CN103461329B - Pesticide composite dispersing agent and application of pesticide composite dispersing agent in preparation of pesticide suspending agent - Google Patents
Pesticide composite dispersing agent and application of pesticide composite dispersing agent in preparation of pesticide suspending agent Download PDFInfo
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Abstract
The invention discloses a pesticide composite dispersing agent and an application of the pesticide composite dispersing agent in preparation of a pesticide suspending agent. According to the pesticide composite dispersing agent and the application of the pesticide composite dispersing agent in the preparation the pesticide suspending agent, tebuconazole and oxine-copper are used as effective constituents of pesticide, properties, such as the suspension percentage, the dispersity and the stability are used as evaluation indexes, combinations and the dosage ratio of different dispersing agent varieties are screened, the best formula is determined, and the composite dispersing agent which can remarkably improve the suspension percentage or the dispersity or the stability of the pesticide suspending agent can be obtained in a screening mode. Due to the large number of screening experiments, a user can finally find that an alkyl naphthalene sulfonic acid formaldehyde condensate sodium salt and xylogen sodium sulfonate have the remarkable synergistic interaction effects, and the composite dispersing agent composed of the alkyl naphthalene sulfonic acid formaldehyde condensate sodium salt and the xylogen sodium sulfonate can remarkably improve the properties, such as the suspension percentage or the dispersity or the stability, of the pesticide suspending agent. The invention further provides an oxine-copper tebuconazole pesticide suspending agent, an oxine-copper pesticide suspending agent and a method for preparing the oxine-copper pesticide suspending agent. The invention further discloses the application of the oxine-copper tebuconazole pesticide suspending agent and the oxine-copper pesticide suspending agent for preventing and treating bacteria or fungous diseases.
Description
Technical field
The present invention relates to a kind of insecticides adjuvant, particularly relate to a kind of composite dispersing agent for agricultural chemicals suspension agent, the invention further relates to this agricultural chemicals composite dispersing agent and preparing the purposes in agricultural chemicals suspension agent, belong to pesticide dispersing agent field.
Background technology
Suspending agent (Suspens ion Concentrat ion, SC) being take water as medium, by some auxiliary agent, pulverized by sand milling, the former medicine of solid that is insoluble or that be slightly soluble in water is scattered in water equably, the stable liquid-solid state system that form the tiny higher suspension of a kind of particle, can flow.Have particle diameter little, good dispersion, good fluidity, suspensibility are high, biologically active is high, using dosage is little, resistance of rainwater washing against, residual low, to features such as people and animals' low toxicities.
Suspending agent can by the former medicine particle of originally insoluble in water or indissoluble by other promoter effect dispersions such as surfactants or be suspended in water, thus the suspension system defining stable chemical nature, be evenly distributed.The main component of suspending agent comprises former medicine, wetting agent, defoamer, dispersant, pH adjusting agent, thickener, antifreezing agent, water etc.The dispersion medium of suspending agent is water, therefore it has the features such as environmentally friendly, cheap, use safety, making is simple, storage is convenient, and can mix under any water temperature, condition of water quality, with arbitrary proportion with water, easy to use.Relative to the formulations of pesticide taking organic solvent as medium, it is to processing and environment for use is all safer, reduce the use of organic solvent, and poisoning degree also reduces greatly.Suspending agent, as a novel agrochemical formulation, obviously can reduce the use of organic solvent in traditional agricultural chemicals, thus reduces environmental pollution, be worth promoting (Liu Bulin. formulations of pesticide process technology [M]. Beijing: Chemical Industry Press, 1998).
Suspending agent main performance index mainly contains: effective content, suspensibility, dispersiveness, mobility, viscosity, fineness, pH value, persistent foamability and normal temperature, thermal storage stability, pourability etc.The height of suspensibility directly affects the quality of drug effect, although the principal element affecting suspensibility is many, principal element has: one is the fineness of preparation, and two is density contrasts, and three is viscositys; Suspensibility and particle diameter have direct relation, and the thinner suspensibility of preparation particle diameter is higher, otherwise lower, and laboratory has also demonstrated the raising along with suspending agent fineness by centrifugal test and storage test result, and stability becomes excellent from difference gradually.So suspending agent not only will have enough fineness also must have good size distribution.Suitable viscosity has good stability and higher suspensibility by making preparation, but the too high formulation flows of viscosity is bad, can bring difficulty to production and processing, and the dispersiveness of preparation is bad even can't disperse automatically.
The composition of preparation also can have an impact to suspensibility, the composition of suspending agent comprises former medicine, water and auxiliary agent, the suspending agent stable in order to excellent, except fineness viscosity requires, also must select suitable auxiliary agent and active constituent content, auxiliary agent in suspending agent has multiple, mainly contain dispersant, wetting agent, thickener, antifreezing agent and defoamer etc., what wherein have the greatest impact is dispersant, wetting agent.In same form formula, different dispersants or wetting agent kind obviously can have influence on the performance of pesticide active ingredient, if pesticide active ingredient and dispersant, wetting agent mismatch 5 time, suspending agent can be caused to place layering for a long time, the knot end, is serious, particle becomes large, thus its suspensibility is declined, affect the absorption of blade face to medicament, this is particularly important to cauline leaf processing-type agricultural chemicals, from chemically unstable medium (impurity as brought in former medicine) or the factor adding various auxiliary agent and additive etc., or when selecting dispersant improper, these all will cause the crosslinked of adsorption layer, gel, electric charge is neutralized or because of the bridging of particle periphery dispersant and overlap joint, thus destroy or change the protective layer of stable particle, thus precipitation and serious caking phenomenon may also be produced.Any step of unstable form of above-mentioned existence can occur simultaneously, and this will depend on former medicine Performance and quality, the type using dispersant and quality and its storage requirement etc.
Agricultural chemicals will arrive in user's hand through links such as processing, storage, transport and commercial distributions, short, within 1 month, reach 2 years even longer, concerning agricultural chemicals suspension agent, along with the prolongation of period of storage, the change of the temperature difference, suspensibility more or less all can change to some extent, and an excellent aqueous suspension formulations product is the test that can withstand time and condition change, and its suspensibility should without obvious reduction.The pharmaceutical formulation of different cultivars, different size all has very big-difference, therefore screens rational pharmaceutical formulation very crucial for suspending agent exploitation.
Tebuconazole belongs to triazole type systemic fungicide, and have protection, treatment and eradicant action, fungicidal spectrum is wide, and the lasting period is long, can prevent and treat plurality of plant diseases, as rust, powdery mildew, root rot, gray mold etc.Tebuconazole to be sprayed on crop and can be partially absorbed and mainly shift to top by plant is vegetative rapidly, not only there is bactericidal activity, also can promote plant growth, make it well developed root system, leaf look dark green, robust plant, effective tiller increase, thus can increase crop yield.
Copper 8-hydroxyquinolinate belongs to organic chelated copper fungicide, there is extremely strong adhesion strength and resistance of rainwater washing against ability, there is the advantages such as safety is high, fungicidal spectrum is wide, the lasting period is long, consumption is low, to bacterial disease, there is special efficacy, for fungal disease, there is higher control efficiency.
After copper 8-hydroxyquinolinate and Tebuconazole are carried out compatibility, the two has certain synergistic function, can increase target action site; expand the control spectrum of disease; the usage amount of pesticide active ingredient can be reduced simultaneously, effectively delay the drug-fast generation of damage by disease and insect, be conducive to preserving the ecological environment.
Publication No. is that the Chinese invention patent of CN101810181A discloses a kind of bactericidal pesticide composition and its production and use, the active ingredient of this bactericidal pesticide composition is made up of according to specific consumption proportion copper 8-hydroxyquinolinate and Tebuconazole, this bactericidal pesticide composition can prevent and treat various bacillary or fungal disease, but the defects such as suspensibility is low, bad dispersibility, stability are bad that the agricultural chemicals suspension agent of this bactericidal pesticide composition exists, have much room for improvement.
Summary of the invention
An object of the present invention is to provide a kind of agricultural chemicals composite dispersing agent of suspensibility, dispersiveness or the stability that effectively can improve agricultural chemicals suspension agent.
Two of object of the present invention is applied to by described agricultural chemicals composite dispersing agent to prepare agricultural chemicals suspension agent.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of agricultural chemicals composite dispersing agent, is made up of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt (D425) and sodium lignin sulfonate (REAX85A); In order to reach better dispersion effect, the mass ratio of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt and sodium lignin sulfonate is preferably 1-3:1-5, more preferably 1:1-2, is particularly preferably 1:2.
The size that pesticide activity component drug effect plays, depend primarily on dilution the soaking and opening up situation on target of pesticidal preparations, dosage surface tension force is lower, and covering surfaces is long-pending larger.Expect agricultural chemicals suspension agent of good performance, select suitable dispersant most important, on the one hand, because former medicine is various in style, its molecular structure, physicochemical property vary, and the dispersant kind of selection is also different.On the other hand, according to different Target crops, select suitable wetting dispersing agent, make the surface tension of the liquid of recommended dose appropriateness be less than the critical surface tension of target plant, namely in liquid, the concentration of auxiliary agent meets or exceeds critical micelle concentration, and reaching increases agricultural chemicals and hold dose at plant surface, reduce agricultural chemicals to run off, thus minimizing pesticide dosage, reduce drug cost, alleviate the pollution of agricultural chemicals to environment.In suspending agent, various auxiliary agent all may impact the physical stability of preparation, and also interacts between auxiliary agent, only has selected auxiliary agent reasonable disposition in certain quality and quantitative range, mutual coordination, just can make preparation become a kind of stable suspended substance.In same form formula, different wetting dispersing agent kinds obviously can have influence on the performance of pesticide active ingredient, if when active ingredient and wetting dispersing agent are incompatible, can cause suspending agent place for a long time layering, knot the end serious, particle becomes large, thus its suspensibility is declined, affect the absorption of blade face to medicament, this is particularly important to cauline leaf processing-type agricultural chemicals.
The kind of dispersant or composition are comparatively large for the performance impact of agricultural chemicals suspension agent each side, comprise the performances such as suspensibility, outward appearance, mobility, viscosity, fineness, pH value, persistent foamability, dispersiveness and bin stability; Even if in same form formula; different dispersants obviously can have influence on the performance of pesticide active ingredient; from chemically unstable medium (impurity as brought in former medicine); or add the factor of various auxiliary agent and additive etc.; or when selecting dispersant improper; these all will cause crosslinked, gel, the electric charge of adsorption layer to be neutralized or because of the bridging of particle periphery dispersant and overlap joint; thus destroy or change the protective layer of stable particle, thus also may produce precipitation and serious caking phenomenon.
When different dispersants is carried out composite, because the physicochemical property between various dispersant differs greatly, also larger difference can be there is in the performance of composite for the different dispersants composite dispersing agent together obtained afterwards, some composite dispersing agents can significantly improve a certain item in the dispersiveness of suspending agent, suspensibility or bin stability or multinomial performance, some composite dispersing agents are not owing to matching each other, compound not only can not improve dispersiveness, the performance such as suspensibility or bin stability of suspending agent, instead can reduce a certain or multiple performance of suspending agent.
The present invention with Tebuconazole and copper 8-hydroxyquinolinate for active ingredient, with performances such as suspensibility, dispersiveness, normal temperature and heat storage stabilities for evaluation index, carry out preferably to the combination of different dispersant kind and different consumption proportions thereof, to screen the composite dispersing agent obtaining suspensibility, dispersiveness or the stability that can significantly improve agricultural chemicals suspension agent.For this reason, the present invention is by naphthalenesulfonate formaldehyde condensation compound (NN0), alkylphenol polyoxyethylene (TX-10), alkyl phenol formaldehyde resin polyoxyethylene ether (Nongru-700 #), alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt (D425), detergent (LS), sodium lignin sulfonate (REAX85A, REAX83A), dispersing agent MF (Dispersant MF), the dispersant kind of the number of different types such as castor oil polyoxyethylene ether (BY130) adopts flow point method to carry out the discovery of Preliminary screening the selection result, dispersant D425, emulsifier TX-10, the flow point of lignin REAX85A and lignin REAX83A is lower, be applicable to the dispersant of this formulation, the compound prescription screening that the present invention tentatively selects dispersant D425, emulsifier TX-10, NNO, lignin REAX85A and REAX83A carry out next step.
The present invention further using flow point method Preliminary screening to dispersant D425, emulsifier TX-10, NNO, 5 alone formulas of lignin REAX85A and REAX83A and 35 compound prescriptions being combined into be prepared into agricultural chemicals suspension agent as dispersant, investigate from performance indications such as suspensibility, dispersiveness and stability, to filter out optimum combination.From the result of the test of screening, dispersant D425 and lignin REAX85A is carried out compatibility according to the mass ratio of 1:1-2 and obtains effect that composite dispersing agent has comparatively significant Synergistic, can not only suspensibility, the dispersiveness of raising suspending agent of highly significant, effectively can also improve normal temperature and the heat storage stability of suspending agent; In other words, compared to other 33 kinds of combinations, during by the mass ratio compatibility of dispersant D425 lignin REAX85A according to 1:1-2, the cooperative effect highly significant of the two, the properties of agricultural chemicals suspension agent can be promoted comprehensively, significantly, be suitable for very much the dispersant as agricultural chemicals suspension agent.Especially, when dispersant D425 lignin REAX85A is carried out compatibility according to the mass ratio of 1:2, compared to other combination, prepared agricultural chemicals suspension agent all significantly will be better than other combination in the performances such as suspensibility, dispersiveness and stability, can say, when dispersant D425 lignin REAX85A is carried out compatibility according to the mass ratio of 1:2, achieve unforeseeable technique effect.
Another object of the present invention using the present invention screen the composite dispersing agent that obtains and to be applied to as insecticides adjuvant and to prepare agricultural chemicals suspension agent; The composition of described agricultural chemicals suspension agent comprises: pesticide active ingredient, composite dispersing agent, wetting agent, thickener, antifreezing agent, preservative; Wherein, pesticide active ingredient in described agricultural chemicals suspension agent can be bactericide, the insecticide with sterilization or disinsection efficiency, or various weed killer herbicide, these active ingredients are active ingredient that can be single, also can by the composite composition together of several active ingredient, such as, can be the mixture that copper 8-hydroxyquinolinate and Tebuconazole form according to the mass ratio of 2:1;
Wherein, calculate by mass percentage, the consumption of each composition can be: pesticide active ingredient 4-70%, composite dispersing agent 2-10%, wetting agent 1-6%, antifreezing agent 1-8%, preservative 0.1-2%, thickener 0.1-3%, and surplus is water.
Further, the invention provides a kind of copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent, its composition comprises: the pesticide active ingredient be made up of copper 8-hydroxyquinolinate and Tebuconazole, composite dispersing agent, wetting agent, thickener, antifreezing agent, preservative and water; By mass percentage, the consumption of each component is preferably: pesticide active ingredient 10-50%, composite dispersing agent 2-10%, wetting agent 1-6%, thickener 0.1-3%, antifreezing agent 1-8%, preservative 0.1-2%, surplus is water.
Specifically, the invention provides a kind of 36% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent, its composition comprises: the pesticide active ingredient be made up of copper 8-hydroxyquinolinate and Tebuconazole, composite dispersing agent, wetting agent, thickener, antifreezing agent, preservative and water; By mass percentage, the consumption of each component is preferably: pesticide active ingredient 36%, composite dispersing agent 6%, wetting agent 2%, thickener 0.7%, antifreezing agent 5%, preservative 0.5%, surplus is water.
Wherein, preferably, described pesticide active ingredient is made up of according to the mass ratio of 1:1-3 Tebuconazole and copper 8-hydroxyquinolinate, preferred, and described pesticide active ingredient is made up of according to the mass ratio of 1:2 Tebuconazole and copper 8-hydroxyquinolinate.
Present invention also offers a kind of copper 8-hydroxyquinolinate agricultural chemicals suspension agent, its constituent is: by mass percentage, and copper 8-hydroxyquinolinate 10-40%, composite dispersing agent 2-10%, wetting agent 1-6%, thickener 0.1-3%, antifreezing agent 1-8%, preservative 0.1-2%, surplus are water; Preferably, the consumption of each component is: copper 8-hydroxyquinolinate 33.5%, composite dispersing agent 6%, wetting agent 2%, thickener 0.7%, antifreezing agent 5%, preservative 0.5%, surplus are water.
Described composite dispersing agent is made up of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt (D425) and sodium lignin sulfonate (REAX85A); Wherein, the mass ratio of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt and sodium lignin sulfonate is preferably 1-3:1-5, is more preferably 1:1-2, is particularly preferably 1:2.
Wetting agent described in the present invention, thickener, antifreezing agent and preservative can be the components of some routines in agricultural chemicals suspension agent, such as, described wetting agent can be lauryl sodium sulfate, alcohol ethoxylate, alkylphenol ethoxylate or octadecyl sodium sulfosuccinate; Described thickener can be in gelatin, sodium carboxymethylcellulose, hydroxyethylcellulose, modified starch, xanthans, bentonite, silica or Magnesiumaluminumsilicate any one or multiple; Described preservative can be in Sodium Benzoate, sodium salicylate, KF88, propionic acid or sorbic acid and sodium salt thereof or other biological bactericide any one or multiple; Described antifreezing agent can be polyalcohols (as ethylene glycol, propane diols, glycerine), glycols (diethylene glycol (DEG), triethylene glycol) or polyethylene glycol etc.
Present invention also offers a kind of method preparing copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent or copper 8-hydroxyquinolinate agricultural chemicals suspension agent, the method comprises: in sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener and water, grinding, (5 μm are preferably) when particle diameter D90 is at 2-15 μm, stop grinding, add after antifreezing agent stirs and add thickener adjustment viscosity again, to obtain final product.
Copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent provided by the invention or copper 8-hydroxyquinolinate agricultural chemicals suspension agent can prevent and treat various bacillary or fungal disease, be widely used in the disease control of the crop such as vegetables, fruit tree (comprising paddy rice, cotton, corn, soybean, tobacco etc.), the control especially for rice sheath blight disease, alternaria leaf spot of apple has significant preventive effect.
Embodiment
The present invention is further described below in conjunction with specific embodiment; these embodiments are only exemplary; what those skilled in the art should understand that is; can modify to the details of technical solution of the present invention and form lower without departing from the spirit and scope of the present invention or replace, but these amendments and replacement all fall within the scope of protection of the present invention.
D425: purchased from Dutch Akzo Nobel N.V. (AkzoNobelN.V).
REAX85A: purchased from American virtue Wei Shiweike company (MWV).
The preparation of embodiment 136% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent
Each component is taken: pesticide active ingredient 36%(copper 8-hydroxyquinolinate 24%, Tebuconazole 12%) according to following mass percent; Composite dispersing agent 6%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:2); Wetting agent lauryl sodium sulfate 2%; Antifreeze glycol 5%; Preservative KF88 0.5%; Aluminium-magnesium silicate 0.5%; Xanthans 0.2%, running water is supplied;
In sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 5 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.3; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.148; Persistent foamability≤20ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 236% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent
Each component is taken: pesticide active ingredient 36%(copper 8-hydroxyquinolinate 24%, Tebuconazole 12%) according to following mass percent; Composite dispersing agent 6%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:1); Wetting agent lauryl sodium sulfate 2%; Antifreeze glycol 5%; Preservative sodium benzoate 0.5%; Aluminium-magnesium silicate 0.5%; Xanthans 0.2%, running water is supplied;
In sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 5 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.2; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.146; Persistent foamability≤21ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 336% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent
Each component is taken: pesticide active ingredient 36%(copper 8-hydroxyquinolinate 24%, Tebuconazole 12%) according to following mass percent; Composite dispersing agent 6%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:2); Wetting agent octadecyl sodium sulfosuccinate 2%; Antifreeze glycol 5%; Preservative sodium benzoate 0.5%; Aluminium-magnesium silicate 0.5%; Xanthans 0.2%, running water is supplied;
In sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 5 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.4; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.141; Persistent foamability≤20ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 448% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent
Each component is taken: pesticide active ingredient 48%(copper 8-hydroxyquinolinate 36%, Tebuconazole 12%) according to following mass percent; Composite dispersing agent 8%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:2); Wetting agent lauryl sodium sulfate 2%; Antifreeze glycol 5%; Preservative KF88 0.5%; Aluminium-magnesium silicate 0.5%; Xanthans 0.1%, running water is supplied;
In sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 15 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.3; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.151; Persistent foamability≤21ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 510% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent
Each component is taken: pesticide active ingredient 10%(copper 8-hydroxyquinolinate 5%, Tebuconazole 5%) according to following mass percent; Composite dispersing agent 4%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:1); Wetting agent lauryl sodium sulfate 1%; Antifreeze glycol 5%; Preservative KF88 0.5%; Aluminium-magnesium silicate 2.0%; Xanthans 0.3%, running water is supplied;
In sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 3 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.0; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.122; Persistent foamability≤19ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 636% copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent
Each component is taken: pesticide active ingredient 36%(copper 8-hydroxyquinolinate 24%, Tebuconazole 12%) according to following mass percent; Composite dispersing agent 10%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:1); Wetting agent lauryl sodium sulfate 3%; Antifreeze glycol 5%; Preservative sodium benzoate 0.4%; Aluminium-magnesium silicate 0.5%; Xanthans 0.1%, running water is supplied;
In sand mill, drop into pesticide active ingredient, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 8 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.2; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.169; Persistent foamability≤20ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 733.5% copper 8-hydroxyquinolinate agricultural chemicals suspension agent
Each component is taken: copper 8-hydroxyquinolinate 33.5% according to following mass percent; Composite dispersing agent 6%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:2); Wetting agent lauryl sodium sulfate 2%; Antifreeze glycol 5%; Preservative sodium benzoate 0.5%; Aluminium-magnesium silicate 0.5%; Xanthans 0.2%, running water is supplied;
In sand mill, drop into copper 8-hydroxyquinolinate, composite dispersing agent, wetting agent, preservative, thickener aluminium-magnesium silicate and water, grinding, when particle diameter D90 is at 5 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.4; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.132; Persistent foamability≤21ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 845% copper 8-hydroxyquinolinate agricultural chemicals suspension agent
Each component is taken: copper 8-hydroxyquinolinate 45% according to following mass percent; Composite dispersing agent 6%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=3:1); Wetting agent octadecyl sodium sulfosuccinate 2%; Antifreeze glycol 5%; Preservative KF88 0.5%; Aluminium-magnesium silicate 0.5%; Xanthans 0.15%, running water is supplied;
In sand mill, drop into pesticide active ingredient copper 8-hydroxyquinolinate, composite dispersing agent, wetting agent, preservative, aluminium-magnesium silicate and water, grinding, when particle diameter D90 is less than 5 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=6.7; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.19; Persistent foamability≤20ml; Pourability is qualified, cold and hot storage qualified stability.
The preparation of embodiment 912% copper 8-hydroxyquinolinate agricultural chemicals suspension agent
Each component is taken: copper 8-hydroxyquinolinate 12% according to following mass percent; Composite dispersing agent 6%(alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425: sodium lignin sulfonate REAX85A=1:2); Wetting agent lauryl sodium sulfate 2%; Antifreeze glycol 5%; Preservative sodium benzoate 0.5%; Aluminium-magnesium silicate 1%; Xanthans 0.2%, running water is supplied;
In sand mill, drop into pesticide active ingredient copper 8-hydroxyquinolinate, composite dispersing agent, wetting agent, preservative, aluminium-magnesium silicate and water, grinding, when particle diameter D90 is less than 5 μm, stop grinding, add after antifreezing agent stirs and add thickener xanthans adjustment viscosity again, to obtain final product.
Product appearance is the green thick liquid that can flow, and product leading indicator content is qualified, pH=7.3; Fineness 100% is by 44 μm of wet screenings, and proportion is 1.05; Persistent foamability≤19ml; Pourability is qualified, cold and hot storage qualified stability.
Experimental example 1 flow point method screening dispersant kind
One, for examination dispersant kind
Dispersant kind: D425, REAX85A, REAX83A, NNO, agriculture breast BY130, Nongru-700 #, emulsifier TX-10, calcium lignosulfonate, detergent LS, BY140, agriculture breast BY110 and agriculture breast 1601#.
D425 is alkyl naphthalene sulfonic acid formaldehyde condensation products, and be a dispersant that Akzo Nobel N.V. produces, advantage is that dispersive property is good, and adaptability is good.It mainly stops the phase inter coagulation of solids in solid-liquid dispersion in suspending agent, makes solia particle in the liquid phase can a kind of uniform dispersion of maintenance of long period.
REAX85A is the sodium lignin sulfonate dipersant of a low sulfonation degree HMW high temperature resistant type, at disperse dyes, reducing dye and comparatively general in pesticide processing, and high heat-resistant stability, low mineral salt, without saponified; REAX83A is the low-molecular-weight sodium lignin sulfonate dipersant of highly sulfonated.
Dispersant NNO outward appearance is rice brown powder solid, acidproof, alkaline-resisting, heat-resisting, resistance to hard water, resistance to mineral salt; Be soluble in the water of any hardness, there is superior proliferating property and protecting colloid performance, but without surface-actives such as permeation blister, be mainly used in making dispersant in disperse dyes, reducing dye, reactive dye, acid dye and leather dye; Also can be used for textile printing and dyeing, dispersant made by wettable agricultural chemicals, paper grade (stock) dispersant, electroplating additive, water soluble paint, pigment dispersing agent, water treatment agent, carbon black disperser etc.Dispersant NNO is main in pesticide producing processing to be used as in the formulation such as wetting powder, suspending agent as helping dispersion to use.
Emulsifier TX-10 is alkylphenol-polyethenoxy (10) ether, and outward appearance is colourless transparent liquid, soluble in water, there is excellent emulsification washing ability, this product is hydrophilic emulsifier, and performances such as having good washing level dyeing, soak, spread, be antistatic is the base stock of multiple washing agent.In textile and dyeing industry, can be used as levelling agent, dispersant, wetting agent and washing agent, in the fine industry of conjunction, do finish monomer.Woolen dyed auxiliary agent and metal detergent.Make emulsifier in agricultural chemicals, medicine, rubber industry, building trade does asphalt emulsifier, is again one of important composition of water-base metal cleaning agent; Oil field wetting agent, foaming agent, mud active treating agent.
BY130 is castor oil polyoxyethylene ether, the transparent oil body of yellowish-brown, has that surface tension is low, emulsibility good, strong detergency, antistatic, nontoxic, the premium properties such as nonirritant, electrolyte-resistant.It is a kind of broad-spectrum novel surfactant, can be used for the emulsifier of daily chemicals, additive, prepare various washing, clean, wash the preparations such as clean and dry-cleaning, dispersant in organic, Polymer Synthesizing, in textile industry, be used as the component of wool wool lubricant and preparation medium, existing emulsification has antistatic effect again, the fatting agent of leather industry, also can be used for preparing slurry, to eliminate the foam in synthetic slurry.
Nongru-700 # is alkyl phenol formaldehyde resin polyoxyethylene ether, and outward appearance is thick pale yellow shape liquid or semisolid, soluble in water and multiple organic solvent.There is good emulsification, dispersion and wettability, be specially adapted to the emulsifiability adjusting agent making organochlorine, organophosphorous pesticide, be the special efficacy monomer of weed killer herbicide emulsifier, also contribute to the solubilising between emulsifier.In addition or the good monomer of disperse dyes high-temperature pressure dyeing levelling agent.
Detergent LS main component is to methoxyl group fatty acyl anilinesulfonic acid, for rice brown ceramic powder, soluble in water, acidproof, alkaline-resisting, resistance to hard water, resistance to general electrolyte, boiling resistance, the not liquid of resistance to hypochlorite bleaching, has the excellent performance such as calcium soap dispersion, washing, infiltration, foaming characteristic, emulsification, level dyeing, softness.Belonging to anion surfactant, is excellent detergent, bleeding agent and lime soap dispersant.
Dispersant MF is brown ceramic powder, soluble in water, and the easy moisture absorption, does not fire, and has excellent diffusibility and heat endurance, and without miserable permeability and foaming characteristic, acid and alkali-resistance, hard water and mineral salt, to fibers such as linen-cottons without affinity; Affinity is had to protein and Fypro; Can use with anionic and nonionic surface active agent simultaneously, but can not with cationic dyes or surfactant used in combination.Dispersant MF has mill and imitates, the advantage that dispersiveness, warm tolerance, High Temperature Disperse have been stablized.
Calcium lignosulfonate (being called for short wooden calcium) is a kind of multicomponent high molecular polymer anion surfactant, outward appearance is light yellow to dark brown powder, slightly aromatic odor, molecular weight, generally between 800 ~ 10000, has very strong dispersiveness, cohesiveness, sequestering.Usually from the cooking waste liquor of acid polishing (or being called sulfite pulping), spray-driedly to form.Water-soluble, but be insoluble to any common organic solvent.
Two, experimental technique
Adopt flow point method to screen dispersant kind, flow point method cardinal principle is with containing 5% dispersant solution, and the pressed powder making unit mass certain fineness be insoluble to this solution becomes pasty state to drip the minimum of required solution to forming drop.
Concrete assay method is first copper 8-hydroxyquinolinate and Original Tebuconazole are pulverized according to 2:1 ratio mixed airflow, then with distilled water, above-mentioned selected dispersant kind is made into respectively the dispersant solution of 5% same amount, take 10 grams of former medicines of the above-mentioned mixing crushed again respectively and put into 50ml beaker, weigh together with medicine spoon, then with graduated pipette, the above-mentioned dispersant solution prepared slowly is added drop-wise in beaker, limit dropping limit medication spoon constantly stirs, frequently medicine spoon is mentioned, until when just formation is dripped, stop dripping, now record the volume of solution used and weigh, then the volume of solution required for Unit Weight active ingredient is calculated, this amount is flow point.
Three, experimental result
Experimental result is in table 1.
Table 1 measures each dispersant flow point tables of data
The comparatively suitable dispersant of dispersant required for these formulations of pesticide that flow point is less; Visible according to the flow point data of table 1, the flow point of dispersant D425, emulsifier TX-10, lignin REAX85A and lignin REAX83A is lower, is applicable to the dispersant of this formulation; The compound prescription screening that the present invention tentatively selects dispersant D425, emulsifier TX-10, NNO, lignin REAX85A and REAX83A carry out next step.
The combination of experimental example 2 composite dispersing agent and consumption screening experiment
One, for examination dispersant kind
The dispersant that the flow point that experimental example 1 screens is less, that is: dispersant D425, emulsifier TX-10, NNO, lignin REAX85A and REAX83A.
Two, experimental technique
According to for the different performance of examination dispersant and effect, carry out suitable be combined into the method that 35 compound prescriptions and 5 alone formulas carry out repeated test and screen.
Each component is taken: pesticide active ingredient (copper 8-hydroxyquinolinate: Tebuconazole=2:1) content is 36% according to following mass percent; Dispersant total amount is that the composition of 6%(dispersant and consumption are in table 2); Wetting agent total amount is 2%; Antifreezing agent (ethylene glycol) total amount is 5%; Preservative (Sodium Benzoate) total amount is 0.5%; Thickener: aluminium-magnesium silicate is 0.5%, xanthans is 0.2%; All the other consumption running water are supplied.
The preparation method of agricultural chemicals suspension agent is as follows: in sand mill, drop into pesticide active ingredient, dispersant, wetting agent, preservative, part thickener and water, grinding, when particle diameter D90 is at 5 μm, stop grinding, add after antifreezing agent stirs and add remaining thickener adjustment viscosity again, to obtain final product.
Measure the indices of prepared suspending agent in accordance with the following methods:
Suspensibility measures: measure by GB/T14825-2006.
Viscosimetric analysis: adopt rotary viscosity design determining.
Dispersed mensuration: in 250m1 graduated cylinder, adds 249mi water and predicts suspending agent sample with the 1ml that syringe measures, instill in water, observe its deployment conditions from apart from graduated cylinder water surface 5cm.Excellent, good, bad three grades are divided into by the quality of its dispersion.
Top grade: in vaporific automatic dispersion in water, sink without visible particle.
Good level: automatically can disperse in water, have particles sink, jetsam can slowly disperse or disperse after gentle agitation.
Bad level: can not automatically disperse in water, sinks in graininess, could disperse after strong shake.
Three, experimental result
Experimental result is in table 2.
Table 2 dispersant various combination and proportioning are on the impact of 36% copper 8-hydroxyquinolinate tebuconazole suspension concentrates performance
As can be seen from Table 2, dispersant D425, emulsifier TX-10, NNO, lignin REAX85A and REAX83A are carried out combining and adopt identical combination variety to carry out combining obtained composite dispersing agent according to different consumptions according to different kinds, the indexs such as suspensibility, dispersiveness, stability and viscosity exist significant difference.Suspensibility is the key important indicator embodying drug effect suspension, and normal temperature and heat storage stability are also another important indicators of reaction suspending agent performance quality.
Visible according to the test data of table 2, dispersant D425 lignin REAX85A is carried out compatibility according to the mass ratio of 1:1-2 and obtains effect that composite dispersing agent has comparatively significant Synergistic, can not only suspensibility, the dispersiveness of raising suspending agent of highly significant, effectively can also improve normal temperature and the heat storage stability of suspending agent; In other words, compared to other 33 kinds of combinations, during by the mass ratio compatibility of dispersant D425 lignin REAX85A according to 1:1-2, the cooperative effect highly significant of the two; Especially, when dispersant D425 lignin REAX85A is carried out compatibility according to the mass ratio of 1:2, compared to other combination, prepared agricultural chemicals suspension agent all significantly will be better than other combination in the performances such as suspensibility, dispersiveness and stability, the properties of agricultural chemicals suspension agent can be promoted comprehensively, significantly, be suitable for very much the dispersant as agricultural chemicals suspension agent.
Claims (8)
1. a copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent, its constituent is: by mass percentage, and pesticide active ingredient 10-50%, composite dispersing agent 2-10%, wetting agent 1-6%, thickener 0.1-3%, antifreezing agent 1-8%, preservative 0.1-2%, surplus are water; Described pesticide active ingredient is made up of copper 8-hydroxyquinolinate and Tebuconazole; It is characterized in that: described composite dispersing agent is made up of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425 and sodium lignin sulfonate REAX85A, wherein, the mass ratio of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425 and sodium lignin sulfonate REAX85A is 1:1-2.
2. according to copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent according to claim 1, it is characterized in that: the mass ratio of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425 and sodium lignin sulfonate REAX85A is 1:2.
3. prepare a method for the copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent described in claim 1 or 2, it is characterized in that, the method comprises: in sand mill, drop into pesticide active ingredient, dispersant, wetting agent, preservative, part thickener and water, grinding; When particle diameter D90 is at 2-15 μm, stop grinding, add after antifreezing agent stirs and add remaining thickener adjustment viscosity again, to obtain final product.
4. a copper 8-hydroxyquinolinate agricultural chemicals suspension agent, its constituent is: by mass percentage, and copper 8-hydroxyquinolinate 10-40%, composite dispersing agent 2-10%, wetting agent 1-6%, thickener 0.1-3%, antifreezing agent 1-8%, preservative 0.1-2%, surplus are water; It is characterized in that: described composite dispersing agent is made up of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425 and sodium lignin sulfonate REAX85A, wherein, the mass ratio of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425 and sodium lignin sulfonate REAX85A is 1:1-2.
5. according to copper 8-hydroxyquinolinate agricultural chemicals suspension agent according to claim 4, it is characterized in that: by mass percentage, copper 8-hydroxyquinolinate 33.5%, composite dispersing agent 6%, wetting agent 2%, thickener 0.7%, antifreezing agent 5%, preservative 0.5%, surplus are water.
6. according to copper 8-hydroxyquinolinate agricultural chemicals suspension agent according to claim 4, it is characterized in that: the mass ratio of alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt D425 and sodium lignin sulfonate REAX85A is 1:2.
7. the application of the copper 8-hydroxyquinolinate Tebuconazole agricultural chemicals suspension agent described in claim 1 or 2 in the bacillary or fungal disease of control crops.
8. the application of claim 4-6 copper 8-hydroxyquinolinate agricultural chemicals suspension agent described in any one control crops in bacillary or fungal disease.
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| CN105284798B (en) * | 2015-11-30 | 2018-01-23 | 浙江海正化工股份有限公司 | A kind of composite dispersing agent for agricultural chemicals suspension agent |
| CN112715564B (en) * | 2020-12-30 | 2022-10-11 | 江阴苏利化学股份有限公司 | Pesticide composition containing tebuconazole and chlorothalonil and application thereof |
| CN113875763B (en) * | 2021-10-29 | 2022-07-22 | 黑龙江省农业科学院植物保护研究所 | Chelerythrine suspending agent and preparation method and application thereof |
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