CN104262525B - A kind of environment-friendly pesticide formulation terpolymer dispersants, preparation method and application - Google Patents
A kind of environment-friendly pesticide formulation terpolymer dispersants, preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of environment-friendly pesticide formulation terpolymer dispersants, preparation method and application.This terpolymer dispersants, it is the copolymer salt of the linear random arrangement being 25-75:13-50:20-54 according to A:B:C molar ratio by the structural unit represented with formula A, B and C, wherein: M is Na
+, K
+or NH
4 +; The weight-average molecular weight of terpolymer is 5000-50000.Described polycarboxylate is made up through emulsion free-radical polymerization reaction, then alkali lye neutralization of monomer methacrylic acid, butyl acrylate and N,N-DMAA.This terpolymer dispersants has excellent dispersion stabilization and slaking, in this dispersion agent building-up process, not with an organic solvent, and three-waste free discharge.
Description
Technical field
The present invention relates to a kind of polymeric dispersant, particularly relate to a kind of methacrylic acid/butyl acrylate/N,N-DMAA terpolymer salt and preparation method thereof.
Background technology
Polymeric dispersant (also known as hyper-dispersant) is a kind of novel dispersing auxiliary, develops the earliest for solving the scattering problem of granules of pigments in organic medium.Polymeric dispersant overcomes inorganic dispersant and easily brings foreign ion and organic molecule dispersant adsorption is insecure, dispersion stabilization is poor shortcoming into.At present, polymeric dispersant has been widely used in the field such as agricultural chemicals, coating, ink, printing and dyeing, filling plastic, pottery dispersion, cement dispersion.
In the application of agricultural chemicals; because most of pesticide original medicine particle is hydrophobic; therefore water spray or otherwise dispersed and be covered on protected crop or controlling object or its playground cannot directly be added in processing use; so must formulation be passed through, just can use after making various different preparation.Dispersion agent is the important component part in the pesticide formulation, macromolecule dispersing agent has special anchoring group structure, ionic linkage, covalent linkage, hydrogen bond and Van der Waals force can be adsorbed on drug particle surface firmly, form one deck adsorption layer, thus make pesticide granules form stable suspension system.At present, polymeric dispersant market being mainly used in agricultural chemicals is polycarboxylate salt dispersant, and polycarboxylate salt dispersant exists molecular weight distribution and is difficult to the problems such as control in building-up process, remains to be further improved.
Summary of the invention
Technical problem solved by the invention is: overcome existing polycarboxylate salt dispersant Problems existing in pesticides application, a kind of terpolymer dispersants with new molecular architecture is provided, there is excellent dispersion stabilization and slaking, in this dispersion agent building-up process, not with an organic solvent, three-waste free discharge, technique is simple, is applicable to suitability for industrialized production.
The present invention is directed to the application demand of agricultural chemicals, synthesized novel tertiary copolymer dispersant, be i.e. methacrylic acid-acrylic acid butyl ester-N,N-DMAA copolymer salt.In application aspect, there is the too much problem of foam in polycarboxylate salt dispersant, introduce ester group structure, significantly reduce foam volume in the present invention on carboxylate salt basis in some pesticide formulation (SC) course of processing.In addition, the N that wetting ability is strong is introduced in macromolecular chain, N-DMAA, the difenoconazole WDG formulation adopting this dispersion agent to process is after entering water, due to N, the water-absorbent of N-DMAA, water molecules can enter in WDG particle fast, improves the disintegration rate of WDG in water.Further, due to N,N-DMAA comparatively acrylamide have two-CH
3structure, effectively can be combined with former medicine particle, provide effectively sterically hindered, form stable pharmaceutical suspension system.
Specifically, the present invention proposes following technical scheme.
First aspect, the invention provides a kind of terpolymer dispersants, and it is the copolymer salt of the linear random arrangement being 25-75:13-50:20-54 according to A:B:C molar ratio by the structural unit represented with formula A, B and C,
Wherein: M is Na
+, K
+or NH
4 +;
The weight-average molecular weight of terpolymer is 5000-50000.
Preferably, the weight-average molecular weight of terpolymer is 10000-30000; The molar ratio of structural unit A:B:C is 35-60:20-40:20-34.
Preferably, the part by weight forming each raw material monomer of terpolymer dispersants is:
Methacrylic acid 20-70 part
Butyl acrylate 20-60 part
N,N-DMAA 20-50 part.
Preferably,
Preferred, the part by weight forming each raw material monomer of terpolymer dispersants is:
Methacrylic acid 30-50 part
Butyl acrylate 30-50 part
N,N-DMAA 20-30 part.
On the other hand, the invention provides a kind of preparation method of terpolymer dispersants, under the method is included in emulsifying agent, initiator and chain-transfer agent existence condition, at 70-90 DEG C, make the methacrylic acid of 20-70 weight part, the butyl acrylate of 20-60 weight part and the N of 20-50 weight part, N-DMAA carries out emulsion free-radical polymerization reaction, then alkali lye is added, form by the structural unit represented with formula A, B and C the copolymer salt of the linear random arrangement according to A:B:C molar ratio being 25-75:13-50:20-54
Wherein: M is Na
+, K
+or NH
4 +; The weight-average molecular weight of terpolymer is 5000-50000.
Preferably, described emulsifier is monomer total mass 0.5-2%, and described initiator amount is monomer total mass 1-5%, and described chain-transfer agent consumption is monomer total mass 1-5%.Here monomer total mass is methacrylic acid, butyl acrylate, and the quality summation of N,N-DMAA three kinds of monomers.
Preferably, by methacrylic acid, butyl acrylate, N,N-DMAA, mixes with chain-transfer agent, makes mixed liquor A; By emulsifying agent, initiator and water mixing, make mixed liquid B; Then, mixed liquor A dropped in mixed liquid B, time for adding is 15-30min.
Preferably, the mixed solution of mixed liquor A and mixed liquid B will be comprised at 70-90 DEG C of insulation reaction 2-3 hour.
Preferably, reaction product is cooled to 40-50 DEG C, then drips alkali lye and be neutralized to pH=7.
Preferably, described initiator is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate; Described emulsifying agent is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; Described chain-transfer agent is ethyl thioglycolate, Thiovanic acid butyl ester, Thiovanic acid, mercaptoethanol, 2 mercapto ethanol or tert-dodecyl mercaptan; Described alkali lye is the aqueous solution of ammoniacal liquor, NaOH or KOH.
Preferably, the part by weight forming each raw material monomer of terpolymer dispersants is:
Methacrylic acid 30-50 part
Butyl acrylate 30-50 part
N,N-DMAA 20-30 part;
The weight-average molecular weight of terpolymer is 10000-30000.
Another aspect, the invention provides a kind of above-mentioned terpolymer dispersants and applies in agricultural chemicals.
Preferably, the described pesticide formulation are pesticide water dispersible granules and pesticide suspension concentrate.
This dispersion agent has broad applicability, and weedicide is atrazine such as, and sterilant is difenoconazole, emamectin benzoate such as, and sterilant is Provado such as, as long as pesticides application formulation is water dispersible granules or water suspending agent, all can apply terpolymer dispersants of the present invention.
Last aspect, the invention provides a kind of pesticide preparation, comprises above-mentioned terpolymer dispersants.
The present invention adopts methacrylic acid by emulsion free-radical polymerization method, and butyl acrylate and N,N-DMAA obtain terpolymer dispersants liquid product, also can obtain solid phase prod by spraying dry further.This terpolymer dispersants can be widely used in the environment-friendly pesticide formulation such as pesticide water dispersible granules (WDG) and water suspending agent (SC).The present invention is compared with the carboxylate salt auxiliary agent of routine, owing to introducing butyl acrylate and N in dispersion agent main chain, N-DMAA, add the branched structure of dispersion agent, add sterically hindered, interaction force between dispersion and pesticide molecule is strengthened, significantly improves the suspension stability of the pesticide formulation.In dispersion agent building-up process of the present invention, not with an organic solvent, three-waste free discharge, technique is simple, is applicable to suitability for industrialized production.
Below in conjunction with accompanying drawing and each embodiment, the present invention and Advantageous Effects thereof are described in detail, wherein:
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the embodiment of the present invention 1 terpolymer dispersants.
Fig. 2 is the H1 nuclear magnetic spectrogram of the embodiment of the present invention 1 terpolymer dispersants.
Fig. 3 is the gel chromatography figure of the embodiment of the present invention 1 terpolymer dispersants.
Embodiment
The present invention overcomes existing polycarboxylate salt dispersant Problems existing in pesticides application, has synthesized novel tertiary copolymer dispersant, i.e. the polycarboxylate of methacrylic acid-acrylic acid butyl ester-N,N-DMAA.
Terpolymer dispersants of the present invention, it is the copolymer salt of the linear random arrangement being 25-75:13-50:20-54 according to A:B:C molar ratio by the structural unit represented with formula A, B and C,
Wherein: M is Na
+, K
+or NH
4 +;
The molar ratio of preferred structural unit A:B:C is 35-60:20-40:20-34; The weight-average molecular weight of terpolymer is 5000-50000, and preferably, weight-average molecular weight is 10000-30000
The part by weight forming each raw material monomer of terpolymer dispersants is:
Methacrylic acid 20-70 part
Butyl acrylate 20-60 part
N,N-DMAA 20-50 part.
Preferably, the part by weight forming each raw material monomer of terpolymer dispersants is:
Methacrylic acid 30-50 part
Butyl acrylate 30-50 part
N,N-DMAA 20-30 part.
The preparation method of this terpolymer dispersants is: under emulsifying agent, initiator and chain-transfer agent existence condition, at 70-90 DEG C, make the methacrylic acid of 20-70 weight part, the butyl acrylate of 20-60 weight part and the N of 20-50 weight part, N-DMAA carries out emulsion free-radical polymerization reaction, then add alkali lye, obtain terpolymer dispersants.
The method specifically comprises the steps:
(1) initiator of the emulsifying agent of monomer total mass 0.5-2%, monomer total mass 1-5% and suitable quantity of water are joined in reactor;
(2) by the methacrylic acid of 20-70 weight part, the butyl acrylate of 20-60 weight part, the N,N-DMAA of 20-50 weight part, mixes with monomer total mass 1-5% chain-transfer agent, makes mixed liquor A;
(3) mixed liquor A being dropped to step 1) in described reactor, time for adding is 15-30min;
(4), after mixed liquor A drips, by the mixed solution in reactor at 70-90 DEG C of insulation 2-3 hour, make monomeric acrylic, butyl acrylate and N,N-DMAA carry out copolyreaction;
(5) step (4) gained reaction product is cooled to 40-50 DEG C, then drips alkali lye and be neutralized to pH=7.The present invention contains ester group, and the too high meeting of pH causes ester-type hydrolysis, and the too low product of pH can present type acidity, can produce flocculation in water, affects the dispersiveness of product.
Initiator of the present invention is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate.Emulsifying agent of the present invention is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.Chain-transfer agent of the present invention is ethyl thioglycolate, Thiovanic acid butyl ester, Thiovanic acid, mercaptoethanol, 2 mercapto ethanol or tert-dodecyl mercaptan; Alkali lye of the present invention is the aqueous solution of ammoniacal liquor, NaOH or KOH.Containing the butyl acrylate being insoluble in water in raw material of the present invention, prior art is solution polymerization for oil-soluble monomer conventional synthesis process, namely adopt alcohols or toluene etc. as solvent, BPO is that initiator reacts, but the dissolvent residual in this polymerization process product is difficult to remove, product is finally dry through high temperature spray, and organic solvent residual directly can be discharged in air and have environmental problem.The present invention adopts letex polymerization to avoid Solvent, selects suitable initiator and chain-transfer agent consumption, obtains the dispersion agent that molecular weight is relatively low.
In dispersion agent building-up process of the present invention, not with an organic solvent, three-waste free discharge, technique is simple, is applicable to suitability for industrialized production.This terpolymer dispersants is applied in agricultural chemicals, such as the environment-friendly pesticide formulation such as pesticide water dispersible granules (WDG) and water suspending agent (SC).Adopting dispersion agent of the present invention to prepare the method for water dispersible granules (WDG) and water suspending agent (SC), is common method well known in the art.
Below by specific embodiment, the preparation method of terpolymer dispersants of the present invention and the properties of terpolymer dispersants are described, and the performance of the agricultural chemicals made with this terpolymer dispersants.
In embodiment, used each reagent and instrument are originated as shown in table 1 and table 2 below.
Table 1: the reagent used in embodiment and type information table
Facility information table look-up used by table 2 embodiment
Embodiment 1
Deionized water 200g, ammonium persulphate 5g and sodium laurylsulfonate 2g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 70 DEG C; then the methacrylic acid containing 50g is dripped; the butyl acrylate of 30g; the N of 20g; the mixing liquid of the Thiovanic acid of N-DMAA and 2g; time for adding 30min; dropping terminates rear insulation 3h; then 40 DEG C are cooled to; then in product, add 30wt%NaOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 17500.The gel chromatography figure of this copolymer dispersant shown in Fig. 3.
infrared analysis
This copolymer dispersant is adopted the sample preparation of KBr compressing tablet, then use PerkinElmerFrontier type infrared spectrometer to carry out infrared analysis.
As shown in Figure 1 FT-IR (KBr): 863cm
-1(C (=O) O vibrates), 1161cm
-1(C-O-C stretching vibration), 1563,1452cm
-1(COO
-absorption band), 1401cm
-1(-C-N vibration), 1449cm
-1(-CH
3middle C-H flexural vibration), 1723cm
-1(C=O stretching vibration), 2880-2960cm
-1(CH
3, CH
2stretching vibration), 3451cm
-1(COO-association).As seen from Figure 1, the present invention obtains the copolymer salt that the structural unit represented with formula A, B and C is the linear random arrangement of 25-75:13-50:20-54 according to A:B:C molar ratio,
polymer core magnetic chart spectrum analysis
Fig. 2 is that copolymer dispersant is under the D2O condition
1h-NMR collection of illustrative plates.(Brooker AV600) nuclear magnetic resonance analyser is used to measure.In Fig. 2, in each monomer, the chemical shift of H is in table 3, and that is, the present invention obtains the terpolymer as structure above.
The chemical shift of table 3H
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 4:
Table 4
| Constituent content % | C | O | N | Na |
| Theoretical value | 56.32 | 27.41 | 2.64 | 13.63 |
| Observed value | 55.59 | 28.12 | 2.61 | 13.68 |
Polymer monomer molar percentage is: A59%B21%C20%
Embodiment 2
Deionized water 200g, Potassium Persulphate 4g and Sodium dodecylbenzene sulfonate 0.5g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 90 DEG C; then the methacrylic acid containing 30g is dripped; the butyl acrylate of 50g; the N of 20g; N-DMAA; the mixing liquid of 1g ethyl thioglycolate; time for adding 20min; dropping terminates rear insulation 2h; then be cooled to 50 DEG C, then in product, add ammonia soln adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 21600.
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 5:
Table 5
| Constituent content % | C | O | N | Na |
| Theoretical value | 66.96 | 21.45 | 3.02 | 8.57 |
| Observed value | 66.45 | 21.94 | 2.97 | 8.64 |
Polymer monomer molar percentage is: A38%B39%C23%
Embodiment 3
Deionized water 200g, Potassium Persulphate 3g and sodium lauryl sulphate 1g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 70 DEG C; then the methacrylic acid containing 30g is dripped; the butyl acrylate of 40g; the N of 30g; the mixing liquid of the Thiovanic acid butyl ester of N-DMAA and 2g; time for adding 20min; dropping terminates rear insulation 3h; then 40 DEG C are cooled to; then in product, add 30wt%KOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 28300.
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 6:
Table 6
| Constituent content % | C | O | N | Na |
| Theoretical value | 66.21 | 20.76 | 4.53 | 8.50 |
| Observed value | 66.12 | 20.81 | 4.51 | 8.56 |
Polymer monomer molar percentage is: A37%B31%C32%
Embodiment 4
Deionized water 200g, ammonium persulphate 1g and sodium laurylsulfonate 1.5g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 90 DEG C; then the methacrylic acid containing 20g is dripped; the butyl acrylate of 60g; the N of 20g; the mixing liquid of the mercaptoethanol of N-DMAA and 2g; time for adding 25min; dropping terminates rear insulation 2h; then 40 DEG C are cooled to; then in product, add 30wt%NaOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 46900.
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 7:
Table 7
| Constituent content % | C | O | N | Na |
| Theoretical value | 68.96 | 22.20 | 3.06 | 5.28 |
| Observed value | 60.09 | 22.46 | 3.04 | 5.41 |
Polymer monomer molar percentage is: A27%B49%C24%
Embodiment 5
Deionized water 200g, ammonium persulphate 2g and Sodium dodecylbenzene sulfonate 2g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 80 DEG C; then the methacrylic acid containing 50g is dripped; the butyl acrylate of 20g; the N of 30g; the mixing liquid of the 2 mercapto ethanol of N-DMAA and 2g; time for adding 25min; dropping terminates rear insulation 3h; then 50 DEG C are cooled to; then in product, add ammonia soln adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 32200.
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 8:
Table 8
| Constituent content % | C | O | N | Na |
| Theoretical value | 62.88 | 18.54 | 4.47 | 14.11 |
| Observed value | 62.39 | 18.87 | 4.42 | 14.32 |
Polymer monomer molar percentage is: A57%B14%C29%
Embodiment 6
Deionized water 200g, Sodium Persulfate 5g and sodium lauryl sulphate 1.5g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 90 DEG C; then the methacrylic acid containing 30g is dripped; the butyl acrylate of 20g; the N of 50g; the mixing liquid of the tert-dodecyl mercaptan of N-DMAA and 5g; time for adding 30min; dropping terminates rear insulation 2h; then 40 DEG C are cooled to; then in product, add 30wt%KOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 6700.
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 9:
Table 9
| Constituent content % | C | O | N | Na |
| Theoretical value | 64.54 | 19.37 | 7.54 | 8.55 |
| Observed value | 64.15 | 19.75 | 7.49 | 8.61 |
Polymer monomer molar percentage is: A35%B14%C51%
Comparative example 1
Deionized water 200g, ammonium persulphate 5g and sodium laurylsulfonate 2g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 70 DEG C; then the methacrylic acid containing 70g is dripped; the butyl acrylate of 25g; the N of 5g; the mixing liquid of the Thiovanic acid of N-DMAA and 1g; time for adding 30min; dropping terminates rear insulation 3h; then 40 DEG C are cooled to; then in product, add 30wt%NaOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH2PO4 solution and methyl alcohol mixed liquor (70:30% (v/v)) for moving phase, PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 14700.
polymkeric substance ultimate analysis
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 10:
Table 10
| Constituent content % | C | O | N | Na |
| Theoretical value | 60.27 | 19.89 | 0.72 | 19.12 |
| Observed value | 60.15 | 20.01 | 0.64 | 19.20 |
Comparative example 2
Deionized water 200g, ammonium persulphate 5g and sodium laurylsulfonate 2g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 70 DEG C; then the methacrylic acid containing 20g is dripped; the butyl acrylate of 10g; the N of 70g; the mixing liquid of the Thiovanic acid of N-DMAA and 1g; time for adding 30min; dropping terminates rear insulation 3h; then 40 DEG C are cooled to; then in product, add 30wt%NaOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 15800.
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 11:
Table 11
| Constituent content % | C | O | N | Na |
| Theoretical value | 64.97 | 18.61 | 10.66 | 5.76 |
| Observed value | 64.80 | 18.74 | 10.64 | 5.82 |
Comparative example 3
Deionized water 200g, ammonium persulphate 0.2g and sodium laurylsulfonate 2g is added in the 500ml four-hole boiling flask with stirring, heating, thermometer, backflow, reinforced and nitrogen protection device; stirring is warming up to 70 DEG C; then the methacrylic acid containing 50g is dripped; the butyl acrylate of 30g; the N of 20g; the mixing liquid of the Thiovanic acid of N-DMAA and 0.2g; time for adding 30min; dropping terminates rear insulation 3h; then 40 DEG C are cooled to; then in product, add 30wt%NaOH solution adjust ph to 7, spraying dry obtains solid product.
Adopt gel chromatography and laser light scattering combined instrument, with 50mMNaH
2pO
4solution and methyl alcohol mixed liquor (70:30% (v/v)) are moving phase, and PEG20000 is standard substance, and the weight-average molecular weight of the copolymer dispersant prepared by mensuration is 635600.
Use (ZSX of science) Xray fluorescence spectrometer to analyze the carrying out of this copolymer dispersant, result is as shown in table 12:
Table 12
| Constituent content % | C | O | N | Na |
| Theoretical value | 56.32 | 27.41 | 2.64 | 13.63 |
| Observed value | 55.52 | 28.15 | 2.68 | 13.65 |
application of dispersant performance evaluation
Be that during 90% atrazine WDG and 10% difenoconazole WDG fill a prescription, evaluate the performance of dispersion agent of the present invention, concrete scheme is as follows at massfraction:
(1) 90% atrazine WDG
By 92.8g atrazine; 5g dispersion agent of the present invention (respectively Example 1, embodiment 2, embodiment 3, comparative example 1 and comparative example 2 dispersion agent); 2gAOS and appropriate amount of deionized water; mediate in kneader; then the material obtained is dropped in rotary extrusion tablets press and carry out granulation; then 70 DEG C of oven dry 1h in constant temperature blast drying oven, screening obtains product.
(2) 10% difenoconazole WDG
By 11g difenoconazole; 4g dispersion agent of the present invention (respectively Example 4, embodiment 5, embodiment 6 dispersion agent); 3gAOS, 3gD425,2g white carbon black; 30g W-Gum; 47g ammonium sulfate and appropriate amount of deionized water, mediate in kneader, then dropped in rotary extrusion tablets press by the material obtained and carry out granulation; then 70 DEG C of oven dry 1h in constant temperature blast drying oven, screening obtains product.
Carry out performance test respectively to the pesticide water dispersible granules (WDG) that above-described embodiment 1-6 and comparative example 1 and comparative example 2 are made, testing method is as follows:
1. suspensibility measures
The suspensibility of the water dispersible granules of preparation is measured according to GB GB/T14825-2006 detection method (method 2).
2. wettability determination
Adopt measuring graduates test method(s), pouring 1.0g sample fast into filling in 500ml deionized water graduated cylinder, not stirring, record 99% sample to sink to tin at the bottom of time.
3. slaking measures
Adopt measuring graduates test method(s), in the 100ml tool plug graduated cylinder that 90ml deionized water is housed, add 0.5g particulate samples at 25 DEG C, clamp the middle part of graduated cylinder afterwards, clog nozzle, with the speed of 8r/min around central rotation, until sample complete disintegration in water, record disintegration time
4. heat storage suspensibility measures
About 5g sample is sealed in 50ml ampoule, is placed in (54 ± 2) DEG C constant temperature oven, store and take out after 14 days, 1. measure suspensibility by method.
Pesticide water dispersible granules (WDG) test result that embodiment 1-6 makes is as shown in table 13 and table 14.
Table 13 polymeric dispersant is applied in 90% atrazine WDG
Table 14 polymeric dispersant is applied in 10% difenoconazole WDG
As can be seen from table 13 and table 14 evaluation result, polymeric dispersant prepared by the present invention has excellent dispersion stabilization and slaking, wetting time and disintegration time short, in 90% atrazine WDG, suspensibility is more than 90.2%, and storage suspensibility is more than 89.5%; In 10% difenoconazole WDG, suspensibility is more than 87.8%, and storage suspensibility is more than 85.6%.In dispersion agent building-up process of the present invention, not with an organic solvent, three-waste free discharge, technique is simple, is applicable to suitability for industrialized production.
Claims (15)
1. be used as a terpolymer for dispersion agent, it is characterized in that, it is the copolymer salt of the linear random arrangement being 25-75:13-50:20-54 according to A:B:C molar ratio by the structural unit represented with formula A, B and C,
Wherein: M is Na
+, K
+or NH
4 +;
The weight-average molecular weight of terpolymer is 5000-50000.
2. terpolymer according to claim 1, is characterized in that, the weight-average molecular weight of terpolymer is 10000-30000, and the molar ratio of structural unit A:B:C is 35-60:20-40:20-34.
3. terpolymer according to claim 1 and 2, is characterized in that, the part by weight forming each raw material monomer of terpolymer is:
Methacrylic acid 20-70 part
Butyl acrylate 20-60 part
N,N-DMAA 20-50 part.
4. terpolymer according to claim 3, is characterized in that, the part by weight forming each raw material monomer of terpolymer is:
Methacrylic acid 30-50 part
Butyl acrylate 30-50 part
N,N-DMAA 20-30 part.
5. terpolymer according to claim 2, is characterized in that, described polycarboxylate is made up through emulsion free-radical polymerization reaction, then alkali lye neutralization of monomer methacrylic acid, butyl acrylate and N,N-DMAA; In emulsion free-radical polymerization reaction, emulsifier is monomer total mass 0.5-2%, and initiator amount is monomer total mass 1%-5%, and chain-transfer agent consumption is monomer total mass 1-5%.
6. the preparation method of a terpolymer, under the method is included in emulsifying agent, initiator and chain-transfer agent existence condition, at 70-90 DEG C, make the methacrylic acid of 20-70 weight part, the butyl acrylate of 20-60 weight part and the N,N-DMAA of 20-50 weight part carry out emulsion free-radical polymerization reaction, then add alkali lye, form by the structural unit represented with formula A, B and C the copolymer salt of the linear random arrangement according to A:B:C molar ratio being 25-75:13-50:20-54
Wherein: M is Na
+, K
+or NH
4 +; The weight-average molecular weight of terpolymer is 5000-50000.
7. preparation method according to claim 6, is characterized in that, described emulsifier is monomer total mass 0.5-2%, and described initiator amount is monomer total mass 1%-5%, and described chain-transfer agent consumption is monomer total mass 1-5%.
8. the preparation method according to claim 6 or 7, is characterized in that, by methacrylic acid, and butyl acrylate, N,N-DMAA, mixes with chain-transfer agent, makes mixed liquor A; By emulsifying agent, initiator and water mixing, make mixed liquid B; Then, mixed liquor A dropped in mixed liquid B, time for adding is 15-30min.
9. preparation method according to claim 8, is characterized in that, will comprise the mixed solution of mixed liquor A and mixed liquid B at 70-90 DEG C of insulation reaction 2-3 hour.
10. preparation method according to claim 9, is characterized in that, reaction product is cooled to 40-50 DEG C, then drips alkali lye and is neutralized to pH=7.
11. preparation methods according to claim 10, is characterized in that, described initiator is selected from Potassium Persulphate, Sodium Persulfate or ammonium persulphate; Described emulsifying agent is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; Described chain-transfer agent is ethyl thioglycolate, Thiovanic acid butyl ester, Thiovanic acid, mercaptoethanol, 2 mercapto ethanol or tert-dodecyl mercaptan; Described alkali lye is the aqueous solution of ammoniacal liquor, NaOH or KOH.
12. 1 kinds of terpolymers as dispersion agent, it is prepared by the preparation method described in any one of claim 6-11.
The terpolymer being used as dispersion agent described in 13. 1 kinds of any one of claim 1-5 is applied in agricultural chemicals.
14. application according to claim 13, is characterized in that, the described pesticide formulation are pesticide water dispersible granules and pesticide suspension concentrate.
15. 1 kinds of pesticide preparation, is characterized in that, comprise the terpolymer being used as dispersion agent described in any one of claim 1-5.
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