CN101664029B - Environment-friendly pesticide formulation special dispersing agent and application thereof - Google Patents
Environment-friendly pesticide formulation special dispersing agent and application thereof Download PDFInfo
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- CN101664029B CN101664029B CN2008101466605A CN200810146660A CN101664029B CN 101664029 B CN101664029 B CN 101664029B CN 2008101466605 A CN2008101466605 A CN 2008101466605A CN 200810146660 A CN200810146660 A CN 200810146660A CN 101664029 B CN101664029 B CN 101664029B
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Abstract
The invention provides a special dispersing agent applied to environment-friendly pesticide formulations. The dispersing agent is prepared by polymerization of maleic anhydride or derivatives thereof and acrylic acid or derivatives thereof, and the molecular weight is between 1,000 and 50,000. The molar ratio of the maleic anhydride or the derivatives thereof to the acrylic acid or the derivatives thereof is 0.1-20:0.1-20. The dispersing agent is used for the environment-friendly pesticide formulations of water dispersible granules and a suspending agent, and the weight percentage of the dispersing agent in the two pesticide formulations is 0.1 to 15 percent.
Description
Technical field
The present invention relates to the synthetic and application technology of a kind of copolymer dispersant, the application of particularly a kind of environment-friendly pesticide formulation special dispersing agent in water dispersible granules and suspending agent.
Background technology
Agricultural chemicals conventional dosage forms missible oil, wetting powder etc. account for 80% in China's preparation total amount, along with the development of pesticide processing technology, problems such as the environment of conventional dosage forms are apparent more outstanding, and environment-friendly pesticide formulations such as water dispersible granules and suspending agent arise at the historic moment.Water dispersible granules is with the powderous preparations spheroidizing, avoids dust pollution, is convenient to packing, during use it is dropped into disintegration dispersion rapidly in the water, forms the dispersion of higher suspension, is convenient to spraying and uses.Suspending agent is representative Water-borne modification novel form, is characterized in water to replace organic solvent, has reduced using and to the pollution of environment, reducing preparation toxicity of organic solvent, improves safety.
Dispersant is a requisite important component in the formulation products such as pesticide water dispersible granules and suspending agent, along with the fast development of agricultural chemicals suspension agent and water dispersible granules, dispersant has been had requirements at the higher level.
Polycarboxylic acid salt's dispersant (like the polycarboxylic acid polymeric dispersant) mainly is that carboxylic unsaturated monomer (like acrylic acid, maleic anhydride etc.) forms with other monomer copolymerizations.Though just polycarboxylic acid salt's dispersant is applied to fields such as papermaking, coating the external seventies, the distribution of the kind of its comonomer, proportioning, molecular weight and dispersion mechanism are the ten minutes active subject always.For example, in the polycarboxylic acid polymer, introduce special functional monomer (like functional monomers such as sulfonic group, amino), to improve the dispersive property of polymeric dispersant, the molecular weight distribution of control polymeric dispersant.According to bibliographical information; Polymer chain will contain the carbon atom more than 65 at least; Just can play effective sterically hindered effect, and molecular weight distribution is narrow as much as possible, " classification " effect can take place in the polymer of molecular weight distribution broad in solution; Be the more particle surface that is adsorbed in of dispersant of a certain segment molecule weight range, remainder then remains in the system.Need control the molecular weight of hydrophilic segment in the polymeric dispersant, hydrophobic part in addition, wherein the molecular weight of water-wet side should be controlled at about 3000～5000.If the molecular weight of water-wet side is too high, then hydrophilic chain is long, makes the polymer dispersed agent molecule be prone to come off from former medicine surface, is prone to the generation entanglement simultaneously between hydrophilic chain and hydrophilic chain and causes flocculation.The molecular weight of hydrophobic segment should be controlled at about 5000～7000; If this part molecular weight is too high, then hydrophobic chain is long, often forms ring or combines with adjacent particles is surperficial because of being adsorbed in particle surface fully; Thereby cause interparticle " bridge formation " flocculation, the dispersion of former medicine is exerted an influence.
The report that novel dispersant is arranged again recently, they are the polycarboxylic-acid dispersants that belong to anionic dispersing agents, can improve disintegrative, dispersiveness, suspension and the storage-stable of water dispersible granules greatly.They are that molecular weight is 5000～20000 following copolymer: the copolymer sodium salt and the ammonium salt of (1) acrylic acid and maleic acid; (2) copolymer sodium salt, amine salt and the ammonium salt of methacrylic acid and maleic acid; (3) butene dioic acid and cinnamic copolymer sodium salt, ammonium salt and amine salt; (4) butene dioic acid and diisobutylene diacid copolymer sodium salt, ammonium salt and amine salt.
In the achievement in research of external dispersant, anionic dispersing agents is more.Outstanding is the acrylic copolymer series that SANYO GS changes into exploitation.Comprise: (1) styrene sulfonic acid-styrene-propene acid copolymer sodium salt; (2) styrene sulfonic acid-p-methylstyrene-acrylic copolymer sodium salt; (3) styrene sulfonic acid-acrylic copolymer sodium salt.The development and production of domestic pesticide dispersing agent are being made significant headway aspect the lignin sulfonic acid salt, but the high molecular polymer carboxylate is as the exploitation of pesticide dispersing agent blank out almost also.
Summary of the invention
The purpose of this invention is to provide a kind of maleic acid anhydride or derivatives thereof and acrylic acid or derivatives thereof copolymer and preparation method thereof and with its as dispersant in special dispersing agent applied, this dispersant is used for dispersion and the suspendability that environment-friendly pesticide formulations such as water dispersible granules and suspending agent can largely improve these formulations.
Dispersant of the present invention comprises: acrylic acid homopolymerization sodium salt, acrylic acid maleic anhydride multipolymer sodium salt and ammonium salt.Wherein maleic acid anhydride or derivatives thereof and acrylic acid or derivatives thereof mol ratio are 0.1～20.0:0.1～20.0.
The preparation method of dispersant of the present invention comprises the steps:
(1) first water is with the dissolving of maleic acid anhydride or derivatives thereof, and solution temperature is controlled at 0～50 ℃, and then the maleic acid anhydride or derivatives thereof being regulated pH with alkali compounds (like sodium hydroxide, potassium hydroxide etc.) down at 0～50 ℃ is 4～6;
(2) be under 0～50 ℃ of condition in temperature, using alkali compounds to be neutralized to pH the acrylic acid or derivatives thereof is 4～6;
(3) will make by oneself molecular weight regulator join alkalize the neutralization acrylic acid or derivatives thereof solution in stir;
(4) in the maleic acid anhydride neutralizer, add reductant, initator is added an amount of water-soluble separating.
(5) under the stirring condition between 90～100 ℃ in maleic acid anhydride or derivatives thereof solution dropwise addition of acrylic acid or derivatives thereof and initiator solution, dropwised in 40 minutes, under 50～90 ℃ of conditions, be incubated again, temperature retention time is 2～6 hours.
(6) under 50～80 ℃ of conditions, in above solution, drip the grafting initator high price cerium salt that has prepared simultaneously, 30min dropwises, insulation 1～4h;
(7) with Highspeedcentrifugingandsprayingdrier above liquid is carried out drying processing, promptly get the solid powdery dispersant;
Maleic acid anhydride or derivatives thereof described in the present invention mainly refers to maleic anhydride, fumaric acid, maleic acid alkali metal salt, maleic acid ammonium salt or organic amine salt, but is not limited to the above compound.Described acrylic acid or derivatives thereof mainly refer to acrylic acid with
The chain-transferring agent that uses among the present invention can be selected for use from following several types: TGA, sodium hydrogensulfite, sodium phosphite, isopropyl alcohol, lauryl mercaptan, n-butyl mercaptan, carbon tetrachloride etc.; Polymerization temperature is between 60～90 ℃ among the present invention, and reaction divides four-stage to carry out, and the phase I is for dripping monomer stage; Time is 40～60min, and variations in temperature is very fast during this period of time, and second stage is a holding stage; Time is 2～4h, and temperature is 80～100 ℃; Phase III is the structure arrangement grafting stage, and the time is 40min, and temperature is relatively stable; Stage is a holding stage, and the time is 2～4h, and temperature is 80～100 ℃;
An advantage of the present invention is to make a kind of redox initiator, uses it can synthesize effective control polymer molecular weight size and range of molecular weight distributions.Polycarboxylic acid salt's dispersant is generally oligomer, and molecular weight is about 1000～20000.Agricultural chemicals is very important to the quality of dispersant dispersive property with the control of macromolecule dispersing agent molecular weight, and the too high meeting of molecular weight causes flocculation; Molecular weight is too small then can not to produce enough negative electrical charges, can't make between particle because of the electrostatic repulsion stable dispersion.For obtaining preferable dispersive property, molecular weight distribution should be narrow as far as possible.To add a large amount of persulfates both uneconomical and can reduce the effect of dispersant for the control molecular weight.Free radical solution polymerization is the synthetic method of using always, and control molecular weight and molecular weight distribution are the keys of entire reaction, and this relates to the influence of many factors such as concentration, solvent species, reactive mode, temperature of initator, chain-transferring agent, monomer.Explore through long-term test; We are optimized selection from aspects such as monomer ratio, feed way, initator, temperature to synthesis technique, and it is simple to optimize a kind of technology, mild condition; Three-waste free discharge; The suitability for industrialized production energy consumption is low, the sintetics stable performance, and this technology has very important good cost performance for the comprehensive utilization of environment and resource;
Another advantage of the present invention is in post-synthesis phase molecular structure further to be adjusted optimization, on the basis that forms high polymer, carries out modification through high price cerium salt pair straight chain molecule, and then forms the pectination macromolecular structure.
The application of dispersant of the present invention in water dispersible granules
The application of dispersant of the present invention in water dispersible granules is to realize through following scheme:
Water dispersible granules, the percentage by weight of each component is in the prescription: former medicine 5～80%, dispersant 1～15%, wetting agent 1～5%, disintegrant 3～8%, adhesive 2～8%, stabilizing agent 1～6%, filler 12～60%.
Described dispersant is an environment-friendly pesticide formulation special dispersing agent of the present invention.
Described wetting agent is a kind of or two or more mixing wetting agents in neopelex, lauryl sodium sulfate, Nekal BX, ethoxylated dodecyl alcohol sodium sulphate, penetrant t, the penetrating agent JFC.
Described disintegrant is a kind of or two or more mixing disintegrants in ammonium sulfate, urea, sodium sulphate, magnesium chloride, sodium chloride, sodium carboxymethyl starch, Ac-Di-Sol, the polyvinylpyrrolidone.
Described adhesive is a kind of or two or more mixing adhesives in carboxymethyl cellulose, hydroxyethylcellulose, starch, dextrin, gum Arabic, the polyvinyl alcohol.
Described stabilizing agent is a kind of or two or more mixed stabilizers in calcium chloride, tributyl phosphate, sodium hydrogen phosphate, the borax.
Described filler is a kind of or two or more mixed fillers in atlapulgite, attapulgite, kaolin, bentonite, white carbon black, precipitated calcium carbonate, diatomite, potter's clay, the talcum powder.
Above auxiliary agent and filler all are known substances, also are the common and materials known in the pesticidal preparations processing.
The processing technology of said water dispersible granules is:
The present invention compared with prior art utilizes autonomous synthetic dispersing agent to carry out water-dispersible grain agent prescription design, the granule that obtains through appropriate process processing, can be in water disintegration rapidly, dispersion, the stable dispersion suspension system of formation.
The application of dispersant in suspending agent
The application of dispersant of the present invention in suspending agent is to realize through following scheme:
Suspending agent, the percentage by weight of each component is in the prescription: former medicine 5～60%, dispersant 1～8%, wetting agent 0～5%, thixotropic agent 0～20%, thickener 0～20%, antifreezing agent 0～10%, preservative 0～2%, water 0～100%.
Described dispersant is for being environment-friendly pesticide formulation special dispersing agent of the present invention.
Described wetting agent is a kind of or two or more mixing wetting agents in neopelex, lauryl sodium sulfate, Nekal BX, ethoxylated dodecyl alcohol sodium sulphate, penetrant t, the penetrating agent JFC.
Described thixotropic agent be sodium silicate, urea, kaolin, sodium bentonite, aluminium-magnesium silicate, a kind of or two or more mixtures.
Described thickener is a kind of or two or more mixing adhesives in carboxymethyl cellulose, hydroxyethylcellulose, starch, dextrin, xanthans, gum Arabic, the polyvinyl alcohol.
Described antifreezing agent is a kind of or two or more mixed stabilizers in urea, ethylene glycol, the glycerine.
Above auxiliary agent and filler all are known substances, also are the common and materials known in the pesticidal preparations processing.
The processing technology of said suspending agent is:
The present invention compared with prior art utilizes the dispersant component design of independent research, utilizes the suspending agent of suspending agent processing technology development suspended dispersed stable homogeneous.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Below prepare embodiment for dispersant:
Embodiment 1
(1) the 49g maleic anhydride is dissolved in the 200mL water, using 30% sodium hydroxide solution to be neutralized to pH then is 4～6;
(2) 25g acrylic acid is dissolved in the 150g water, uses 30% sodium hydroxide to be neutralized to pH and be 4-6;
(3) 2g TGA and 0.5g isopropyl alcohol are joined in the 114g acrylic acid solution of the neutralization of alkalizing stir, in the maleic acid anhydride solution, add the 0.8g sodium hydrogensulfite, the 10g ammonium persulfate is added an amount of water-soluble separating.
(4) at 90～100 ℃, under the stirring condition in the maleic acid anhydride solution dropwise addition of acrylic acid and ammonium persulfate solution, dropwised in 40 minutes, under 50～90 ℃ of conditions, be incubated again, temperature retention time is 2-6 hour.
(5) under 50～80 ℃ of conditions, in above solution, drip 54g ammonium ceric nitrate (0.5g cerous nitrate+53.4g running water) and the 62g acrylic acid aqueous solution that has prepared simultaneously, 30min dropwises, insulation 1～4h;
(6) using 30% sodium hydrate aqueous solution to be neutralized to pH is 7～8, molecular weight is 8000～15000 maleic anhydride acrylic copolymer sodium salt
(7) with Highspeedcentrifugingandsprayingdrier above liquid is carried out drying processing, promptly get the solid powdery dispersant
Embodiment 2
(1) with the 300g running water 98g maleic acid ammonium salt is dissolved earlier, transferring pH is 4～6;
(2) be under 0～50 ℃ of condition in temperature, with the PAA dissolving, accent pH is 4-6;
(3) 200g running water, 2.5g TGA, 0.8g isopropyl alcohol are joined in the PAA solution and stir;
(4) the 10g ammonium persulfate is added 150g is water-soluble to be separated.
(5) under the stirring condition between 90～100 ℃ in the maleic acid ammonium salt solution dropwise addition of acrylic acid sodium solution and initiator solution, dropwised in 40 minutes, under 50～90 ℃ of conditions, be incubated again, temperature retention time is 2-6 hour.
(6) under 50～80 ℃ of conditions, in above solution, drip 36g ammonium ceric nitrate and the 58g acrylic acid aqueous solution that has prepared simultaneously, 30min dropwises, insulation 1～4h;
(7) using in 30% sodium hydrate aqueous solution with above polymer solution pH is 7～8, molecular weight is 15000～30000 maleic anhydride acrylic copolymer sodium salt
(8) with Highspeedcentrifugingandsprayingdrier above liquid is carried out drying processing, promptly get the solid powdery dispersant
Below be dispersant application implementation example:
Embodiment 1
75% tribenuron-methyl WDG mass fraction/%
The former medicine 75 of tribenuron-methyl
Acrylic acid maleic anhydride multipolymer 5
Sodium salt (M=10000-20000)
Ammonium persulfate 8
Neopelex 3
Sodium bentonite
Embodiment 2
80% fluorine worm nitrile WDG mass fraction/%
The former medicine 80 of fluorine worm nitrile
Acrylic acid maleic anhydride multipolymer 5
Sodium salt (M=6000-15000)
Sodium bicarbonate 7
Lauryl sodium sulfate 2
Sodium bentonite
Embodiment 3
60% metsulfuron-methyl WDG mass fraction/%
The former medicine 60 of metsulfuron-methyl
Acrylic acid maleic anhydride multipolymer 8
Sodium salt (M=5000-10000)
NNO 5
Sodium bicarbonate 12
Lauryl sodium sulfate 3
Sodium bentonite
Embodiment 4
25% thiophene worm piperazine WDG mass fraction/%
The former medicine 25 of thiophene worm piperazine
Acrylic acid maleic anhydride multipolymer 6
Ammonium salt (M=5000-10000)
NNO 3
Ammonium sulfate 35
GY-W01 3
Common bentonite 2
Kaolin
Embodiment 5
20% Imidacloprid SC mass fraction/%
The former medicine 20 of Imidacloprid
Acrylic acid maleic anhydride multipolymer 2
Sodium salt (M=10000-20000)
NNO 2
Neopelex 1
Antifreezing agent 5
Thickener 0.15
Antifoaming agent 2
Water
Embodiment 6
5% fluorine worm nitrile SC mass fraction/%
The former medicine 5 of fluorine worm nitrile
Acrylic acid maleic anhydride multipolymer 2
Sodium salt (M=6000-15000)
Neopelex 1
Antifreezing agent 5
Thickener 0.2
Antifoaming agent 2
Water
Embodiment 7
38% atrazine SC mass fraction/%
The former medicine 38 of atrazine
Acrylic acid maleic anhydride multipolymer 2
Sodium salt (M=6000-15000)
Neopelex 1
Antifreezing agent 5
Thickener 10
Antifoaming agent 2
Preservative 0.2
Water
Embodiment 8
25% 2 chloroquine phosphoric acid SC mass fraction/%
Two chloroquine phosphagen medicines 25
Acrylic acid maleic anhydride multipolymer 2
Sodium salt (M=6000-15000)
BC/10 1
Antifreezing agent 5
Thickener 10
Antifoaming agent 2
Preservative 0.2
Water
Claims (2)
1. the preparation method of an environment-friendly pesticide formulation specialty polymer dispersant is characterized in that this method comprises the steps:
(1) the 49g maleic anhydride is dissolved in the 200mL water, using 30% sodium hydroxide solution to be neutralized to pH then is 4～6;
(2) 25g acrylic acid is dissolved in the 150g water, uses 30% sodium hydroxide to be neutralized to pH and be 4-6;
(3) 2g TGA and 0.5g isopropyl alcohol are joined in the 114g acrylic acid solution of the neutralization of alkalizing stir, in the maleic acid anhydride solution, add the 0.8g sodium hydrogensulfite, the 10g ammonium persulfate is added an amount of water-soluble separating;
(4) at 90～100 ℃, under the stirring condition in the maleic acid anhydride solution dropwise addition of acrylic acid and ammonium persulfate solution, dropwised in 40 minutes, under 50～90 ℃ of conditions, be incubated again, temperature retention time is 2-6 hour;
(5) under 50～80 ℃ of conditions, in above solution, drip 54g ammonium ceric nitrate and the 62g acrylic acid aqueous solution that has prepared simultaneously, 30min dropwises, insulation 1～4h;
(6) using 30% sodium hydrate aqueous solution to be neutralized to pH is 7～8, molecular weight is 8000～15000 maleic anhydride acrylic copolymer sodium salt;
(7) with Highspeedcentrifugingandsprayingdrier above liquid is carried out drying processing, promptly get the solid powdery dispersant.
2. the preparation method of an environment-friendly pesticide formulation specialty polymer dispersant is characterized in that this method comprises the steps:
(1) with the 300g running water 98g maleic acid ammonium salt is dissolved earlier, transferring pH is 4～6;
(2) be under 0～50 ℃ of condition in temperature, with the PAA dissolving, accent pH is 4-6;
(3) 200g running water, 2.5g TGA, 0.8g isopropyl alcohol are joined in the PAA solution and stir;
(4) the 10g ammonium persulfate is added 150g is water-soluble to be separated;
(5) under the stirring condition between 90～100 ℃ in the maleic acid ammonium salt solution dropwise addition of acrylic acid sodium solution and initiator solution, dropwised in 40 minutes, under 50～90 ℃ of conditions, be incubated again, temperature retention time is 2-6 hour;
(6) under 50～80 ℃ of conditions, in above solution, drip 36g ammonium ceric nitrate and the 58g acrylic acid aqueous solution that has prepared simultaneously, 30min dropwises, insulation 1～4h;
(7) using in 30% sodium hydrate aqueous solution with above polymer solution pH is 7～8, molecular weight is 15000～30000 maleic anhydride acrylic copolymer sodium salt;
(8) with Highspeedcentrifugingandsprayingdrier above liquid is carried out drying processing, promptly get the solid powdery dispersant.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101466605A CN101664029B (en) | 2008-09-04 | 2008-09-04 | Environment-friendly pesticide formulation special dispersing agent and application thereof |
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| CN2008101466605A CN101664029B (en) | 2008-09-04 | 2008-09-04 | Environment-friendly pesticide formulation special dispersing agent and application thereof |
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| CN101664029A CN101664029A (en) | 2010-03-10 |
| CN101664029B true CN101664029B (en) | 2012-07-25 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102308798A (en) * | 2011-04-22 | 2012-01-11 | 扬州斯培德化工有限公司 | Agricultural macromolecular surfactant and preparation method and application thereof |
| CN105386333A (en) * | 2015-12-17 | 2016-03-09 | 常熟市创裕印染有限公司 | Environmentally-friendly dye |
| CN106577642A (en) * | 2016-11-29 | 2017-04-26 | 上海师范大学 | Pesticide spraying additive, preparation method, and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140376A (en) * | 1996-12-27 | 2000-10-31 | Imerys Minerals, Ltd. | Dispersed aqueous suspensions |
| CN1526663A (en) * | 2003-03-04 | 2004-09-08 | 上海焦化有限公司 | A scale inhibitor and dispersant for high temperature gas washing water system |
| CN1837096A (en) * | 2005-03-23 | 2006-09-27 | 上海万森水处理有限公司 | Dirt dispersion agent |
| CN1986581A (en) * | 2006-11-29 | 2007-06-27 | 淮阴工学院 | Production process of low molecular weight polysodium acrylate as papermaking dispersant |
-
2008
- 2008-09-04 CN CN2008101466605A patent/CN101664029B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140376A (en) * | 1996-12-27 | 2000-10-31 | Imerys Minerals, Ltd. | Dispersed aqueous suspensions |
| CN1526663A (en) * | 2003-03-04 | 2004-09-08 | 上海焦化有限公司 | A scale inhibitor and dispersant for high temperature gas washing water system |
| CN1837096A (en) * | 2005-03-23 | 2006-09-27 | 上海万森水处理有限公司 | Dirt dispersion agent |
| CN1986581A (en) * | 2006-11-29 | 2007-06-27 | 淮阴工学院 | Production process of low molecular weight polysodium acrylate as papermaking dispersant |
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