CN104322489B - A kind of montmorillonite Composite pesticide dispersing agent and its preparation method and application - Google Patents
A kind of montmorillonite Composite pesticide dispersing agent and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to pesticide formulation process technology region, it is specifically related to a kind of montmorillonite Composite pesticide dispersing agent and preparation method thereof and application, described composite pesticide dispersant is acrylic copolymer salt/nano imvite composite pesticide dispersant, described acrylic copolymer salt is selected from sodium salt, potassium salt, ammonium salt or organic amine salt, wherein, the monomer of described acrylic copolymer includes that monomer A and monomer B, described monomer A are selected from acrylic or methacrylic acid；Described monomer B is selected from styrene, methyl styrene or t-butyl styrene, and the quality of described nano imvite accounts for the 4～25% of described montmorillonite Composite pesticide dispersing agent quality.This dispersant is obtained by Raolical polymerizable by monomer A, monomer B and montmorillonite, composite pesticide dispersant of the present invention can significantly improve dispersant to by the suspension stability of dispersed substance, is a kind of high-performance, low cost pesticide water dispersible granules special utility macromolecule dispersing agent.
Description
Technical field
The present invention relates to pesticide formulation process technology region, be specifically related to a kind of montmorillonite Composite pesticide dispersing agent
And its preparation method and application.
Background technology
Pesticide active ingredient just can be sent out after only contacting with harmful organism or protected object, absorb or absorb
Wave effect.Generally pesticide cannot be directly used to the parasite killing of crops, sterilization and weeding, it is necessary to is processed into
The formulations of pesticide of various specific physical and chemical performances.Pesticide, by being processed into dosage form, is possible not only to live pesticide
Property composition is transported to the target site of crop, weeds, insect and other harmful organisms so that it is biological activity obtains
To giving full play to, and applications of pesticide amount can be reduced, alleviate environmental pollution.Along with people's environmental consciousness
Day by day strengthening, the Traditional Agricultural pharmaceutically dosage form such as cream with organic solvent as main carriers can not meet the need of people
, safe and environment-friendly water dispersible granules (WDG) becomes the leading dosage form in 21 century pesticide processing field
One of.In WDG formula, dispersant is most important auxiliary agent, effective in preparation and the imparting of the formulations of pesticide
The aspects such as the optimal effect of composition have played important function.
Polycarboxylate salt dispersant is the novel product released the eighties in 20th century, owing to it has longer molecule
Chain and special architectural feature so that dispersant can form stable interaction with solid particle, strengthen
The suspension stability of granule.Therefore polycarboxylate salt dispersant is widely used in the field such as dyestuff and pesticide.For
Former powder keeping environmental protection formulations of pesticide WDG disperses and stable suspersion in aqueous, to dispersant
Requirement should have hydrophilic group；Ensure there is good sympathy between dispersant and former medicine the most again, keep away
Exempt to dissolve the utilization rate reducing dispersant in the solution, need suitably to improve the hydrophobicity of dispersant molecule.
The kind of the more external excellent performances of the patent reports such as US2003/0150578A1, CN1197597A is being divided
Introduce lipophilic group on the main chain of powder, as sieve sub-T36 on the main chain of dispersant, introduce two isobutyls
Alkene, Heng Zi Man T-2700 introduces styrene hydrophobic group on main chain；CN102188929A reports
Styrene, methacrylic acid and the preparation technology of 2-(Acryloyloxy)ethanol ternary polymerization dispersant.
In recent years, with polymer as matrix, MMT be Polymer/nano prepared by inorganic intercalated main body
MMT composite, owing to it has the mechanical property of excellence, heat stability, high gas-liquid barrier, knot
Crystalline substance and fire resistance etc..As Chinese patent CN101570623A reports p-phthalic acid ring glycol ester
Method is obtained with nanometer MMT in-situ polymerization；CN101864119A reports polyacrylate/MMT and is combined
The preparation method of material；CN101812167A reports waterborne polyurethane/organosilicon MMT composite
Preparation method etc..For dispersant, it is desirable to both there is hydrophobic group, must have again hydrophilic group,
Obviously these polymer/MMT nano composite material cannot use as dispersant.
Summary of the invention
Present invention solves the technical problem that and be: in the market the most all have the polymerization of production and selling
Carboxylate dispersants is on the high side, and the performance of product needs to be improved further；With polymerization of carboxylic acid salt intercalation
MMT prepares novel agrochemical hyper-dispersant, utilizes that MMT lamella is sterically hindered improves macromolecule dispersing agent
Performance, and reduce the production cost of dispersant, the method was not the most appeared in the newspapers.
It is an object of the invention to provide a kind of composite pesticide dispersant and preparation method thereof and application, building-up process is without three
Useless discharge, this dispersant can largely improve its dispersion and suspendability for pesticide water dispersible granules,
And reduce processing cost.
In a preferred embodiment of the present invention, the composite pesticide dispersant provided is by methacrylic acid, benzene second
Alkene and montmorillonite (MMT) are obtained by Solution Free Radical in-site intercalation polymerization mode, and its advantage is: by
It is combined with styrene/methacrylic acid copolymer sodium salt in montmorillonite layer, makes the sterically hindered increasing of dispersant
Greatly, dispersant is significantly improved to by the suspension stability of dispersed substance；Simultaneously because MMT is cheap,
Reduce the production cost of dispersant, be a kind of high-performance, low cost pesticide water dispersible granules special utility height
Dispersal agent molecule, it is adaptable to the environmental protection dosage forms such as pesticide water dispersible granules (WDG).
Specifically, for the deficiencies in the prior art, the technical scheme is that
A kind of montmorillonite Composite pesticide dispersing agent, it is characterised in that described montmorillonite Composite pesticide dispersing agent is
Acrylic copolymer salt/nano imvite composite pesticide dispersant, wherein, described acrylic copolymer
Salt is selected from sodium salt, potassium salt, ammonium salt or organic amine salt, and wherein, the monomer of described acrylic copolymer includes
Monomer A and monomer B, described monomer A are selected from acrylic or methacrylic acid；Described monomer B is selected from benzene
Ethylene, methyl styrene or t-butyl styrene；And the quality of described nano imvite to account for described montmorillonite multiple
Close the 4～25% of pesticide dispersing agent quality.
Preferably, in above-mentioned montmorillonite Composite pesticide dispersing agent, the quality of described nano imvite accounts for montmorillonite
The 4～7.5% of composite pesticide dispersant quality.
Preferably, in above-mentioned montmorillonite Composite pesticide dispersing agent, described monomer A is methacrylic acid.
Preferably, in above-mentioned montmorillonite Composite pesticide dispersing agent, described monomer B is styrene.
Preferably, in above-mentioned montmorillonite Composite pesticide dispersing agent, described monomer A with the mol ratio of monomer is
1.5～10:1.
Preferably, in above-mentioned montmorillonite Composite pesticide dispersing agent, the weight average of described acrylic copolymer salt divides
Son amount is 8000-15000g/mol.
Preferably, in above-mentioned montmorillonite Composite pesticide dispersing agent, described acrylic copolymer is random copolymerization
Thing.
The present invention also provides for the preparation method of a kind of montmorillonite Composite pesticide dispersing agent, comprises the steps:
Under molecular weight regulator and initiator existence condition, monomer mixed reactant, nano imvite are entered
Row polyreaction, after adding alkali liquor, prepares montmorillonite Composite pesticide dispersing agent, and wherein, described monomer mixes
Reactant includes that monomer A and monomer B, described monomer A are selected from acrylic or methacrylic acid；Described list
Body B is selected from styrene, methyl styrene or t-butyl styrene, and the quality of described nano imvite is single
The 5～40% of body mixed reactant gross mass.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, first by nano imvite and point
It is warming up to solution backflow after son amount regulator mixing；Add monomer mixed reactant and initiator, control back
Stream, carries out polyreaction；After through in alkali liquor and after, by solvent recovery use, prepare montmorillonite Composite agriculture
Medicine dispersant.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, the quality of described montmorillonite is
The 5～10% of monomer mixed reactant gross mass.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, described monomer A and monomer
Mol ratio be 1.5～10:1.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, described molecular weight regulator is
Alcohol, preferably isopropanol, and described isopropyl alcohol and water is the solvent of polyreaction, wherein, isopropanol and water
Mass ratio be 3～9:1.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, described initiator is selected from over cure
One or more in acid potassium, sodium peroxydisulfate or Ammonium persulfate., and the consumption of initiator is monomer mixing
The 1～10% of reactant gross mass.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, described alkali liquor is selected from hydroxide
One or more of sodium, potassium hydroxide, ammonia, triethylamine or organic amine.
Preferably, in the preparation method of above-mentioned montmorillonite Composite pesticide dispersing agent, with rear solution in alkali liquor
PH is 8.5～9.5.
The present invention also provides for a kind of montmorillonite Composite pesticide dispersing agent, by above-mentioned montmorillonite Composite pesticide dispersing agent
Preparation method prepare.
The present invention also provides for a kind of pesticide, and wherein, the dosage form of described pesticide is water dispersible granules, comprises above-mentioned
Montmorillonite Composite pesticide dispersing agent, and the mass percent that montmorillonite Composite pesticide dispersing agent is in the formulations of pesticide
It is 0.5～10%.
The present invention also provides for the application at pesticide field of the above-mentioned montmorillonite Composite pesticide dispersing agent.
The invention has the beneficial effects as follows: described pesticide dispersing agent is by monomer A, styrene etc. such as methacrylic acids
Monomer B and MMT is obtained by Solution Free Radical in-site intercalation polymerization mode, and this dispersant is due to MMT
Lamella is combined with acrylic copolymer salt, makes the sterically hindered increase of dispersant, significantly improves dispersant pair
By the suspension stability (suspensibility can improve 5%) of dispersed substance；Simultaneously because MMT is cheap,
Reduce the cost of raw material (more than 10% can be reduced) of dispersant, be a kind of high-performance, low cost pesticide
Water dispersible granules special utility macromolecule dispersing agent, it is adaptable to the environmental protection dosage forms such as pesticide WDG.
Accompanying drawing explanation
Fig. 1 is the composite pesticide dispersant prepared by pure montmorillonite (MMT) and embodiment two～embodiment seven
X-ray diffraction pattern, wherein, percentage ratio described in embodiment is that montmorillonite quality accounts for monomer hybrid reaction
The percent of material amount, B is pure montmorillonite (MMT), and D, F, H, J, L, N are respectively and implement
The x-ray diffraction pattern of the composite pesticide dispersant prepared by example two, three, four, five, six, seven.
Fig. 2-a is the scanning electron microscope (SEM) photograph of montmorillonite (MMT).
Fig. 2-b be embodiment three preparation composite pesticide dispersant (MMT mass accounts for monomer mixed reactant
10%) scanning electron microscope (SEM) photograph.
Fig. 3 is that (MMT mass accounts for monomer mixed reactant to the composite pesticide dispersant prepared by embodiment three
10%) infrared spectrum.
Fig. 4 is differential thermal analysis (DSC) figure of the composite pesticide dispersant prepared by embodiment, wherein, institute
Stating percentage ratio is the percent that montmorillonite quality accounts for monomer mixed reactant quality, a, b, c, d, e, f
The respectively differential thermal analysis curve of the composite pesticide dispersant prepared by embodiment one, three, four, five, six, seven.
Detailed description of the invention
The present invention one preferred embodiment in, acrylic copolymer sodium salt/nanometer MMT is multiple
The synthetic method closing pesticide dispersing agent is as follows:
A) equipped with agitator, condensing tube, thermometer, dropper 500ml four-hole boiling flask in add
Enter a certain amount of isopropanol and deionized water, the MMT of different quality is added in solvent, under stirring slowly
It is warming up to solution backflow；
B) methacrylic acid and cinnamic mixed liquor, the aqueous solution of sodium peroxydisulfate initiator it are subsequently adding,
Charging 1～3 hours, controls back flow reaction 3 hours；
C), after the reaction of step b terminates, dropping aqueous slkali is to about pH=9.5, and then normal pressure steams isopropyl
Alcohol and portions of de-ionized water, discharging i.e. obtains liquid methyl acrylic copolymer/nanometer MMT composite diffusion
Agent；
D) step c obtains fluid product be spray-dried, i.e. obtain methacrylic acid copolymer/nanometer MMT
Composite dispersing agent dry powder solid.
Described methacrylic copolymer sodium salt/nanometer MMT composite pesticide dispersant liq product is solid
Content is 20%～40%, and pH value is 9.5.
Described dispersant is exclusively used in the environment-friendly pesticide formulations such as pesticide WDG, the matter of application in the formulations of pesticide
Amount percentage ratio is 0.5～10%.
Acrylic copolymer salt/the nanometer of the present invention is further illustrated below by specific embodiment
MMT composite dispersing agent and its preparation method and application.
In the following embodiments, each reagent used and the information of instrument are as shown in Table 1 and Table 2.
Agents useful for same information table in table 1 embodiment
Device therefor information table in table 2 embodiment
Embodiment one
63g methacrylic acid and 26g styrene are mixed, stirs 20min under room temperature and make monomer mixing instead
Answer thing, standby.
It is dissolved in 68g deionized water under 3.38g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds 68g75% isopropanol/water mixed liquor (mass ratio), under stirring, is heated to backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip 25% hydroxide
Sodium solution, distills out isopropanol/water azeotropic mixture simultaneously, distills the temperature about 100 DEG C to product liquid, pH
Value, to 9.0, is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Spray drying obtains 109g
White powder product 1.
Wherein, owing to styrene has stronger hydrophobicity, therefore, isopropanol is except as molecular weight regulator
Outward, another effect be mix with water after as the solvent reacted, and the isopropanol/water azeotropic mixture distilled out
It is not required to process, can be directly as reaction dissolvent reuse, three-waste free discharge.
Embodiment two
63g methacrylic acid and 26g styrene are mixed, stirs 20min under room temperature and make monomer mixing instead
Answer thing, standby.
It is dissolved in 68g deionized water under 3.38g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds 68g75% isopropanol/water mixed liquor (mass ratio) and 4.5gMMT, the lower heating of stirring
To backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip 25% hydroxide
Sodium solution, distills out isopropanol/water azeotropic mixture simultaneously, distills the temperature about 100 DEG C to product liquid, pH
Value, to 9.0, is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Spray drying obtains 113.5g
White powder product 2.
Example three～example seven concrete steps are identical with example two, but MMT content in example three～example seven
Different.
The evaluation methodology of the application performance of the dispersant prepared by embodiment one～embodiment seven is as follows:
Application of dispersant prepared by embodiment one～seven is joined at the atrazine WDG that mass fraction is 90%
Fang Zhong, is evaluated the performance of dispersant, and concrete scheme is as follows:
Raw material: the former medicine of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazines, 97%, Shan Dongbin
Agriculture Science and Technology Ltd.), before using, through jet mill (LZQS-100 type, Fauna of Kunshan, Jiangsu strong prestige powder
Body equipment company limited) it is crushed to below particle diameter 10 μm；Wetting agent α-sodium olefin sulfonate (beautiful minister in Hunan
Ao Wei Industrial Co., Ltd.)；Disintegrating agent ammonium sulfate (Baoqing, Hunan Yueyang Chemical Co., Ltd.)；Point
Powder is the acrylic copolymer salt/nanometer MMT composite dispersing agent of the present invention.
Processing: by 93g97% atrazine, 5g inventive dispersant, 2g α-sodium olefin sulfonate and 15g go
Ionized water, mediates in kneader, and the material obtained puts in rotary extrusion comminutor and carries out pelletize, so
After in constant temperature blast drying oven 70 DEG C dry 1h, screening obtain apparent particle size 0.8～1.2mm product.
Performance test:
1. suspensibility measures: according to international analysis of agricultural drugs coordination board (CIPAC) MT168 detection side
Method measures the suspensibility of the water dispersible granules of preparation.I.e. weigh appropriate sample 1.0000g, be placed in and fill 50mL
In the 200mL beaker of water, circle with hand swinging, 120 times the most per minute, carry out 2min, will
This suspension places 13min in the water-bath of same temperature, then with water, it is all washed 250mL and measures
In Tong, and be diluted to scale, cover stopper, as axle center bottom graduated cylinder, by graduated cylinder in 1min up and down
Reverse 30 times (graduated cylinder is inverted and recovers to being once in situ, about 2s).Open stopper, more vertically put
Enter in vibrationless water bath with thermostatic control, place 30min.With suction pipe in 10-15s by the 9/10 of content (i.e.
225mL) suspension removal, the precipitum not shaking or stirring in graduated cylinder, it is ensured that the top of suction pipe is always
Under liquid level at several millimeters.Measure sample and stay bottom graduated cylinder active constituent content in 25mL suspension.
Specimen suspension rate X is calculated as follows:
X=(10/9) × (1-m1/m2) × 100%
Wherein, m1Materialsed by formulated suspension the quality of middle effective ingredient；m2For staying bottom graduated cylinder
Effective ingredient quality in 25mL suspension.
2. wettability determination: use graduated cylinder test method(s), quick to filling in 500ml deionized water graduated cylinder
The sample of falling 1.0g, does not stirs, and records the time at the bottom of 99% sample sinks to tin.
3. disintegrative measures: use graduated cylinder test method(s), to equipped with 90ml deionized water at 25 DEG C
100ml tool plug graduated cylinder adds sample 0.5g granule, sandwiches the middle part of graduated cylinder afterwards, clog nozzle, with
The speed of 8r/min is around central rotation, until sample complete disintegrate in water, records disintegrate desired times.
4. heat storage suspensibility measures: 90% atrazine WDG about 5g sample is sealed in 50ml ampoule bottle
In, it is placed in (54 ± 2) DEG C constant temperature oven, takes out after storing 14 days, 1. measure suspensibility by method.
Table 3 be the preparation of embodiment one～embodiment seven products obtained therefrom WDG heat storage before and after suspensibility, profit
Moist, the test result of disintegrative, wherein said MMT (%) is that MMT mass accounts for monomer mixing instead
Answer the percent of thing.
Suspensibility, wettability, the test result of disintegrative before and after the storage of table 3 90% atrazine WDG heat
The XRD figure of the product of MMT and embodiment two～embodiment seven preparation is as it is shown in figure 1, wherein, real
Executing MMT percent described in example two～seven is the percent that MMT mass accounts for monomer mixed reactant quality.
Test condition is graphite C u target, K α radiation source (λ=0.15405nm), 4 °/min of sweep speed, scanning
Scope is 0～30 °.As seen from Figure 1, for the MMT of 100%, when 2 θ are about 7 °, occur
001 crystallographic plane diffraction peak of MMT；The product of embodiment two and embodiment three occurs when 2 θ are about 5 °
Significantly diffraction maximum, has illustrated in methacrylic acid copolymer intercalation MMT so that it is interlamellar spacing becomes big；Real
Execute the product of example four～embodiment seven to weaken, 7 with the increase of MMT content the diffraction maximum of about 5 °
Peak about ° increases with the increase of MMT content, illustrates in the presence of a large amount of MMT, only
There is part MMT by intercalation, and major part is still presented in original soil.
Can be drawn by experimental data in table 3, MMT content 5～10% atrazine water dispersible granule outstanding
Floating rate reaches 98.89%, improves more than 3% with being not added with MMT, and after heat storage, suspensibility varies less, less than
2%, wettability and disintegrative are basically unchanged；But after MMT content is more than 10%, the suspensibility of WDG by
Gradually declining, wetting time substantially increases；When MMT content is 50%, suspensibility drops to 62.22%,
It is 41.11% after heat storage.This change is consistent with XRD analysis.When MMT content is few, metering system
In acid copolymer intercalation MMT, particle is not easily formed reunion, and MMT interlamellar spacing increases, and is uniformly dispersed,
Enhance the polymer dispersive property to pesticide；But after MMT content is more than 10%, polyalcohol intercalation is uneven
Even, with the presence of part MMT not by intercalation still with agglomerated particles, MMT granule dispersion inequality, cause poly-
The decline of compound dispersive property, after heat storage, suspensibility is decreased obviously.
Fig. 2-a is the scanning electron microscope (SEM) photograph of MMT, and amplification is 1000 times, by figure it can be seen that MMT
Granule is relatively big, and particle diameter is in 20～50 μm.
Fig. 2-b is the scanning electron microscope (SEM) photograph of embodiment three products obtained therefrom, and amplification is 800 times, permissible by figure
Finding out, MMT is after the in-situ polymerization intercalated reaction of methacrylic acid and styrene, and particle diameter significantly diminishes, and sends out
Generating layer sheet peeling, this result is consistent with XRD analysis result.
Composite pesticide dispersant KBr tabletting embodiment three synthesized, at NicoletMAGNA-IR560
Its infrared spectrogram measured by type infrared spectrometer as it is shown on figure 3, wave-number range 4000-400cm-1.From figure
It will be seen that 1041cm-1For the asymmetrical stretching vibration peak of the Si-O-Si of MMT, 523cm-1
Neighbouring for Si-O-Mg bending vibration absorption spectral peak；The stretching vibration absworption peak of-C=O is positioned at 1556cm-1
And 1398cm-1Place, 2960cm-1It is-CH3Stretching vibration peak, 1450cm-1And 700cm-1The suction at place
Receiving peak is phenyl ring characteristic absorption peak.Result shows by intercalated polymerization, methacrylic acid/benzene second
Alkene copolymer sodium salt is combined with the success of montmorillonite.
Under the protection of nitrogen, with the programming rate of 15 DEG C/min, the composite pesticide dispersant of synthesis is carried out
Dsc analysis, is shown in Fig. 4.As can be seen from Figure, synthesis composite pesticide dispersant all only one of which vitrifications
Temperature, for random copolymer.
Embodiment eight
63g methacrylic acid and 26g styrene are mixed, stirs 20min under room temperature and make monomer mixing instead
Answer thing, standby.
It is dissolved in 68g deionized water under 0.89g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds 68g90% isopropanol/water mixed liquor (mass ratio) and 9gMMT, the lower heating of stirring
To backflow.
Then, under stirring, in four-hole boiling flask, it is slowly added dropwise above-mentioned all monomer mixed reactants and initiation simultaneously
Agent solution, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip 25% hydrogen
Potassium oxide solution, distills out isopropanol/water azeotropic mixture simultaneously, distills the temperature about 100 DEG C to product liquid,
PH value, to 9.5, is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Spray drying obtains 115g
White powder product 8.
By application of dispersant method of evaluating performance prepared in previous embodiment one～embodiment seven, record enforcement
The performance parameter of example eight dispersant is: suspensibility 95.61%, suspensibility 92.83% after heat storage, wetting time
300s, disintegrate more than 30 times.
Embodiment nine
63g methacrylic acid and 26g styrene are mixed, stirs 20min under room temperature and make monomer mixing instead
Answer thing, standby.
It is dissolved in 68g deionized water under 8.9g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds 68g80% isopropanol/water mixed liquor (mass ratio) and 9gMMT, the lower heating of stirring
To backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip 25% hydroxide
Sodium solution, distills out isopropanol/water azeotropic mixture simultaneously, distills the temperature about 100 DEG C to product liquid, pH
Value, to 8.5, is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Spray drying obtains 124.6g
White powder product 9.
By application of dispersant method of evaluating performance prepared in previous embodiment one～embodiment seven, record enforcement
The performance parameter of example JIUFEN POWDER agent is: suspensibility 96.15%, suspensibility 93.68% after heat storage, wetting time
110s, disintegrate 8 times.
Embodiment ten
47.32g methacrylic acid and 32.68g styrene are mixed, stirs 20min under room temperature and make monomer
Mixed reactant, standby.
It is dissolved in 68g deionized water under 3.38g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds under 68g75% isopropanol/water mixed liquor (mass ratio) and 9gMMT, stirring and be heated to
Backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip ammonia, simultaneously
Distill out isopropanol/water azeotropic mixture, distill the temperature about 100 DEG C to product liquid, pH value to 9.5, cooling
To 40 DEG C of dischargings, obtain light yellow clear product liquid.Spray drying obtains 105g white powder product 10.
By application of dispersant method of evaluating performance prepared in previous embodiment one～embodiment seven, record enforcement
The performance parameter of example ten dispersant is: suspensibility 97.55%, suspensibility 94.85% after heat storage, wetting time
230s, disintegrate 8 times.
Embodiment 11
79.49g methacrylic acid and 9.51g styrene are mixed, stirs 20min under room temperature and make monomer and mix
Close reactant, standby.
It is dissolved in 68g deionized water under 3.38g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds under 68g75% isopropanol/water mixed liquor (mass ratio) and 9gMMT, stirring and be heated to
Backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip triethylamine solution,
Distill out isopropanol/water azeotropic mixture simultaneously, distill the temperature about 100 DEG C to product liquid, pH value to 9.0,
It is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Obtain yellow transparent liquid.It is spray-dried
Obtain 122g white powder product 11.
By application of dispersant method of evaluating performance prepared in previous embodiment one～embodiment seven, record enforcement
The performance parameter of example 11 dispersant is: suspensibility 97.05%, and suspensibility 93.63% after heat storage, during moistening
Between 110s, disintegrate 10 times.
Embodiment 12
63g methacrylic acid and 30g methyl styrene are mixed, stirs 20min under room temperature and make monomer and mix
Close reactant, standby.
It is dissolved in 68g deionized water under 3.38g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds 68g75% isopropanol/water mixed liquor (mass ratio) and 4.5gMMT, the lower heating of stirring
To backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip 25% hydroxide
Sodium solution, distills out isopropanol/water azeotropic mixture simultaneously, distills the temperature about 100 DEG C to product liquid, pH
Value, to 9.0, is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Spray drying obtains 117.6g
White powder product 12.
By application of dispersant method of evaluating performance prepared in previous embodiment one～embodiment seven, record enforcement
The performance parameter of example 12 dispersant is: suspensibility 95.65%, and suspensibility 94.18% after heat storage, during moistening
Between 160s, disintegrate 8 times.
Embodiment 13
53g acrylic acid and 40g p-tert-butylstyrene are mixed, stirs 20min under room temperature and make monomer and mix
Close reactant, standby.
It is dissolved in 68g deionized water under 3.38g sodium peroxydisulfate is stirred, makes initiator solution, standby.
With stirring, heating, thermometer, reflux, feed and nitrogen protection device 500mL four
Mouth flask adds 68g75% isopropanol/water mixed liquor (mass ratio) and 4.5gMMT, the lower heating of stirring
To backflow.
Then, under stirring, in four-hole boiling flask, it is simultaneously added dropwise above-mentioned all monomer mixed reactants and initiator is molten
Liquid, time for adding 1h.Charging is further continued for reacting 2h after terminating, after insulation terminates, drip 25% hydroxide
Sodium solution, distills out isopropanol/water azeotropic mixture simultaneously, distills the temperature about 100 DEG C to product liquid, pH
Value, to 9.0, is cooled to 40 DEG C of dischargings, obtains light yellow clear product liquid.Spray drying obtains 117.7g
White powder product 13.
By application of dispersant method of evaluating performance prepared in previous embodiment one～embodiment seven, record enforcement
The performance parameter of example 13 dispersant is: suspensibility 97.21%, and suspensibility 93.88% after heat storage, during moistening
Between 210s, disintegrate 10 times.
Use gel chromatography and laser light scattering combined instrument (SEM-MALLS), with methanol and 10mM
NaH2PO4It is flowing phase with the mixed liquor that 38.6mMNaCl volume of buffer solution percentage ratio is 70:30, poly-
Ethylene glycol 10000 is standard substance, measures composite pesticide dispersion prepared in embodiment one～embodiment 13
In agent, the weight average absolute molecular weight range of acrylic copolymer salt is 8000-15000g/mol.
Comparative example one
International similar dispersant (such as U.S.'s Huntsman company's T ERSPERSE2700) is applied in matter
Amount mark is in the atrazine WDG formula of 90%, is evaluated the performance of dispersant, concrete scheme
As follows:
Raw material: the former medicine of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazines, 97%, Shan Dongbin
Agriculture Science and Technology Ltd.), before using, through jet mill (LZQS-100 type, Fauna of Kunshan, Jiangsu strong prestige powder
Body equipment company limited) it is crushed to below particle diameter 10 μm；Wetting agent α-sodium olefin sulfonate (beautiful minister in Hunan
Ao Wei Industrial Co., Ltd.)；Disintegrating agent ammonium sulfate (Baoqing, Hunan Yueyang Chemical Co., Ltd.)；Point
Powder is U.S.'s Huntsman company's T ERSPERSE2700, for the methyl-prop that a kind of hydrophobic group is modified
Olefin(e) acid copolymer sodium salt.
Processing: by 93g97% atrazine, 5g TERSPERSE2700 polycarboxylate salt dispersant, 2g α-
Sodium olefin sulfonate and 15g deionized water, mediate in kneader, and the material obtained puts into rotary extrusion and makes
Carrying out pelletize, then 70 DEG C of drying 1h in constant temperature blast drying oven in grain machine, screening obtains apparent particle size
The product of 0.8～1.2mm.
As prepared by previous embodiment one～embodiment seven, the Performance Properties Evaluation method of dispersant, records
90% atrazine WDG performance parameter prepared by TERSPERSE2700 polycarboxylate salt dispersant is: suspend
Rate 94.33%, suspensibility 92.91% after heat storage, wetting time 110s, disintegrate 8 times.
Gained montmorillonite Composite pesticide dispersing agent of the present invention significantly improves 90% atrazine water dispersible granule
Suspensibility, reaches 98.89%, is 97.78% after heat storage, dispersant more similar than the world being not added with montmorillonite
(such as U.S.'s Huntsman company's T ERSPERSE2700) improves 3%～5%；Gained montmorillonite of the present invention
Composite pesticide dispersant, while improving formulations of pesticide performance, can significantly reduce the production cost of dispersant,
As a example by compound 10% montmorillonite dispersant, it is possible to decrease the cost of raw material 8%～10%.Additionally, institute of the present invention
State the preparation method technique environmental protection of montmorillonite Composite pesticide dispersing agent, with low cost, due to sulfur alcohol compound
After reaction, remaining has the most unpleasant taste in the product, and therefore, the present invention combines user's request, preferably
Isopropanol is molecular weight regulator, and used by the isopropanol/water azeotropic mixture that distills out be not required to process, can be direct
As reaction dissolvent reuse, three-waste free discharge.Therefore, the present invention is macromolecule dispersing agent high-performance, low one-tenth
Basis, the production technology of environmental protection, have extraordinary application prospect.
Claims (28)
1. a montmorillonite Composite pesticide dispersing agent, it is characterised in that described montmorillonite Composite pesticide dispersing agent is acrylic compounds
Copolymer salt/nano imvite composite pesticide dispersant, wherein, described acrylic copolymer salt is selected from sodium salt, potassium salt, ammonium
Salt or organic amine salt, wherein, the monomer of described acrylic copolymer includes that monomer A and monomer B, described monomer A are selected from third
Olefin(e) acid or methacrylic acid；Described monomer B is selected from styrene, methyl styrene or t-butyl styrene；And described nanometer covers de-
The quality of soil accounts for the 4～25% of described montmorillonite Composite pesticide dispersing agent quality.
Montmorillonite Composite pesticide dispersing agent the most according to claim 1, wherein, the quality of described nano imvite accounts for institute
State the 4～7.5% of montmorillonite Composite pesticide dispersing agent quality.
Montmorillonite Composite pesticide dispersing agent the most according to claim 1, wherein, described monomer A is methacrylic acid.
Montmorillonite Composite pesticide dispersing agent the most according to claim 2, wherein, described monomer A is methacrylic acid.
Montmorillonite Composite pesticide dispersing agent the most according to claim 1, wherein, described monomer B is styrene.
Montmorillonite Composite pesticide dispersing agent the most according to claim 2, wherein, described monomer B is styrene.
Montmorillonite Composite pesticide dispersing agent the most according to claim 3, wherein, described monomer B is styrene.
Montmorillonite Composite pesticide dispersing agent the most according to claim 4, wherein, described monomer B is styrene.
9. according to the montmorillonite Composite pesticide dispersing agent described in any one of claim 1～8, wherein, described monomer A and monomer B
Mol ratio be 1.5～10:1.
10. according to the montmorillonite Composite pesticide dispersing agent described in any one of claim 1～8, wherein, described acrylic compounds is altogether
The weight average molecular weight of polymers salt is 8000-15000g/mol.
11. montmorillonite Composite pesticide dispersing agents according to claim 9, wherein, the weight of described acrylic copolymer salt
Average molecular weight is 8000-15000g/mol.
The preparation method of 12. 1 kinds of montmorillonite Composite pesticide dispersing agents, comprises the steps:
Under molecular weight regulator and initiator existence condition, monomer mixed reactant, nano imvite are carried out polyreaction,
After adding alkali liquor, preparing montmorillonite Composite pesticide dispersing agent, wherein, described monomer mixed reactant includes monomer A and monomer B,
Described monomer A is selected from acrylic or methacrylic acid；Described monomer B is selected from styrene, methyl styrene or t-butyl styrene,
The quality of described nano imvite is the 5～40% of monomer mixed reactant gross mass.
The preparation method of 13. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, first covers de-by nanometer
Soil and molecular weight regulator are warming up to solution backflow after mixing；Add monomer mixed reactant and initiator, control backflow,
Carry out polyreaction；After through in alkali liquor and after, by solvent recovery use, prepare montmorillonite Composite pesticide dispersing agent.
The preparation method of 14. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, described nanometer is covered de-
Quality is monomer mixed reactant gross mass the 5～10% of soil.
The preparation method of 15. montmorillonite Composite pesticide dispersing agents according to claim 13, wherein, described nanometer is covered de-
Quality is monomer mixed reactant gross mass the 5～10% of soil.
The preparation method of 16. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, described monomer A and list
The mol ratio of body B is 1.5～10:1.
The preparation method of 17. montmorillonite Composite pesticide dispersing agents according to claim 13, wherein, described monomer A and list
The mol ratio of body B is 1.5～10:1.
The preparation method of 18. montmorillonite Composite pesticide dispersing agents according to claim 14, wherein, described monomer A and list
The mol ratio of body B is 1.5～10:1.
The preparation method of 19. montmorillonite Composite pesticide dispersing agents according to claim 15, wherein, described monomer A and list
The mol ratio of body B is 1.5～10:1.
The preparation method of 20. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, described molecular weight is adjusted
Joint agent is alcohol.
The preparation method of 21. montmorillonite Composite pesticide dispersing agents according to claim 20, wherein, described alcohol is isopropyl
Alcohol, and described isopropyl alcohol and water is the solvent of polyreaction, wherein, isopropanol is 3～9:1 with the mass ratio of water.
The preparation method of 22. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, described initiator selects
One or more in potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate., and the consumption of initiator is monomer hybrid reaction
The 1～10% of thing gross mass.
The preparation method of 23. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, described alkali liquor is selected from
One or more of sodium hydroxide, potassium hydroxide, ammonia or organic amine.
The preparation method of 24. montmorillonite Composite pesticide dispersing agents according to claim 23, wherein, described organic amine is
Triethylamine.
The preparation method of 25. montmorillonite Composite pesticide dispersing agents according to claim 12, wherein, with rear molten in alkali liquor
The pH of liquid is 8.5～9.5.
26. 1 kinds of montmorillonite Composite pesticide dispersing agents, are divided by the montmorillonite Composite pesticide described in any one of claim 12～25
The preparation method of powder prepares.
27. 1 kinds of pesticide, wherein, the dosage form of described pesticide is water dispersible granules, comprises claim 1～11 or claim
Montmorillonite Composite pesticide dispersing agent described in 26 any one, and the quality hundred that montmorillonite Composite pesticide dispersing agent is in the formulations of pesticide
Mark is 0.5～10%.
28. claim 1～11 or any one of claim 26 described in montmorillonite Composite pesticide dispersing agent at pesticide field
Application.
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