CN102349509A - Method for preparing lignin urea-formaldehyde pesticide microcapsule - Google Patents
Method for preparing lignin urea-formaldehyde pesticide microcapsule Download PDFInfo
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Abstract
The invention discloses a method for preparing a lignin urea-formaldehyde pesticide microcapsule. According to the invention, the method comprises the following steps: taking modified lignin, formaldehyde and urea as a monomer, forming a water-soluble performed polymer under base catalysis, diluting and forming continuous phase, forming dispersed phase by pesticide, an organic solvent and a surfactant, mixing and stirring the continuous phase and the dispersed phase to form an oil-in-water emulsion, performing in situ condensation polymerization under the acidic condition, heating and solidifying, pumping filtration and washing, drying to obtain the solid microcapsule particles. The modified lignin is obtained by formaldehyde hydroxymethyl modification of the industrial grade wheat straw soda lignin. According to the invention, the waste wheat straw soda lignin in paper industry is taken as the main wall material, so that the production cost of the microcapsule can be effectively reduced and the resource utilization of waste biomass can be realized. The preparation method of the invention has the advantages of simple process, rapidity and controllable microcapsule particle size, and is capable of realizing the industrial production, increasing the pesticide utilization rate, prolonging the persistent period, minimizing the environmental pollution in the process of agricultural production, reducing the agriculture production cost and the like, and has good market prospect.
Description
Technical field
The invention belongs to the pesticide micro capsule preparing technical field, be specifically related to a kind of preparation method of lignin urea aldehyde radical pesticide micro capsule.
Background technology
Characteristics such as the pesticide micro capsule preparation has safety, low toxicity, efficient, low-residual, Environmental compatibility is good, the lasting period is long become the new direction that modern agricultural chemicals develops.But owing to the microcapsules preparation cost too high with reason such as unstable properties, the microencapsulation of pesticide preparation fails in actual production, to be used widely.How reducing cost, the envelop rate and the sustained release performance that improve microcapsules are the key points that microcapsule formulation obtains applying.
Lignin is the aromatic polymer that is present in one type of complicacy in the plant corpus, is only second to cellulose at the reserves of occurring in nature, and annual according to incompletely statistics global plant growing can produce 1,500 hundred million tons of lignin.The enhancing day by day of and human environmental consciousness exhausted day by day along with petroleum resources, the higher value application of this natural reproducible resource of lignin has received common concern.
At present, the modification derivant sodium lignin sulfonate of lignin is widely used as the dispersant in pesticide water dispersible granules, suspending agent and the wetting powder.Process the particle slow release agricultural chemicals after also having report with the alkali lignin of drying and crushing and agricultural chemicals and auxiliary agent mixing, granulation, drying, and carried out field trial, but do not see the report of lignin in the existing document as microcapsule wall material.
Summary of the invention
The object of the invention provides a kind of preparation method of lignin urea aldehyde radical pesticide micro capsule; Prepare pesticide micro capsule through seeking suitable preparation method; Improve the envelop rate and the sustained release performance of microcapsules, and reduce cost, solve the deficiency in existing pesticide micro capsule preparation technique field.
The object of the invention is achieved through following technical scheme:
The present invention provides a kind of preparation method of lignin urea aldehyde radical pesticide micro capsule, is monomer with modified lignin resin, formaldehyde and urea, water as solvent, and base catalysis forms soluble prepolymer down, forms continuous phase behind the dilute with water; Become disperse phase with agricultural chemicals, organic solvent and group of surfactants; After continuous phase and disperse phase mixing; Under the certain speed mechanical agitation, form stable O/w emulsion; Through the acid catalysis home position polymerization reaction; At oil droplets coated high molecular wall material; Heat up and solidify, suction filtration obtains the solid microcapsule granule after washing, the drying.
The preparation method of said lignin urea aldehyde radical pesticide micro capsule specifically may further comprise the steps:
(1) preparation lignin urea aldehyde performed polymer;
Urea is soluble in water, and alkali condition adds down formalin, and stirring reaction adds the lignin aqueous solution after the modification then, continues reaction and obtaining prepolymer solution; Fat-soluble agricultural chemicals and surfactant are dissolved in the core of organic solvent as microcapsules;
The proportioning of the lignin after the said modification, formaldehyde and urea is confirmed according to following ratio: formaldehyde: urea=1.5～2.0 (amount of substance ratio), in the microcapsules, modified lignin resin: wall material (formaldehyde+urea+modified lignin resin)=27～45% (mass ratio);
Said alkali condition is that the pH value of adjusting aqueous solution of urea is 8～9, preferably adopts the 0.2mol/L sodium hydroxide solution to regulate the pH value of aqueous solution of urea; The mass fraction of formaldehyde is 37% in the said formalin; Said stirring reaction is that bath temperature is slowly risen to 70～75 ℃ of (programming rate of normal water bath, about 1 ℃/min), and under this temperature, continue stirring reaction 80min from room temperature.
The lignin of described modification is a gained solution after the modification of technical grade wheat straw alkali lignin process formaldehyde methylolation.
The method of modifying of said lignin is: according to the 20g alkali lignin: the ratio of 60～70 ml distilled water is dissolved in alkali lignin in the distilled water; According to the 20g alkali lignin: the ratio of 5.70ml formalin (formalin of mass fraction 37%) adds formalin; Using the NaOH aqueous solution to transfer the pH value of system is 10～11; Water-bath is heated to 90 ℃; Reaction time 3h; Obtain dissolving the solution of modified lignin resin; Being diluted to 100ml and adjust pH is 8～9, and the concentration of gained modified lignin resin solution is 2g/10ml.
The organic solvent of said preparation microcapsules core can adopt the mixture of chlorobenzene, tetrachloro-ethylene or toluene one of them and chlorobenzene, and the mass ratio of said chlorobenzene, tetrachloro-ethylene or toluene and chlorobenzene is 3:2; Perhaps can to adopt tetrachloro-ethylene and toluene be the mixture of 3:2 according to mass ratio to organic solvent, organic solvent for the dilution performed polymer with 1/5 of water volume.Said fat-soluble agricultural chemicals be for being dissolved in the solid-state or liquid pesticide of above-mentioned organic solvent, as Avermectin, chlopyrifos,
α-naphthoic acid etc.; Said surfactant is a nonionic surface active agent, like span80, span85, and Tween80 etc., the quality of surfactant is 2～3% of a thinned water quality.
(2) the water miscible lignin urea aldehyde performed polymer after the core of the said microcapsules of step (1) and the dilution is mixed the emulsion of high-speed stirred formation O/W;
Preferably in above-mentioned prepolymer solution; Add sodium chloride, deionized water successively; Under the room temperature after the stirring and dissolving; Under 600～1400rpm speed of agitator; Add a certain amount of core for preparing (agricultural chemicals+surfactant+organic solvent) fast; Under above-mentioned speed conditions, continue to stir 30～35min, form stable o/w type emulsion; Microcapsule wall can be effectively reinforced in the adding of said sodium chloride, and preferably according to sodium chloride (gram): deionized water (gram) is that the ratio of 1:10～17 adds sodium chloride; Deionized water can be used to dilute performed polymer, and preferably according to prepolymer solution (ml): deionized water (ml) is that the ratio of 1:15～20 adds deionized water;
(3) lignin urea aldehyde performed polymer further polymerization under acid condition of water in the O/W emulsion that step (2) is made forms polymeric membrane on oil phase drop surface, makes pesticide micro capsule through the intensification curing reaction;
Preferred scheme is that rotating speed is transferred to 300～500rpm, uses acid solution slowly to regulate under the water bath condition that O/W type ph value of emulsion is 2～4,30～35 ℃ of temperature, continues to stir polycondensation reaction 50～70min; With warming-in-water to 65～75 ℃, curing reaction 90～120min, suction filtration is used water washing, about freeze drying or 30～50 ℃ of following vacuum drying 10～24h or freeze drying 30h, the drug-loading microcapsule particle.
The aqueous solution such as said acid solution preferred mass mark 4% oxalic acid, 0.2mol/L hydrochloric acid, 0.2mol/L sulfuric acid, the time that drips acid solution is controlled in 20 ~ 30min, and is best with mass fraction 4% oxalic acid solution effect.
Preferably, the bath temperature of said polycondensation reaction is preferably 30 ℃, and polycondensation reaction time is 60min.
Preferably, the bath temperature of said curing reaction is preferably 65 ℃, and the curing reaction time is 120min.
The computing formula of medicine carrying amount and envelop rate institute foundation is among the present invention:
Slow-release time is meant that sample accumulative total release rate under certain release conditions reached for 100% used time.
Testing used instrument is U.S. Agilent 1100 Series high performance liquid chromatographs, is determined at the absworption peak area of measuring wavelength.
Beneficial effect of the present invention:
The prior art for preparing pesticide micro capsule; Exist always the microcapsules preparation cost too high with technical problem such as unstable properties; It is the technical barrier in puzzlement present technique field that envelop rate and the sustained release performance that how to improve microcapsules reduces cost simultaneously always, has also restricted applying of pesticide micro capsule to a great extent.
The present invention utilizes and has alcoholic extract hydroxyl group, phenolic hydroxyl group, carbonyl isoreactivity group in the lignin molecule, generates the methylolation lignin through the formaldehyde modification, and it is active to increase lignin reaction, generates lignin Lauxite wall material with urea aldehyde blend condensation.The present invention uses abandoned biomass----lignin to replace part urea; Practice thrift cost; Modified lignin resin can with formaldehyde further condensation under alkali condition, improve the physicochemical property of Lauxite, the microcapsule wall material of formation has permeability, film forming and biodegradability preferably.
Further; In the methods of the invention; Form the performed polymer elementary reaction and begin slowly to be warming up to design temperature from room temperature; The addition reaction of urea and formaldehyde is exothermic reaction; If firing rate is too fast during beginning, temperature of reaction system is too high, reacts very violent; Can be with the generation of side reaction, envelop rate will be very low.PH value during pre-polymerization preferably is controlled at 8～9, when pH less than 4 the time, the prepolymer solution muddiness of preparation is homogeneous phase not, has generated the methylene urea deposition, this performed polymer is difficult to prepare microcapsules; When the pH value was 4～6, the further condensation under acid condition of the methylolurea of generation was polymethylene urea deposition, when coating the agricultural chemicals core with this performed polymer, can contain a large amount of depositions in the final microcapsules product, only obtains a small amount of microcapsule granule; When system is neutrality or alkalescent (the pH value is 7～10), generate stable water-soluble methylolurea, it is transparent thick that this performed polymer is, and the surface of microcapsule form that continuation polycondensation coating oil phase drop obtains is good, and smooth surface is fine and close; Under strong alkaline condition (pH>10), the intermolecular dehydration of methylolurea generates dimethylene ether, and the performed polymer aqueous solution becomes not homogeneous phase of muddiness; The same coating that influences microcapsules; Have only a small amount of microcapsules to form, and the insecure easy of crack of microcapsules that forms, configuration of surface is coarse.
In the methods of the invention, the pH value in further polycondensation reaction stage of performed polymer is controlled at 2～4, and the speed that drips acid solution is slower.When the pH value is lower than 1.5, the formation excessive velocities of cyst wall, the surface is comparatively coarse.If disposable adding acid solution, curing reaction is too violent, and the polymer of formation has little time to coat film forming in oil droplets, just separate out the deposition frustillatum rapidly at aqueous phase.
The surface of microcapsule that adopts the inventive method to prepare is smooth, sound construction, and form is better, and very high medicine carrying amount and envelop rate are arranged, and slow releasing function is obvious.
The present invention is the main wall material of microcapsules with paper-making industry discarded object wheat straw alkali lignin, effectively reduces the production cost of microcapsules, realizes the recycling of abandoned biomass; Simultaneously owing to form in the microcapsule wall material process; Radical change does not take place in the basic structure of lignin; This natural biomass is that the microcapsules of main wall material can slowly be degraded at natural world; Change into humus; The long-term use has improving effect to soil; Thereby lignin is main substrate preparation pesticide micro capsule, and having solved great majority is the environmental problem of the microcapsules difficult degradation of wall material with the synthetic macromolecular compound, realizes the target of pesticide micro capsule preparation green non-pollution.
Preparation technology of the present invention is easy; Fast; The microcapsules size is controlled, can realize suitability for industrialized production, and said pesticide micro capsule has good market prospects at aspects such as the availability that improves agricultural chemicals, prolongation lasting period, the pollution that reduces environment in the agricultural production process, reduction agriculture production costs.
Description of drawings
The pesticide micro capsule particle diameter distribution map of Fig. 1 the inventive method preparation;
The pesticide micro capsule microscope figure of Fig. 2 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Fig. 3 the inventive method preparation;
The pesticide micro capsule microscope figure of Fig. 4 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Fig. 5 the inventive method preparation;
The pesticide micro capsule microscope figure of Fig. 6 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Fig. 7 the inventive method preparation;
The pesticide micro capsule microscope figure of Fig. 8 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Fig. 9 the inventive method preparation;
The pesticide micro capsule microscope figure of Figure 10 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Figure 11 the inventive method preparation;
The pesticide micro capsule microscope figure of Figure 12 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Figure 13 the inventive method preparation;
The pesticide micro capsule microscope figure of Figure 14 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Figure 15 the inventive method preparation;
The pesticide micro capsule microscope figure of Figure 16 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Figure 17 the inventive method preparation;
The pesticide micro capsule microscope figure of Figure 18 the inventive method preparation;
The pesticide micro capsule particle diameter distribution map of Figure 19 the inventive method preparation;
The pesticide micro capsule microscope figure of Figure 20 the inventive method preparation.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and specific embodiment.Unless stated otherwise, the reagent that the embodiment of the invention adopts, raw material etc. are conventional reagent, raw material etc., and the method that embodiment adopts is all present technique field conventional method unless stated otherwise.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (amount of substance ratio); Surfactant span85: deionized water=3% (mass ratio); Modified lignin resin: wall material (formaldehyde+urea+modified lignin resin)=37.6% (mass ratio), Avermectin: wall material (urea+formaldehyde+modified lignin resin)=1 (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9 (using value range); Add 3.0ml formaldehyde then; Under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under this temperature, continue stirring reaction 80min.The aqueous solution 7.5ml that adds modified lignin resin continues reaction 120min and obtains prepolymer solution, is cooled to room temperature and places.
The method of modifying of said lignin is: according to the 20g alkali lignin: the ratio of 60～70ml distilled water is dissolved in alkali lignin in the distilled water; According to the 20g alkali lignin: the ratio of 5.70ml formalin (formalin of mass fraction 37%) adds formalin; Using the NaOH aqueous solution to transfer the pH value of system is 10～11; Water-bath is heated to 90 ℃; Reaction time 3h; Obtain dissolving the solution of modified lignin resin; Being diluted to 100ml and adjust pH is 8～9, and the concentration of gained modified lignin resin solution is 2g/10ml.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 1000rpm speed of agitator, add core solution (2.0g Avermectin+6.0g span85+50.0g chlorobenzene) fast, under this rotating speed, continue to stir 35min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.
Rotating speed is transferred to 300rpm; In above-mentioned O/W type emulsion, slowly dripping mass fraction and be 4% oxalic acid aqueous solution, to regulate the pH value of emulsion be 2～3; Bath temperature is transferred to 30 ℃ then; After continuing to stir 60min, bath temperature is warming up to 65 ℃, behind the curing reaction 120min; Suction filtration; Use water washing, 50 ℃ of following vacuum drying 10h get the solid microcapsule granule.See and attach shown in Fig. 1 and 2 that said microcapsules particle diameter mainly is distributed in 10～20um, average grain diameter is 15.77um, and the medicine carrying amount is 24.5%, and envelop rate is 69.2%, and slow-release time is 121h.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (ratio of amount); Surfactant span85: deionized water=3% (mass ratio); Avermectin: wall material (urea+formaldehyde+modified lignin resin)=1 (mass ratio), wooden modification quality: wall material (urea+formaldehyde+modified lignin resin)=37.6% (mass ratio).
In there-necked flask, be weighed into 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.0ml formaldehyde then, under the 300rmp mixing speed, bath temperature slowly is warming up to 75 ℃, and under this temperature, continue stirring reaction 80min.Add modified lignin resin solution (preparation method is with reference to embodiment 1) 7.5ml, continue reaction 120min and form prepolymer solution.Being cooled to room temperature afterwards places.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 800rpm speed of agitator, add core solution (2.0g Avermectin+6.0g span85+70.0g tetrachloro-ethylene) fast, under this rotating speed, continue to stir 35min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, use mass fraction be 4% oxalic acid aqueous solution slowly to drip regulator solution pH value be 2～3, water-bath is transferred to 30 ℃ then; After continue stirring 60min, with warming-in-water to 75 ℃, behind the curing reaction 60min; Suction filtration, use water washing, 30 ℃ of following vacuum drying 24h, the solid microcapsule granule; See shown in accompanying drawing 3 and 4; Said microcapsules particle diameter mainly is distributed in 6～30um, and average grain diameter is 16.19um, and the medicine carrying amount is 20.3%; Envelop rate is 70.3%, and slow-release time is 126h.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (ratio of amount); Surfactant span85: deionized water=3% (mass ratio), modified lignin resin: wall material (formaldehyde+urea+modified lignin resin)=44.6% (mass ratio) Avermectin: wall material (urea+formaldehyde+modified lignin resin)=0.5 (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.0ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under temperature, continue stirring reaction 70min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 10.0ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution; Add sodium chloride 15.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 800rpm speed of agitator, add core solution (1.0g Avermectin+6.0g span85+20.0g chlorobenzene+30.0g toluene) fast, under this rotating speed, continue to stir 30min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, use mass fraction be 4% oxalic acid solution slowly to drip regulator solution pH value be 2～3, water-bath is transferred to 30 ℃ then; After continue stirring 60min, with warming-in-water to 60 ℃, behind the curing reaction 120min; Suction filtration, use water washing, 40 ℃ of following vacuum drying 14h, the solid microcapsule granule; See shown in accompanying drawing 5 and 6; Particle diameter mainly is distributed in 20～50um, and average grain diameter is 26.52um, and the medicine carrying amount is 13.4%; Envelop rate is 79.1%, and slow-release time is 113h.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (amount of substance ratio); Emulsifier span85: deionized water=3% (mass ratio); Modified lignin resin: wall material (formaldehyde+urea+modified lignin resin)=37.6% (mass ratio), Avermectin: wall material (urea+formaldehyde+modified lignin resin)=1 (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.0ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under temperature, continue stirring reaction 80min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 7.5ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 600rpm speed of agitator, add core solution (2.0g Avermectin+6.0g span85+50.0g chlorobenzene) fast, under this rotating speed, continue to stir 35min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, use mass fraction be 4% oxalic acid solution slowly to drip regulator solution pH value be 2～3, water-bath is transferred to 30 ℃ then; After continue stirring 60min, with warming-in-water to 65 ℃, behind the curing reaction 120min; Suction filtration, with 40 ℃ of following vacuum drying 14h of water washing; Get the solid microcapsule granule, see that shown in accompanying drawing 7 and 8, the microcapsules particle diameter mainly is distributed in 20～70um; Average grain diameter is 30.99um; The medicine carrying amount is 18.7%, and envelop rate is 69.4%, and slow-release time is 128h.
Said raw material is according to following proportioning:
Formaldehyde: urea=2.0 (amount of substance ratio); Emulsifier span85: deionized water=2.5% (mass ratio); Chlopyrifos: wall material (urea+formaldehyde+modified lignin resin)=2 (mass ratio), modified lignin resin: wall material (urea+formaldehyde+modified lignin resin)=32.5% (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.46ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under this temperature, continue stirring reaction 75min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 6.0ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 1000rpm speed of agitator, add core solution (4.0g chlopyrifos+5.0g span85+50.0g chlorobenzene) fast, under this rotating speed, continue to stir 35min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, and using the slow regulator solution pH of 4% oxalic acid solution value is 2～3, water-bath is transferred to 30 ℃ then; After continuing stirring reaction 70min, with warming-in-water to 70 ℃, behind the curing reaction 70min; Filter, use water washing, 30 ℃ of following vacuum drying 24h get the solid microcapsule granule; See shown in accompanying drawing 9 and 10; The microcapsules particle diameter mainly is distributed in 20～50um, and average grain diameter is 32.47um, and the medicine carrying amount is 33.3%; Envelop rate is 65.7%, and slow-release time is 116h.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.5 (ratio of amount); Surfactant span80: deionized water=2.5% (mass ratio); Chlopyrifos: wall material (urea+formaldehyde+modified lignin resin)=1 (mass ratio), modified lignin resin: wall material (urea+formaldehyde+modified lignin resin)=28.6% (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 2.6ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under temperature, continue stirring reaction 75min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 5.0ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 250ml; Under the room temperature after the stirring and dissolving; Under the 600rpm speed of agitator, add core solution (3.50g chlopyrifos+6.0g span85+70.0g tetrachloro-ethylene) fast, under this rotating speed, continue to stir 35min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, and using the slow regulator solution pH of 4% oxalic acid solution value is 2～3, water-bath is transferred to 35 ℃ then; After continuing stirring reaction 60min, with warming-in-water to 65 ℃, behind the curing reaction 100min; Suction filtration, use water washing, 40 ℃ of following vacuum drying 24h, the solid microcapsule granule; See shown in accompanying drawing 11 and 12; The microcapsules particle diameter mainly is distributed in 20～50um, and average grain diameter is 24.04um, and the medicine carrying amount is 30.9%; Envelop rate is 66.8%, and slow-release time is 124h.
Said raw material is according to following proportioning:
Formaldehyde: urea=2.0 (amount of substance ratio); Emulsifier span85: deionized water=2.5% (mass ratio); Chlopyrifos: wall material (urea+formaldehyde+modified lignin resin)=2 (mass ratio), modified lignin resin: wall material (urea+formaldehyde+modified lignin resin)=32.5% (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.46ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under this temperature, continue stirring reaction 75min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 6.0ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 1000rpm speed of agitator, add core solution (3.0g chlopyrifos+5.0g span85+50.0g chlorobenzene) fast, under this rotating speed, continue to stir 35min; The microscopically change of size tends towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, and using the slow regulator solution pH of 0.2mol/L hydrochloric acid solution value is 2～3, water-bath is transferred to 30 ℃ then; After continuing stirring reaction 70min, with warming-in-water to 70 ℃, behind the curing reaction 70min; Filter, use water washing, freeze drying 30h gets the solid microcapsule granule; See and attach shown in Figure 13 and 14; The microcapsules particle diameter mainly is distributed in 20～50um, and average grain diameter is 32.47um, and the medicine carrying amount is 31.3%; Envelop rate is 68.7%, and slow-release time is 112h.
Embodiment 8
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (amount of substance ratio); Emulsifier span85: deionized water=3% (mass ratio); Modified lignin resin: wall material (formaldehyde+urea+modified lignin resin)=37.6% (mass ratio), Avermectin: wall material (urea+formaldehyde+modified lignin resin)=1 (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.0ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under temperature, continue stirring reaction 80min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 7.5ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution, add sodium chloride 12.0g successively, deionized water 200ml after the stirring and dissolving, under the 800rpm speed of agitator, adds core solution (1.2g under the room temperature fast
α-naphthoic acid+6.0g span85+50.0g chlorobenzene), under this rotating speed, continue to stir 30min, microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, and using mass fraction slowly to drip regulator solution pH value as the 0.2mol/L sulfuric acid solution is 2～3, water-bath is transferred to 35 ℃ then; After continue stirring 60min, with warming-in-water to 75 ℃, behind the curing reaction 90min; Suction filtration, with 40 ℃ of following vacuum drying 14h of water washing; Get the solid microcapsule granule, see that shown in accompanying drawing 15 and 16, the microcapsules particle diameter mainly is distributed in 10～50um; Average grain diameter is 24.90um; The medicine carrying amount is 19.7%, and envelop rate is 65.4%, and slow-release time is 105h.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (ratio of amount); Surfactant span85: deionized water=3% (mass ratio), modified lignin resin: wall material (formaldehyde+urea+modified lignin resin)=44.6% (mass ratio) Avermectin: wall material (urea+formaldehyde+modified lignin resin)=0.5 (mass ratio).
In there-necked flask, add 1.333g urea, 2.5ml deionized water; Using mass fraction 4% solution adjust pH after the stirring and dissolving is 4～5; Add 3.0ml formaldehyde then, under the 300rpm mixing speed, bath temperature is slowly risen to 75 ℃, and under temperature, continue stirring reaction 70min.Add the modified lignin resin aqueous solution (preparation method is with reference to embodiment 1) 10.0ml, continue reaction 120min and obtain prepolymer solution, be cooled to room temperature and place.
In above-mentioned prepolymer solution; Add sodium chloride 15.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 800rpm speed of agitator, add core solution (1.0g Avermectin+6.0g span85+20.0g chlorobenzene+30.0g toluene) fast, under this rotating speed, continue to stir 30min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, use mass fraction be 4% oxalic acid solution slowly to drip regulator solution pH value be 1～2, water-bath is transferred to 30 ℃ then; After continue stirring 60min, with warming-in-water to 60 ℃, behind the curing reaction 120min; Suction filtration, use water washing, 40 ℃ of following vacuum drying 14h, the solid microcapsule granule; See shown in accompanying drawing 17 and 18; Particle diameter mainly is distributed in 20～60um, and average grain diameter is 32.132um, and the medicine carrying amount is 2.7%; Envelop rate is 9.1%, and slow-release time is 23h.
Said raw material is according to following proportioning:
Formaldehyde: urea=1.75 (ratio of amount); Surfactant span85: deionized water=3% (mass ratio); Avermectin: wall material (urea+formaldehyde+modified lignin resin)=1 (mass ratio), wooden modification quality: wall material (urea+formaldehyde+modified lignin resin)=37.6% (mass ratio).
In there-necked flask, be weighed into 1.333g urea, 2.5ml deionized water; Using 0.2mol/L sodium hydroxide solution adjust pH after the stirring and dissolving is 8～9; Add 3.0ml formaldehyde then, under the 300rmp mixing speed, bath temperature slowly is warming up to 75 ℃, and under this temperature, continue stirring reaction 80min.Add modified lignin resin solution (preparation method is with reference to embodiment 1) 7.5ml, continue reaction 120min and form prepolymer solution.Being cooled to room temperature afterwards places.
In above-mentioned prepolymer solution; Add sodium chloride 12.0g successively; Deionized water 200ml; Under the room temperature after the stirring and dissolving; Under the 800rpm speed of agitator, add core solution (2.3g Avermectin+6.0g span85+70.0g tetrachloro-ethylene) fast, under this rotating speed, continue to stir 35min; Microscopically is observed change of size and is tended towards stability, and forms stable O/W type emulsion.Rotating speed is transferred to 300rpm, use mass fraction be 4% oxalic acid solution slowly to drip regulator solution pH value be 3～4, water-bath is transferred to 35 ℃ then; After continue stirring 50min, with warming-in-water to 75 ℃, behind the curing reaction 90min; Suction filtration, use water washing, 30 ℃ of following vacuum drying 24h, the solid microcapsule granule; See shown in accompanying drawing 19 and 20; The microcapsules particle diameter mainly is distributed in 20～80um, and average grain diameter is 31.19um, and the medicine carrying amount is 20.5%; Envelop rate is 68.3%, and slow-release time is 115h.
Claims (10)
1. the preparation method of a lignin urea aldehyde radical pesticide micro capsule is characterized in that being is monomer with modified lignin resin, formaldehyde and urea, water as solvent, and base catalysis forms soluble prepolymer down, forms continuous phase behind the said performed polymer dilute with water; Become disperse phase with agricultural chemicals, organic solvent and group of surfactants; Continuous phase and disperse phase mix through stirring the stable O/w emulsion of formation; Catalysis and in situ polycondensation reaction under acid condition heats up and solidifies, and suction filtration obtains the solid microcapsule granule after washing, the drying;
The lignin of said modification for the technical grade wheat straw alkali lignin through the modification of formaldehyde methylolation after gained solution.
2. according to the preparation method of the said lignin urea of claim 1 aldehyde radical pesticide micro capsule, it is characterized in that may further comprise the steps:
Urea is soluble in water, and alkali condition adds down formalin, and stirring reaction adds the lignin aqueous solution after the modification then, continues prepared in reaction and obtains lignin urea aldehyde prepolymer solution;
Agricultural chemicals and surfactant are dissolved in the core of organic solvent as microcapsules;
(2) the water miscible lignin urea aldehyde performed polymer after the core of the said microcapsules of step (1) and the dilution is mixed high-speed stirred formation O/w emulsion;
(3) lignin urea aldehyde performed polymer polycondensation reaction under acid condition of water in the O/w emulsion that step (2) is made forms polymeric membrane on oil phase drop surface, makes pesticide micro capsule through the intensification curing reaction.
3. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, it is characterized in that the quality of modified lignin resin accounts for 27～44% of formaldehyde, urea and modified lignin resin gross mass in the microcapsules.
4. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, the concentration that it is characterized in that said modified lignin resin solution is 2g/10ml.
5. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules; The preparation method who it is characterized in that the lignin of said modification is: according to the 20g alkali lignin: the ratio of 60～70ml distilled water is dissolved in alkali lignin in the distilled water; Ratio according to 20g alkali lignin: 5.7ml 37% formalin adds formalin; The pH value of accent system is 10～11; Water-bath is heated to 90 ℃; Reaction time 3h obtains the solution of modified lignin resin.
6. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, it is characterized in that said organic solvent is that in chlorobenzene, tetrachloro-ethylene or the toluene any is the mixture that 3:2 mixes with chlorobenzene according to mass ratio; Perhaps said organic solvent is that tetrachloro-ethylene is the mixture that 3:2 mixes with toluene according to mass ratio.
7. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, it is characterized in that said agricultural chemicals is fat-soluble solid-state or liquid pesticide.
8. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, it is characterized in that said surfactant is a nonionic surface active agent.
9. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, it is characterized in that said acid condition is that to adopt acid solution to regulate said O/w emulsion pH value be 2～4; Said acid solution is the oxalic acid of mass fraction 4%, the hydrochloric acid of 0.2mol/L or the sulfuric acid of 0.2mol/L.
10. according to the preparation method of claim 1 or 2 said lignin urea aldehyde radical pesticide micro capsules, the bath temperature that it is characterized in that said polycondensation reaction is 30 ℃, and polycondensation reaction time is 60min.
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