CN105850992B - Nano silica is grafted organic functional polymer macrolide insecticide sustained release agent and preparation method thereof - Google Patents
Nano silica is grafted organic functional polymer macrolide insecticide sustained 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
- A01N25/10—Macromolecular compounds
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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
- A01N43/02—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
- A01N43/22—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 rings with more than six members
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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
This application involves a kind of nano silicas to be grafted organic functional polymer macrolide insecticide sustained release agent and preparation method thereof, and limits the insecticide as one of avermectin, ethyl pleocidin or more than one any combination.The preparation method includes: to prepare hollow Nano silica A first, amino modified hollow Nano silica B is prepared with amino silicane coupling agent again, and then C is prepared with water, unsaturated monomer compound, initiator, catalyst and surfactant, then insecticide nano slow release agent is prepared with insecticide.Preparation method of the invention, at low cost, reaction condition is mild, and energy consumption is few, three-waste free discharge；Products obtained therefrom load factor is high, and Environmental compatibility is good, has the longer lasting period, solves the problems, such as that pesticide is released in certain carriers, is reduced spraying times, is improved pesticide utilization rate.
Description
Technical field
The present invention relates to a kind of nano silica be grafted organic functional polymer macrolide insecticide sustained release agent and
Preparation method belongs to the technical field of insecticide novel form.
Background technique
2014, the chemical pesticide output in China reached 3,700,000 tons, and usage amount is close to 2,000,000 tons.Pesticide is big for a long time
Amount and inefficient application (effective rate of utilization only has 10%-30%, and turnover rate is up to 70%-90%), make vegetables, the water in China
Excessive pesticide residues in fruit, grain and soil, water body not only constitute serious prestige to non-target organism and human health
The side of body, also results in the destruction of the structure and function of the ecosystem.
Currently, China's production and the pesticidal preparations used are based on the conventional pesticides dosage form such as missible oil, wettable powder.These
Dosage form exists largely using limitations such as organic solvent, dust drift, bad dispersibilities, and does not have the control release of active constituent
Ability causes pesticide in the environment near target body or target by fast hydrolyzing, photodissociation or microbial metabolism, drops its concentration
To effective concentration, it is difficult to play drug effect.Existing research shows that traditional formulations of pesticide, which are processed into sustained release agent, can extend agriculture
The lasting period of medicine achievees the purpose that reduce spraying times, to increase economic efficiency, mitigates adverse effect of the pesticide to environment.
Therefore, with modern frontier science and technology means, develop advanced formulations of pesticide processing technology, improve pesticide efficacy, reduce
Its injected volume and residual contamination in non-target region and environment, it is dirty for alleviating the current pesticide residue in China and environment
Dye ensures national food, food and ecological safety, and the sustainable development of pesticide industry is promoted to be of great significance.
In recent years, research of the nano material in terms of the drug controlled release of medical domain achieves significant progress, quilt
Be widely used in the transport of gene, albumen and anti-tumor drug etc., can slow release, fixed-point drug releasing, reach long-acting, target
To the purpose for the treatment of.In pesticide field, develops nano pesticide novel form using nanometer material and technology, have become international nanometer
One of research hotspot of agriculture field.Since pesticide nano sustained release agent has many advantages, such as that the lasting period is long, safe to environment user,
Therefore, it develops pesticide nano sustained release agent and is not only able to reduce pesticide to environment, non-target organism and the harm of the mankind, and can
Improve agriculture production benefit.
Summary of the invention
In the prior art, largely (effective rate of utilization only has 10%-30%, and turnover rate is up to 70%- with inefficient application
90%) pesticide, the excessive pesticide residues in bring veterinary antibiotics, grain and soil, water body, endangers in ecological environment
Beneficial insect, birds safety, while the safety such as food, water source for also influencing human society.
To solve the above-mentioned problems, the present invention provides a kind of nano silica grafting organic functional polymer macrolide
Insecticides sustained release agent.
The present invention also provides a kind of nano silicas to be grafted organic functional polymer macrolide insecticide sustained release agent
And preparation method thereof.
Nano silica provided by the present invention be grafted organic functional polymer macrolide insecticide sustained release agent and
Preparation method specifically comprises the following steps:
(1) small to flask addition nanometer calcium carbonate, cetyl trimethylammonium bromide (CTAB) and ethyl alcohol, ultrasonic disperse half
When after be added ammonium hydroxide, open stirring, water-bath controls reaction temperature at 25-50 DEG C, ethyl orthosilicate is added to above-mentioned reaction system,
React 24-72h；
(2) excessive dilute hydrochloric acid is added, removes nanometer calcium carbonate template, supernatant is removed in centrifugation, washs obtained solid, repeats three
It is secondary, obtain hollow Nano silica A；
(3) gained hollow Nano silica A in water and ethyl alcohol, step (2), ultrasonic disperse half are added into three-necked flask
Amino silicane coupling agent, reaction is added dropwise at 25-70 DEG C in control reaction temperature after hour, and supernatant is removed in centrifugation, and washing gained is solid
Body obtains amino modified hollow Nano silica B in triplicate；
(4) it is added the amino modified hollow Nano silica B of gained, water, unsaturated monomer compound, draws into flask
Agent, catalyst and surfactant are sent out, under the conditions of nitrogen protection, reacts 2-4h at room temperature, centrifugation goes supernatant washing gained solid
Body obtains product C in triplicate；
(5) product C and insecticide acetone soln, stirring are added into flask, centrifugation goes supernatant to obtain insecticide nano controlled-release
Agent；
Wherein, in step (1), nanometer calcium carbonate partial size is 200-500nm, and nanometer calcium carbonate dosage accounts for the reactant
It is mass percent for 0.5%-2%, preferred mass percentage is 0.8%-1.5%, and CTAB dosage accounts for the reaction system matter
Amount percentage is 0.01%-2%, and preferred mass percentage is 0.1%-1%, and the volume ratio of 27wt% ammonium hydroxide and ethyl alcohol is 1.0:
(4.0-10.0), is preferably in a proportion of 1.0:(5.0-8.0)；The concentration of the ammonium hydroxide is 27wt%.
Wherein, in step (1) and (3), the molar ratio of ethyl orthosilicate and amino silicane coupling agent is 1.0:(0.5-
2.0), it is preferably in a proportion of 1.0:(0.6-1.2).
The 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)2NH2One of or more than one any group
It closes.
The volume ratio of water described in step (3) and ethyl alcohol is 1:1；Reaction time is not less than 2 hours.
Wherein, in step (1) and (4), the molar ratio of ethyl orthosilicate and unsaturated monomer compound is 1.0:
(0.8-3.0), is preferably in a proportion of 1.0:(1.0-2.0).
Wherein, in step (4), it is 0.01%- that the dosage of the initiator, which accounts for the reaction system mass percent,
8%, preferred mass percentage is 0.05%-0.5%.
It is 0.001%-4%, preferred mass percentage that the dosage of the catalyst, which accounts for the reaction system mass percent,
For 0.005%-2%.
It is 0.1%-8%, preferred mass that the dosage of the surfactant, which accounts for the copolymerization system mass percent,
Percentage is 0.2%-4%.
The unsaturated monomer compound is acrylamide, methacrylic acid, methyl acrylate, ethyl acrylate, propylene
Acid butyl ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxy-ethyl acrylate, acrylic acid hydroxypropyl
Ester, glycidyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, glycidyl methacrylate and
One of Diacetone Acrylamide or more than one any combination.
The catalyst is ethylenediamine, propane diamine, 1,4- butanediamine and tetramethylethylenediamine, phosphine nitrile alkali and tetrabutyl sulfuric acid
One of hydrogen ammonium or more than one any combination.
The initiator is hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sodium hydrogensulfite, benzoyl peroxide first
One of acyl, cumyl peroxide, azodiisobutyronitrile, azobisisoheptonitrile and tert-butyl hydroperoxide or more than one
Any combination.
The surfactant is polyoxyethylene 20 sorbitan monolaurate, anhydrous sorbitol lauric acid monoester, nonyl
One of base phenol polyethenoxy ether, octyl phenol polyoxyethylene ether, neopelex, calcium dodecyl benzene sulfonate or one
Kind any of the above combination.
Wherein, in step (5), the insecticide be dimension one of rhzomorph and ethyl pleocidin or more than one
Meaning combination.
The load factor of macrolide insecticide sustained release agent provided by the invention is 66.8%-77.9%, and the sustained release phase reaches 35-
47 days.
Beneficial effects of the present invention: preparation method of the invention, at low cost, reaction condition is mild, and energy consumption is few, no three wastes row
It puts；Products obtained therefrom load factor is high, and Environmental compatibility is good, has the longer lasting period, solves what pesticide in certain carriers was released
Problem reduces spraying times, improves pesticide utilization rate.
Detailed description of the invention
Fig. 1 avermectin nanometer sustained release agent elution profiles.
Fig. 2 ethyl pleocidin nano slow release agent elution profiles.
Specific embodiment
Following embodiments by the following method evaluate the load factor of gained insecticide nano slow release agent:
By 1.0g C (mc) be placed in the flask for filling 50mL insecticide acetone soln, it is centrifuged after stirring 72h, detects supernatant
The content of insecticide in liquid.
Following embodiments by the following method evaluate the sustained release performance of gained insecticide nano slow release agent:
1.0g nano slow release agent is placed in the bag filter that molecular cut off is 3500-5000, is then placed in bag filter
In the D-800LS dissolving-out tester for filling 100mL methanol/water (v/v, 30:70) mixed liquor, stirred with the speed of 100rpm,
Different time intervals sample 1.0mL from digestion instrument, dilute feed liquor spectrum detection after certain multiple, the 1mL sustained-release liquid 1mL of taking-up
Methanol/water (v/v, 30:70) mixed liquor is supplied.
The present invention will be further described combined with specific embodiments below.
Embodiment 1
(1) to 250mL flask be added 1.0g nanometer calcium carbonate, 0.5g cetyl trimethylammonium bromide (CTAB) and
13mL 27wt% ammonium hydroxide is added in 104mL ethyl alcohol after ultrasonic disperse half an hour, open stirring, and water-bath controls reaction temperature 50
DEG C, 0.02mol ethyl orthosilicate is added to above-mentioned reaction system, reacts 72h；
(2) excessive dilute hydrochloric acid is added, removes nanometer calcium carbonate template, centrifugation goes supernatant to wash obtained solid, in triplicate,
Obtain hollow nano silica A；
(3) gained A in water and ethyl alcohol (V/V=1:1) 100mL, step (2), ultrasonic disperse half are added into three-necked flask
0.01mol (CH is added dropwise at 70 DEG C in control reaction temperature after hour3CH2O)2CH3Si(CH2)3NH2, 2h is reacted, supernatant is removed in centrifugation
Washing obtained solid obtains amino modified hollow Nano silica B in triplicate；
(4) into flask be added by gained B, 84.0g water, 0.06mol methyl methacrylate, 0.01g ammonium persulfate,
1.0g tetramethylethylenediamine and 8.0g nonylphenol polyoxyethylene ether react 4h under the conditions of nitrogen protection at room temperature, and centrifugation is gone
Obtained solid is washed in cleaning, in triplicate, obtains C；
(5) C and avermectin acetone soln are added into flask, stirs 72h, it is slow that centrifugation goes supernatant to obtain avermectin nanometer
Release agent.
By 1.0g C (mc) be placed in the flask for the avermectin acetone soln for filling 50mL 100000mg/L, stir 72h
After be centrifuged, by formula (1) calculate load factor be 77.9%.
1.0g avermectin nanometer sustained release agent is placed in the bag filter that molecular cut off is 3500-5000, it then will be saturating
Analysis bag is placed in the D-800LS dissolving-out tester for filling 100mL methanol/water (v/v, 30:70) mixed liquor, with the speed of 100rpm
Stirring samples 1.0mL in different time intervals from digestion instrument, dilutes feed liquor spectrum detection after certain multiple, the 1mL sustained release of taking-up
Liquid is supplied with 1mL methanol/water (v/v, 30:70) mixed liquor, it follows that the sustained release agent of avermectin nanometer sustained release agent is 47 days.
The load factor of avermectin nanometer sustained release agent manufactured in the present embodiment is 77.9%, and the sustained release phase is 47 days.
Avermectin nanometer sustained release agent elution profiles are shown in Fig. 1.
Embodiment 2
(1) 1.5g nanometer calcium carbonate, 2.0g cetyl trimethylammonium bromide (CTAB) and 99mL is added to 250mL flask
Ethyl alcohol, after ultrasonic disperse half an hour be added 16.5mL 27wt% ammonium hydroxide, open stirring, water-bath control reaction temperature at 40 DEG C, to
0.02mol ethyl orthosilicate is added in above-mentioned reaction system, reacts 36h；
(2) excessive dilute hydrochloric acid is added, removes nanometer calcium carbonate template, centrifugation goes supernatant to wash obtained solid, in triplicate,
Obtain hollow nano silica A；
(3) gained A in water and ethyl alcohol (V/V=1:1) 100mL, step (2), ultrasonic disperse half are added into three-necked flask
0.04mol (CH is added dropwise at 40 DEG C in control reaction temperature after hour3O)3Si(CH2)3NH2, 2h is reacted, centrifugation goes supernatant to wash institute
It obtains solid and obtains amino modified hollow Nano silica B in triplicate；
(4) it is added into flask by gained B, 89.0g water, 0.016mol glycidyl acrylate, 4.0g tert-butyl mistake
Hydrogen oxide, 4.0g ethylenediamine and 0.1g polyoxyethylene 20 sorbitan monolaurate, under the conditions of nitrogen protection, at room temperature instead
2h is answered, centrifugation goes supernatant washing obtained solid to obtain C in triplicate；
(5) C and ethyl pleocidin acetone soln are added into flask, stirs 72h, centrifugation goes supernatant to obtain ethyl mostly sterilization
Plain nano slow release agent.
The load factor of ethyl pleocidin nano slow release agent and the calculating of sustained release phase are referring to embodiment 1.
The load factor of ethyl pleocidin nano slow release agent manufactured in the present embodiment is 66.8%, and the sustained release phase is 35 days.
Embodiment 3
(1) to 250mL flask be added 1.5g nanometer calcium carbonate, 0.05g cetyl trimethylammonium bromide (CTAB) and
23.5mL 27wt% ammonium hydroxide is added in 94mL ethyl alcohol after ultrasonic disperse half an hour, open stirring, and water-bath controls reaction temperature 25
DEG C, 0.02mol ethyl orthosilicate is added to above-mentioned reaction system, reacts 72h；
(2) excessive dilute hydrochloric acid is added, removes nanometer calcium carbonate template, centrifugation goes supernatant to wash obtained solid, in triplicate,
Obtain hollow nano silica A；
(3) gained A in water and ethyl alcohol (V/V=1:1) 100mL, step (2), ultrasonic disperse half are added into three-necked flask
0.03mol (CH is added dropwise at 50 DEG C in control reaction temperature after hour3CH2O)2CH3Si(CH2)3NH2, 2h is reacted, supernatant is removed in centrifugation
Washing obtained solid obtains amino modified hollow Nano silica B in triplicate；
(4) into flask be added by gained B, 90.0g water, 0.05mol methyl methacrylate, 0.05g ammonium persulfate,
0.05g Putriscine and 4.0g anhydrous sorbitol lauric acid monoester react 4h under the conditions of nitrogen protection at room temperature, centrifugation
Supernatant washing obtained solid is gone to obtain C in triplicate；
(5) C and avermectin acetone soln are added into flask, stirs 72h, it is slow that centrifugation goes supernatant to obtain avermectin nanometer
Release agent.
The load factor of avermectin nanometer sustained release agent and the calculating of sustained release phase are referring to embodiment 1.
The load factor of avermectin nanometer sustained release agent manufactured in the present embodiment is 67.1%, and the sustained release phase is 35 days.
Embodiment 4
(1) 0.5g nanometer calcium carbonate, 1.5g cetyl trimethylammonium bromide (CTAB) and 99mL is added to 250mL flask
Ethyl alcohol, after ultrasonic disperse half an hour be added 16.5mL 27wt% ammonium hydroxide, open stirring, water-bath control reaction temperature at 30 DEG C, to
0.02mol ethyl orthosilicate is added in above-mentioned reaction system, reacts 36h；
(2) excessive dilute hydrochloric acid is added, removes nanometer calcium carbonate template, centrifugation goes supernatant to wash obtained solid, in triplicate,
Obtain hollow nano silica A；
(3) gained A in water and ethyl alcohol (V/V=1:1) 100mL, step (2), ultrasonic disperse half are added into three-necked flask
0.04mol (CH is added dropwise at 25 DEG C in control reaction temperature after hour3O)3Si(CH2)3NH2, 2h is reacted, centrifugation goes supernatant to wash institute
It obtains solid and obtains amino modified hollow Nano silica B in triplicate；
(4) into flask be added by gained B, 90.0g water, 0.03mol glycidyl acrylate, 2.0g sodium peroxydisulfate,
4.0g propane diamine and 0.1g octyl phenol polyoxyethylene ether react 2h under the conditions of nitrogen protection at room temperature, and centrifugation goes supernatant to wash
Obtained solid obtains C in triplicate；
(5) C and ethyl pleocidin acetone soln are added into flask, stirs 72h, centrifugation goes supernatant to obtain ethyl mostly sterilization
Plain nano slow release agent.
The load factor of ethyl pleocidin nano slow release agent and the calculating of sustained release phase are referring to embodiment 1.
The load factor of ethyl pleocidin nano slow release agent manufactured in the present embodiment is 69.5%, and the sustained release phase is 37 days.
Comparative example
To measure the sustained release phase with test method identical in embodiment 1, there is following tests result:
The Liang Xudong of Beijing University of Chemical Technology is using more empty nano silica load dicambas and Prochloraz, drug loading rate
50.8% and 51.9% have been respectively reached, has been sustained less than 2 days phase (Liang Xudong, Beijing University of Chemical Technology's master thesis, 2008).
The Xia Chunmiao of University of Anhui is prepared for cypermethrin Nano capsule using miniemulsion interfacial polymerization, and load factor was 61.2% (summer
Spring seedling, University of Anhui's master thesis, 2012).The Qin Xingmin of Agricultural University Of He'nan is with Lauxite, polyethylene glycol
(PEG6000), beta-cyclodextrin is material, is prepared for 20% chlopyrifos microcapsule suspending agent, chlopyrifos-PEG6000 solid point respectively
Three kinds of granular media, chlopyrifos-Benexate Hydrochloride carried medicine sustained-release preparations, for drug loading rate less than 5%, the sustained release phase is no more than 26
Its (Qin Xingmin, Agricultural University Of He'nan's master thesis, 2014).The Jiang Jianfang of the Chinese Academy of Agricultural Sciences is prepared for jinggangmeisu
Calcium alginate Nano capsule, drug loading rate are up to 62.64%, and the sustained release phase is that (Jiang Jianfang, the Chinese Academy of Agricultural Sciences were rich in 8 days
Bachelorship paper, 2014).The Yang Qian of Southwest University is prepared for Tebuconazole calcium silicates Nano capsule sustained release agent, and drug loading rate is
62.8%, it is sustained less than 10 days phase (Yang Qian, Southwest University's master thesis, 2015).
Claims (2)
1. a kind of nano silica is grafted the preparation method of organic functional polymer macrolide insecticide sustained release agent, special
Sign is that the insecticide is one of avermectin, ethyl pleocidin or more than one any combination, according to following step
It is rapid to carry out:
(1) nanometer calcium carbonate, cetyl trimethylammonium bromide (CTAB) and ethyl alcohol is added to flask, after ultrasonic disperse half an hour
Ammonium hydroxide is added, opens stirring, water-bath controls reaction temperature at 25-50 DEG C, ethyl orthosilicate, reaction is added to above-mentioned reaction system
24-72h；
(2) excessive dilute hydrochloric acid is added, removes nanometer calcium carbonate template, centrifugation goes supernatant washing obtained solid to have leisure in triplicate
Heart nano silica A；
(3) gained A in water and ethyl alcohol, step (2) is added into three-necked flask, reaction temperature is controlled after ultrasonic disperse half an hour and is existed
25-70 DEG C, amino silicane coupling agent, reaction is added dropwise, centrifugation goes supernatant washing obtained solid to obtain amino modified sky in triplicate
Heart nano silica B；
(4) it is added the amino modified hollow Nano silica B of gained, water, unsaturated monomer compound, causes into flask
Agent, catalyst and surfactant react 2-4h under the conditions of nitrogen protection at room temperature, and centrifugation goes supernatant to wash obtained solid,
In triplicate, C is obtained；
(5) acetone soln of C and insecticide, stirring are added into flask, centrifugation goes supernatant to obtain insecticide nano slow release agent；
The 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)2NH2One of or more than one any group
It closes；
The unsaturated monomer compound is acrylamide, methacrylic acid, methyl acrylate, ethyl acrylate, acrylic acid fourth
Ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, third
Olefin(e) acid ethylene oxidic ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, glycidyl methacrylate and diacetone
One of acrylamide or more than one any combination；
The catalyst is ethylenediamine, propane diamine, 1,4- butanediamine and tetramethylethylenediamine, phosphine nitrile alkali and 4-butyl ammonium hydrogen sulfate
One of or more than one any combination；The initiator is hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sulfurous
Sour hydrogen sodium, benzoyl peroxide, cumyl peroxide, azodiisobutyronitrile, azobisisoheptonitrile and tert-butyl hydroperoxide
One of or more than one any combination；
The surfactant is polyoxyethylene 20 sorbitan monolaurate, anhydrous sorbitol lauric acid monoester, nonyl phenol
One of polyoxyethylene ether, octyl phenol polyoxyethylene ether, neopelex, calcium dodecyl benzene sulfonate or it is a kind of with
Upper any combination；
In step (1), nanometer calcium carbonate partial size is 200-500nm, and nanometer calcium carbonate dosage accounts for the reaction system quality percentage
Than for 0.5%-2%, it is 0.01%-2%, the volume ratio of ammonium hydroxide and ethyl alcohol that CTAB dosage, which accounts for the reaction system mass percent,
For 1.0:(4.0-10.0)；The concentration of the ammonium hydroxide is 27wt%；
The ethyl orthosilicate of step (1) and the molar ratio of the amino silicane coupling agent in step (3) are 1.0:(0.5-2.0)；
The volume ratio of water described in step (3) and ethyl alcohol is 1:1；Reaction time is not less than 2 hours；
The molar ratio of ethyl 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 dosage of the initiator, which accounts for the reaction system mass percent,；The catalyst
Dosage account for the reaction system mass percent be 0.001%-4%；The dosage of the surfactant accounts for the reactant
Be mass percent be 0.1%-8%.
2. the nano silica of the preparation of method described in claim 1 is grafted organic functional polymer macrolides desinsection
Agent sustained release agent, the load factor of the macrolide insecticide sustained release agent are 66.8%-77.9%, and the sustained release phase is 35-47 days.
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| CN105850992B true CN105850992B (en) | 2019-02-05 |
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| CN108642869B (en) * | 2018-04-12 | 2020-08-18 | 华南理工大学 | Preparation method of super-hydrophobic anti-ultraviolet fabric |
| CN108703958B (en) * | 2018-08-11 | 2021-02-23 | 西华大学 | Method for preparing anti-tumor nano combined medicine by cooperating with streptonigrin |
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| 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 |
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| WO2014017981A1 (en) * | 2012-07-25 | 2014-01-30 | Agency For Science, Technology And Research | Stimuli-responsive interpolymer complex coated hollow silica vesicles |
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