption of Cu/Cu2O composite nanoparticle, forms complex therewith；Again
It is centrifuged, is dried in vacuo to obtain Cu/Cu2O composite nano powder.
(4) Cu/Cu made from 300g above-mentioned steps (3) is weighed260g waterglass is added in O composite nano powder, sufficiently mixed
It is even, algicide-antifoulant is made；It being added it in polyolefins plastic masterbatch again, high temperature melting pulls into filament, networking is worked out,
Obtain the mesh sheet with good antifouling anti-algae performance.
Above embodiment is only that preferred embodiments of the present invention will be described, and other preferred embodiments are herein
Do not tire out one by one and state, and is not intended to limit the scope of the present invention, without departing from the spirit of the design of the present invention, this field
The various changes and improvements that ordinary engineering and technical personnel makes technical solution of the present invention should all fall within right of the invention and want
In the protection scope for asking book to determine.
Claims (5)
1. a kind of preparation method of composite Nano algicide-antifoulant, it is characterised in that it includes the following steps:
(1) CuSO is weighed4·5H2O is added in deionized water, agitating and heating, and Cu is made after dissolution2+Solution；Then poly- second is added
Dissolution is sufficiently stirred in allyl diglycol, 40% hydrazine hydrate solution is added dropwise in the case where constantly stirring, and gradually heat solution
To 50 DEG C~70 DEG C, continue to stir at least 30 minutes to fully reacting；It is dense by reaction product with deionized water centrifuge washing 3 times
Contraction obtains the Cu of 10~15nm2O suspension；The polyethylene glycol and CuSO4·5H2The mol ratio of O be 0.01~
0.1:1；N in 40% hydrazine hydrate solution2H4·H2O and CuSO4·5H2The molar ratio of O is 1~2:1；
(2) CuSO is weighed again4·5H2O is added in deionized water, and Cu is made after agitating and heating dissolution2+Solution；Dodecyl is added
Benzene sulfonic acid sodium salt stirring and dissolving, then by Cu made from step (1)2O suspension is added thereto, and is stirred evenly；The dodecyl
Benzene sulfonic acid sodium salt and CuSO4·5H2O、Cu2The mol ratio of O suspension is 0.01~0.2:2:1；
(3) taking concentration is 6% NaOH solution, and NaHB is added4NaHB is made in stirring and dissolving4Alkaline solution adjusts control solution
PH value is 10~12, and solution made from above-mentioned steps (2) is added slowly thereto under constant stirring, is stirred for reaction 10 minutes
To fully reacting, Cu/Cu is formed2O composite nanoparticle is centrifuged, washs 2-3 obtained Cu/Cu after2O composite nanoparticle slurry
Material, at this time by the quality proportioning of 1:1 in Cu/Cu2Organic diatomite is added in O composite nanoparticle slurry, is sufficiently stirred
20min absorbs Adsorption of Cu/Cu2O composite nanoparticle, forms complex therewith；It is centrifuged again, is dried in vacuo to obtain Cu/Cu2O is multiple
Close nano-powder；The NaHB4With the CuSO of step (2)4·5H2The molar ratio of O is 1~2:1；
(4) Cu/Cu made from above-mentioned steps (3) is weighed2Waterglass is added in O composite nano powder, mixes well, and is made antifouling anti-
Algae agent is added in polyolefins plastic masterbatch, and high temperature melting pulls into filament, works out networking to get good antifouling to having
The mesh sheet of anti-algae performance；The waterglass and Cu/Cu2The quality proportioning of O composite nano powder is 0.01~0.2:1.
2. a kind of preparation method of composite Nano algicide-antifoulant according to claim 1, it is characterised in that the step
Suddenly polyethylene glycol and CuSO in (1)4·5H2The mol ratio of O is 0.05:1；N in 40% hydrazine hydrate solution2H4·H2O with
CuSO4·5H2The molar ratio of O is 1.5:1.
3. a kind of preparation method of composite Nano algicide-antifoulant according to claim 1, it is characterised in that the step
Suddenly neopelex and CuSO in (2)4·5H2O、Cu2The mol ratio of O suspension is 0.1:2:1.
4. a kind of preparation method of composite Nano algicide-antifoulant according to claim 1, it is characterised in that the step
Suddenly the NaHB in (3)4With the CuSO of step (2)4·5H2The molar ratio of O is 1.5:1.
5. a kind of preparation method of composite Nano algicide-antifoulant according to claim 1, it is characterised in that the step
Suddenly waterglass and Cu/Cu in (4)2The quality proportioning of O composite nano powder is 0.1:1.
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