CN105850992A - Nano silicon dioxide grafted organic functional polymer macrolide insecticide slow-release agent and preparation method thereof - Google Patents
Nano silicon dioxide grafted organic functional polymer macrolide insecticide slow-release agent and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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Abstract
The application relates to a nano silicon dioxide grafted organic functional polymer macrolide insecticide slow-release agent and a preparation method thereof, and limits the insecticide as one of or any combination of more of abamectin and spinetoram. The preparation method comprises: firstly, preparing hollow nano silicon dioxide A, then preparing amino modified hollow nano silicon dioxide B from the hollow nano silicon dioxide A together with an amino silane coupling agent, then preparing C from the amino modified hollow nano silicon dioxide B together with water, an unsaturated monomer compound, an initiator, a catalyst and a surfactant, and preparing an insecticide nano slow-release agent from C together with an insecticide. The preparation method provided by the invention is low in cost, mild in reaction condition and low in energy consumption, and avoids emission of three wastes; and the obtained product is high in load rate and good in environmental compatibility, and has a relatively long lasting period, the problem of burst release of pesticides in certain carriers is solved, the times of pesticide application is reduced, and the utilization ratio of the pesticides is improved.
Description
Technical field
The present invention relates to a kind of nano silicon and be grafted organic functional polymer macrolide insecticide slow releasing agent and preparation method thereof, belong to parasite killing
The technical field of agent novel form.
Background technology
2014, the chemical pesticide volume of production of China reached 3,700,000 tons, and usage amount is close to 2,000,000 tons.Pesticide a large amount of using with poor efficiency for a long time (has
Effect utilization rate only has 10%-30%, and its turnover rate is up to 70%-90%), make the pesticide in the veterinary antibiotics of China, grain and soil, water body
Residual exceeds standard, and not only non-target organism and health is constituted serious threat, result also in the destruction of the 26S Proteasome Structure and Function of ecosystem.
At present, the pesticidal preparations of China's production and use is based on the conventional pesticide dosage form such as cream, wettable powder.There is a large amount of use in these dosage forms
The limitation such as organic solvent, dust drift, bad dispersibility, and do not possess the control releasability of active component, cause pesticide at target body or target
By fast hydrolyzing, photodissociation or microbial metabolism in neighbouring environment so that it is concentration is down to below valid density, it is difficult to play drug effect.Study table
Bright, Traditional Agricultural pharmaceutically dosage form is processed into slow releasing agent and can extend the lasting period of pesticide, reach to reduce the purpose of spraying times, thus increase economic efficiency,
Alleviate the pesticide harmful effect to environment.Therefore, using modern frontier science and technology means, the formulations of pesticide process technology that development is advanced, improving pesticide has
Effect utilization rate, reduces its injected volume in non-targeting regions and environment and residual contamination, for alleviating the current pesticide residues of China and environmental pollution,
Ensure national food, food and ecological safety, promote that the sustainable development of pesticide industry is significant.
In recent years, nano material research in terms of the drug controlled release of medical domain achieves significant progress, is widely used in gene, egg
The transport of white and antitumor drug etc. so that it is can slowly discharge, fixed-point drug releasing, reaches long-acting, the purpose of targeted therapy.In pesticide field, profit
Develop nano pesticide novel form with nanometer material and technology, have become as one of study hotspot of international nanometer agriculture field.Due to pesticide nano slow release
Agent has lasting period length, to the environment user advantage such as safely, therefore, develop pesticide nano slow releasing agent and be not only able to reduce pesticide to environment, non-target
The biological harm with the mankind of mark, and agriculture production benefit can be improved.
Summary of the invention
In the prior art, a large amount of and poor efficiency uses (effective rate of utilization only has 10%-30%, and its turnover rate is up to 70%-90%) pesticide, brings
Veterinary antibiotics, grain and soil, pesticide residues in water body exceed standard, the beneficial insect in harm ecological environment, birds safety, also affect simultaneously
The safety such as the food of human society, water source.
In order to solve the problems referred to above, the present invention provides a kind of nano silicon to be grafted organic functional polymer macrolide insecticide slow releasing agent.
The present invention also provides for a kind of nano silicon and is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation method thereof.
Nano silicon provided by the present invention is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation method thereof, specifically includes
Following steps:
(1) adding nano-calcium carbonate, cetyl trimethylammonium bromide (CTAB) and ethanol to flask, ultrasonic disperse adds ammonia after half an hour,
Opening stirring, water-bath control reaction temperature, at 25-50 DEG C, adds tetraethyl orthosilicate to above-mentioned reaction system, reacts 24-72h；
(2) add excess dilute hydrochloric acid, remove nano-calcium carbonate template, the centrifugal supernatant that goes, washing gained solid, in triplicate, obtain hollow
Nano silicon A；
(3) adding gained hollow Nano silicon dioxide A in water and ethanol, step (2) in there-necked flask, ultrasonic disperse controls anti-after half an hour
Answer temperature at 25-70 DEG C, drip amino silicane coupling agent, reaction, the centrifugal supernatant that goes, washing gained solid, in triplicate, obtain amino and change
Property hollow Nano silicon dioxide B；
(4) add amino modified for gained hollow Nano silicon dioxide B, water, unsaturated monomer compound, initiator, catalyst in flask
And surfactant, under nitrogen protective condition, under room temperature, react 2-4h, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain product C；
(5) in flask, add product C and insecticide acetone soln, stirring, be centrifuged and go supernatant to obtain insecticide nano slow release agent；
Wherein, in step (1), nano-calcium carbonate particle diameter is 200-500nm, and nano-calcium carbonate consumption accounts for described reaction system mass percent
For 0.5%-2%, preferred mass percentage ratio is that to account for described reaction system mass percent be 0.01%-2%, preferably matter to 0.8%-1.5%, CTAB consumption
Amount percentage ratio be the volume ratio of 0.1%-1%, 27wt% ammonia and ethanol be 1.0:(4.0-10.0), be preferably in a proportion of 1.0:(5.0-8.0)；Described ammonia
The concentration of water is 27wt%.
Wherein, in step (1) and (3), the molar ratio of tetraethyl orthosilicate and amino silicane coupling agent is 1.0:(0.5-2.0), preferred proportion
For 1.0:(0.6-1.2).
Described amino silicane coupling agent is (CH3O)3Si(CH2)3NH2、(CH3CH2O)3Si(CH2)3NH2、(CH3O)3Si(CH2)4NH2、
(CH3CH2O)3Si(CH2)4NH2、(CH3CH2O)3Si(CH2)3NHCH2NH2、(CH3CH2O)2CH3Si(CH2)3NH2、
(CH3O)3Si(CH2)3NH(CH2)2NH2(CH3CH2O)3Si(CH2)3NH(CH2)2NH2In one or more combination in any.
The volume ratio of the water described in step (3) and ethanol is 1:1；Response time is not less than 2 hours.
Wherein, in step (1) and (4), the molar ratio of tetraethyl orthosilicate and unsaturated monomer compound is 1.0:(0.8-3.0), preferably than
Example is 1.0:(1.0-2.0).
Wherein, in step (4), it is 0.01%-8% that the consumption of described initiator accounts for described reaction system mass percent, preferred mass percentage ratio
For 0.05%-0.5%.
It is 0.001%-4% that the consumption of described catalyst accounts for described reaction system mass percent, and preferred mass percentage ratio is 0.005%-2%.
It is 0.1%-8% that the consumption of described surfactant accounts for described copolymerization system mass percent, and preferred mass percentage ratio is 0.2%-4%.
Described unsaturated monomer compound is acrylamide, methacrylic acid, acrylic acid methyl ester., ethyl acrylate, butyl acrylate, metering system
Acid methyl ester, ethyl methacrylate, butyl methacrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, glycidyl acrylate, methyl-prop
One or more combination in any in olefin(e) acid hydroxyl ethyl ester, Hydroxypropyl methacrylate, glycidyl methacrylate and N-[2-(2-methyl-4-oxopentyl).
Described catalyst is the one or in ethylenediamine, propane diamine, 1,4-butanediamine and tetramethylethylenediamine, phosphine nitrile alkali and 4-butyl ammonium hydrogen sulfate
Plant any of the above combination.
Described initiator is hydrogen peroxide, Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, sodium sulfite, benzoyl peroxide, peroxidating diisopropyl
One or more combination in any in benzene, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) and tert-butyl hydroperoxide.
Described surfactant is polyoxyethylene 20 sorbitan monolaurate, anhydrous sorbitol lauric acid monoester, NPE, pungent
One or more combination in any in base phenol polyethenoxy ether, dodecylbenzene sodium sulfonate, calcium dodecyl benzene sulfonate.
Wherein, in step (5), described insecticide is one or more combination in any in dimension rhzomorph and ethyl pleocidin.
The load factor of the macrolide insecticide slow releasing agent that the present invention provides is 66.8%-77.9%, and slow-release period reaches 35-47 days.
Beneficial effects of the present invention: the preparation method of the present invention, low cost, reaction condition is gentle, and power consumption is few, three-waste free discharge；Products obtained therefrom is born
Load rate is high, and Environmental compatibility is good, has the longer lasting period, solves some carrier Pesticides and dashes forward the problem released, decreases spraying times, improve
Pesticide utilization rate.
Accompanying drawing explanation
Fig. 1 avermectin nanometer slow releasing agent elution profiles.
Fig. 2 ethyl pleocidin nano slow release agent elution profiles.
Detailed description of the invention
The load factor of gained insecticide nano slow release agent is evaluated by following embodiment the most by the following method:
By 1.0g C (mc) be placed in the flask filling 50mL insecticide acetone soln, centrifugal after stirring 72h, insecticide in detection supernatant
Content.
The sustained release performance of gained insecticide nano slow release agent is evaluated by following embodiment the most by the following method:
1.0g nano slow release agent is placed in the bag filter that molecular cut off is 3500-5000, then bag filter is placed in fill 100mL methanol/
In the D-800LS dissolving-out tester of water (v/v, 30:70) mixed liquor, stir with the speed of 100rpm, be spaced from digestion instrument at different time
Sampling 1.0mL, feed liquor spectrum detection after dilution certain multiple, the 1mL sustained-release liquid of taking-up 1mL methanol/water (v/v, 30:70) mixed liquor is supplied.
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
(1) 1.0g nano-calcium carbonate, 0.5g cetyl trimethylammonium bromide (CTAB) and 104mL ethanol are added to 250mL flask,
Ultrasonic disperse adds 13mL 27wt% ammonia after half an hour, opens stirring, and water-bath control reaction temperature, at 50 DEG C, adds to above-mentioned reaction system
0.02mol tetraethyl orthosilicate, reacts 72h；
(2) add excess dilute hydrochloric acid, remove nano-calcium carbonate template, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain hollow Nano two
Silicon oxide A；
(3) adding gained A in water and ethanol (V/V=1:1) 100mL, step (2) in there-necked flask, ultrasonic disperse controls after half an hour
Reaction temperature, at 70 DEG C, drips 0.01mol (CH3CH2O)2CH3Si(CH2)3NH2, react 2h, be centrifuged and go supernatant to wash gained solid, weight
Multiple three times, obtain amino modified hollow Nano silicon dioxide B；
(4) add gained B, 84.0g water, 0.06mol methyl methacrylate, 0.01g Ammonium persulfate., 1.0g tetramethyl second in flask
Diamidogen and 8.0g NPE, under nitrogen protective condition, react 4h, be centrifuged and go supernatant to wash gained solid, repeat three under room temperature
Secondary, obtain C；
(5) in flask, add C and avilamycin acetone soln, stir 72h, be centrifuged and go supernatant to obtain avermectin nanometer slow releasing agent.
By 1.0g C (mc) be placed in the flask of the avilamycin acetone soln filling 50mL 100000mg/L, centrifugal, by formula after stirring 72h
(1) calculating load factor is 77.9%.
1.0g avermectin nanometer slow releasing agent is placed in the bag filter that molecular cut off is 3500-5000, then bag filter is placed in and fills 100mL
In the D-800LS dissolving-out tester of methanol/water (v/v, 30:70) mixed liquor, stir with the speed of 100rpm, be spaced from dissolution at different time
Instrument samples 1.0mL, the detection of feed liquor spectrum, the 1mL sustained-release liquid of taking-up 1mL methanol/water (v/v, 30:70) mixed liquor after dilution certain multiple
Supply, it follows that the slow releasing agent of avermectin nanometer slow releasing agent is 47 days.
The load factor of avermectin nanometer slow releasing agent prepared by the present embodiment is 77.9%, and slow-release period is 47 days.
Avermectin nanometer slow releasing agent elution profiles is shown in Fig. 1.
Embodiment 2
(1) 1.5g nano-calcium carbonate, 2.0g cetyl trimethylammonium bromide (CTAB) and 99mL ethanol are added to 250mL flask,
Ultrasonic disperse adds 16.5mL 27wt% ammonia after half an hour, opens stirring, and water-bath control reaction temperature, at 40 DEG C, adds to above-mentioned reaction system
Enter 0.02mol tetraethyl orthosilicate, react 36h；
(2) add excess dilute hydrochloric acid, remove nano-calcium carbonate template, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain hollow Nano two
Silicon oxide A；
(3) adding gained A in water and ethanol (V/V=1:1) 100mL, step (2) in there-necked flask, ultrasonic disperse controls after half an hour
Reaction temperature, at 40 DEG C, drips 0.04mol (CH3O)3Si(CH2)3NH2, react 2h, be centrifuged and remove supernatant washing gained solid, in triplicate,
Obtain amino modified hollow Nano silicon dioxide B；
(4) add gained B, 89.0g water, 0.016mol glycidyl acrylate, 4.0g tert-butyl hydroperoxide, 4.0g in flask
Ethylenediamine and 0.1g polyoxyethylene 20 sorbitan monolaurate, under nitrogen protective condition, react 2h, be centrifuged and go supernatant to wash institute under room temperature
Obtain solid, in triplicate, obtain C；
(5) in flask, add C and ethyl pleocidin acetone soln, stir 72h, be centrifuged and go supernatant to obtain ethyl pleocidin nano slow release agent.
The load factor of ethyl pleocidin nano slow release agent and the calculating of slow-release period are with reference to embodiment 1.
The load factor of ethyl pleocidin nano slow release agent prepared by the present embodiment is 66.8%, and slow-release period is 35 days.
Embodiment 3
(1) 1.5g nano-calcium carbonate, 0.05g cetyl trimethylammonium bromide (CTAB) and 94mL ethanol are added to 250mL flask,
Ultrasonic disperse adds 23.5mL 27wt% ammonia after half an hour, opens stirring, and water-bath control reaction temperature, at 25 DEG C, adds to above-mentioned reaction system
Enter 0.02mol tetraethyl orthosilicate, react 72h；
(2) add excess dilute hydrochloric acid, remove nano-calcium carbonate template, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain hollow Nano two
Silicon oxide A；
(3) adding gained A in water and ethanol (V/V=1:1) 100mL, step (2) in there-necked flask, ultrasonic disperse controls after half an hour
Reaction temperature, at 50 DEG C, drips 0.03mol (CH3CH2O)2CH3Si(CH2)3NH2, react 2h, be centrifuged and go supernatant to wash gained solid, weight
Multiple three times, obtain amino modified hollow Nano silicon dioxide B；
(4) add gained B, 90.0g water, 0.05mol methyl methacrylate, 0.05g Ammonium persulfate., 0.05g 1,4-fourth two in flask
Amine and 4.0g anhydrous sorbitol lauric acid monoester, under nitrogen protective condition, react 4h, be centrifuged and go supernatant to wash gained solid, repeat under room temperature
Three times, obtain C；
(5) in flask, add C and avilamycin acetone soln, stir 72h, be centrifuged and go supernatant to obtain avermectin nanometer slow releasing agent.
The load factor of avermectin nanometer slow releasing agent and the calculating of slow-release period are with reference to embodiment 1.
The load factor of avermectin nanometer slow releasing agent prepared by the present embodiment is 67.1%, and slow-release period is 35 days.
Embodiment 4
(1) 0.5g nano-calcium carbonate, 1.5g cetyl trimethylammonium bromide (CTAB) and 99mL ethanol are added to 250mL flask,
Ultrasonic disperse adds 16.5mL 27wt% ammonia after half an hour, opens stirring, and water-bath control reaction temperature, at 30 DEG C, adds to above-mentioned reaction system
Enter 0.02mol tetraethyl orthosilicate, react 36h；
(2) add excess dilute hydrochloric acid, remove nano-calcium carbonate template, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain hollow Nano two
Silicon oxide A；
(3) adding gained A in water and ethanol (V/V=1:1) 100mL, step (2) in there-necked flask, ultrasonic disperse controls after half an hour
Reaction temperature, at 25 DEG C, drips 0.04mol (CH3O)3Si(CH2)3NH2, react 2h, be centrifuged and remove supernatant washing gained solid, in triplicate,
Obtain amino modified hollow Nano silicon dioxide B；
(4) add gained B, 90.0g water, 0.03mol glycidyl acrylate, 2.0g sodium peroxydisulfate, 4.0g propane diamine in flask
With 0.1g OPEO, under nitrogen protective condition, under room temperature, react 2h, be centrifuged and remove supernatant washing gained solid, in triplicate,
Obtain C；
(5) in flask, add C and ethyl pleocidin acetone soln, stir 72h, be centrifuged and go supernatant to obtain ethyl pleocidin nano slow release agent.
The load factor of ethyl pleocidin nano slow release agent and the calculating of slow-release period are with reference to embodiment 1.
The load factor of ethyl pleocidin nano slow release agent prepared by the present embodiment is 69.5%, and slow-release period is 37 days.
Comparative example
With the determination of test method slow-release period identical with in embodiment 1, there is a tests below result:
The Liang Xudong of Beijing University of Chemical Technology uses many empty nano silicon load Medibens and Prochloraz, and drug loading rate has respectively reached 50.8% He
51.9%, slow-release period was less than 2 days (Liang Xudong, Beijing University of Chemical Technology's master thesis, 2008).Spring in the summer Seedling of University of Anhui utilizes miniemulsion circle
Face polymerization is prepared for cypermethrin Nano capsule, load factor be 61.2% (Xia Chunmiao, University of Anhui's master thesis, 2012).Henan Agriculture
The Qin Xingmin of university with Lauxite, Polyethylene Glycol (PEG6000), beta-schardinger dextrin-as material, be prepared for respectively 20% chlopyrifos microcapsule suspending agent,
Chlopyrifos-PEG6000 solid dispersion, three kinds of carried medicine sustained-release preparations of chlopyrifos-Benexate Hydrochloride, drug loading rate all less than 5%, slow-release period
Less than 26 days (Qin Xingmin, Agricultural University Of He'nan's master thesis, 2014).The Jiang Jianfang of the Chinese Academy of Agricultural Sciences is prepared for jingganmycin sea
Calcium alginate Nano capsule, drug loading rate is up to 62.64%, slow-release period be 8 days (Jiang Jianfang, Chinese Academy of Agricultural Sciences Ph.D. Dissertation, 2014).
The Yang Qian of Southwest University is prepared for Tebuconazole calcium silicates Nano capsule slow releasing agent, and drug loading rate is 62.8%, and slow-release period was less than 10 days (Yang Qian, west
South university master thesis, 2015).
Claims (8)
1. a nano silicon is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation method thereof, it is characterised in that described parasite killing
Agent is one or more combination in any in avilamycin, ethyl pleocidin, follows the steps below:
(1) adding nano-calcium carbonate, cetyl trimethylammonium bromide (CTAB) and ethanol to flask, ultrasonic disperse adds ammonia after half an hour,
Opening stirring, water-bath control reaction temperature, at 25-50 DEG C, adds tetraethyl orthosilicate to above-mentioned reaction system, reacts 24-72h；
(2) add excess dilute hydrochloric acid, remove nano-calcium carbonate template, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain hollow Nano two
Silicon oxide A；
(3) adding gained A in water and ethanol, step (2) in there-necked flask, ultrasonic disperse controls reaction temperature at 25-70 DEG C after half an hour,
Dropping amino silicane coupling agent, reaction, it is centrifuged and goes supernatant to wash gained solid, in triplicate, obtain amino modified hollow Nano silicon dioxide B；
(4) add amino modified for gained hollow Nano silicon dioxide B, water, unsaturated monomer compound, initiator, catalyst in flask
And surfactant, under nitrogen protective condition, under room temperature, react 2-4h, be centrifuged and go supernatant to wash gained solid, in triplicate, obtain C；
(5) in flask, add C and the acetone soln of insecticide, stirring, be centrifuged and go supernatant to obtain insecticide nano slow release agent.
Nano silicon the most according to claim 1 is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation method thereof, its
Being characterised by: in step (1), nano-calcium carbonate particle diameter is 200-500nm, and nano-calcium carbonate consumption accounts for described reaction system mass percent and is
It is 1.0:(4.0-10.0 that 0.5%-2%, CTAB consumption accounts for the volume ratio that described reaction system mass percent is 0.01%-2%, ammonia and ethanol)；
The concentration of described ammonia is 27wt%.
3. it is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation side thereof according to the arbitrary described nano silicon of claim 1-2
Method, it is characterised in that: the molar ratio of the amino silicane coupling agent in the tetraethyl orthosilicate of step (1) and step (3) is 1.0:(0.5-2.0)；
Described amino silicane coupling agent is (CH3O)3Si(CH2)3NH2、(CH3CH2O)3Si(CH2)3NH2、(CH3O)3Si(CH2)4NH2、
(CH3CH2O)3Si(CH2)4NH2、(CH3CH2O)3Si(CH2)3NHCH2NH2、(CH3CH2O)2CH3Si(CH2)3NH2、
(CH3O)3Si(CH2)3NH(CH2)2NH2(CH3CH2O)3Si(CH2)3NH(CH2)2NH2In one or more combination in any；
The volume ratio of the water described in step (3) and ethanol is 1:1；Response time is not less than 2 hours.
4. it is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation side thereof according to the arbitrary described nano silicon of claim 1-3
Method, it is characterised in that: the molar ratio of the tetraethyl orthosilicate in step (1) and the unsaturated monomer compound in step (4) is 1.0:(0.8-3.0)；
In step (4), it is 0.01%-8% that the consumption of described initiator accounts for described reaction system mass percent；
It is 0.001%-4% that the consumption of described catalyst accounts for described reaction system mass percent；
It is 0.1%-8% that the consumption of described surfactant accounts for described copolymerization system mass percent.
5. it is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation side thereof according to the arbitrary described nano silicon of claim 1-4
Method, it is characterised in that: described unsaturated monomer compound is acrylamide, methacrylic acid, acrylic acid methyl ester., ethyl acrylate, acrylic acid fourth
Ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, acrylic acid shrink sweet
One in grease, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, glycidyl methacrylate and N-[2-(2-methyl-4-oxopentyl) or one
Any of the above combines；
Described catalyst be the one in ethylenediamine, propane diamine, 1,4-butanediamine and tetramethylethylenediamine, phosphine nitrile alkali and 4-butyl ammonium hydrogen sulfate or one with
Upper combination in any；
Described initiator be hydrogen peroxide, Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, sodium sulfite, benzoyl peroxide, cumyl peroxide,
One or more combination in any in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) and tert-butyl hydroperoxide；
Described surfactant is polyoxyethylene 20 sorbitan monolaurate, anhydrous sorbitol lauric acid monoester, NPE, octyl phenol
One or more combination in any in polyoxyethylene ether, dodecylbenzene sodium sulfonate, calcium dodecyl benzene sulfonate.
Nano silicon the most according to claim 1 is grafted organic functional polymer macrolide insecticide slow releasing agent and preparation method thereof, its
It is characterised by: described mixing time is for not less than 48 hours.
7. the nano silicon that prepared by the method according to any one of claim 1-6 is grafted organic functional polymer macrolide insecticide slow releasing agent.
Nano silicon the most according to claim 7 is grafted organic functional polymer macrolide insecticide slow releasing agent, it is characterised in that: institute
The load factor stating macrolide insecticide slow releasing agent is 66.8%-77.9%, and slow-release period is 35-47 days.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107251896A (en) * | 2017-07-18 | 2017-10-17 | 华中农业大学 | A kind of enzyme response desinsection sustained release agent and preparation method thereof |
| CN108642869A (en) * | 2018-04-12 | 2018-10-12 | 华南理工大学 | A kind of preparation method of super-hydrophobic anti-UV fabric |
| CN108703958A (en) * | 2018-08-11 | 2018-10-26 | 西华大学 | A method of collaboration streptonigrin prepares anti-tumor nano composition of medicine |
| CN113016791A (en) * | 2021-03-26 | 2021-06-25 | 扬州大学 | Preparation method of avermectin-loaded mesoporous silica nanoparticle controlled release agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210302A (en) * | 2011-04-13 | 2011-10-12 | 华南理工大学 | Porous inorganic material with insecticidal and mothproof function and preparation method thereof |
| WO2014017981A1 (en) * | 2012-07-25 | 2014-01-30 | Agency For Science, Technology And Research | Stimuli-responsive interpolymer complex coated hollow silica vesicles |
| CN104521955A (en) * | 2014-12-14 | 2015-04-22 | 仲恺农业工程学院 | Pesticide microcapsule and preparation method thereof |
| WO2015195053A1 (en) * | 2014-06-20 | 2015-12-23 | Agency For Science, Technology And Research | Stimulus-responsive core-shell particles |
-
2016
- 2016-03-30 CN CN201610191303.5A patent/CN105850992B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102210302A (en) * | 2011-04-13 | 2011-10-12 | 华南理工大学 | Porous inorganic material with insecticidal and mothproof function and preparation method thereof |
| WO2014017981A1 (en) * | 2012-07-25 | 2014-01-30 | Agency For Science, Technology And Research | Stimuli-responsive interpolymer complex coated hollow silica vesicles |
| WO2015195053A1 (en) * | 2014-06-20 | 2015-12-23 | Agency For Science, Technology And Research | Stimulus-responsive core-shell particles |
| CN104521955A (en) * | 2014-12-14 | 2015-04-22 | 仲恺农业工程学院 | Pesticide microcapsule and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI YUAN 等: "Preparation of pH-Responsive Mesoporous Silica Nanoparticles and Their Application in Controlled Drug Delivery", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107251896A (en) * | 2017-07-18 | 2017-10-17 | 华中农业大学 | A kind of enzyme response desinsection sustained release agent and preparation method thereof |
| CN108642869A (en) * | 2018-04-12 | 2018-10-12 | 华南理工大学 | A kind of preparation method of super-hydrophobic anti-UV fabric |
| CN108642869B (en) * | 2018-04-12 | 2020-08-18 | 华南理工大学 | Preparation method of super-hydrophobic anti-ultraviolet fabric |
| CN108703958A (en) * | 2018-08-11 | 2018-10-26 | 西华大学 | A method of collaboration streptonigrin prepares anti-tumor nano composition of medicine |
| CN108703958B (en) * | 2018-08-11 | 2021-02-23 | 西华大学 | Method for preparing anti-tumor nano combined medicine by cooperating with streptonigrin |
| CN113016791A (en) * | 2021-03-26 | 2021-06-25 | 扬州大学 | Preparation method of avermectin-loaded mesoporous silica nanoparticle controlled release agent |
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