CN101147480B - Modified lignosulfonate pesticide dispersing agent and its preparation method - Google Patents

Abstract

The present invention discloses a preparation method of modified lignosulfate agricultural chemical dispersion agent. Said preparation method includes the following steps: (1), adding water and making lignosulfonate be mixed with water, uniformly stirring them to obtain lignosulfonate solution whose concentration is 40%, utilizing alkaline regulator to regulate pH valve of system to 8.0-10.0, adding redox initiator and oxidant, heating to 80-100deg.C and making reaction for 0.5-2h; (2), using alkaline regulato to regulate pH valve of system to 9.0-11.0, adding sulfonating agent and making reaction for 2-4h at 90-100deg.C; (3), using acid regulato to regulate pH value of system to 4.0-6.0, adding polycondensation reaction monomer and making reaction for 1-3h at 90-100deg.C; and (4), adding modifying agent, after above-mentioned materials are stirred and heat-insulated for 1-2h, cooling so as to obtain the invented product.

Description

Modified lignosulfonate pesticide dispersing agent and preparation method thereof

Technical field

The present invention relates to a kind of pesticide dispersing agent and preparation method thereof, the recovery product lignosulfonates of more specifically saying so with acid polishing effluent are raw material, the pesticide dispersing agent that is prepared from through modification.

Background technology

Estimate that according to FAO (Food and Agriculture Organization of the United Nation) (FAO) crops that the whole world is lost in damage by disease and insect every year are about 10%～30% of total harvest then; Agricultural chemicals plays irreplaceable important function as the important means of insect pests crop smothering, cover crop in agricultural production.Auxiliary agent alleviates agricultural chemicals environmental pollution aspect and plays important effect at the performance pesticide efficacy, and the development of agricultural chemicals be unable to do without the development of auxiliary agent.At present pesticidal preparations develops to safety, low toxicity, efficient, no dust and new formulation direction easy to use, and wherein pesticides new formulation such as water dispersible granules, suspending agent has demonstrated great potential and wide prospect.

Pesticide water dispersible granules (WG) is a kind of granular preparation of being made through mixing, pulverizing and prilling by pesticide active ingredient, various auxiliary agent and filler.During dilute with water, disintegration rapidly, dispersion form steady suspension, for spray application.Water dispersible granules has been avoided dust pollution and harm operator and surrounding environment safety, disintegration rapidly when converting the water dilution, and dispersiveness, wetability and suspension are good, easy to use, can give full play to drug effect.Therefore, water dispersible granules development is considered to one of formulations of pesticide of tool development prospect of 21st century rapidly.

Water dispersible granules is a kind of thermodynamics and kinetics Unstable Systems, need to add auxiliary agent preventing the gathering of solid in the system or liquid particle, and makes it keep in a long time evenly disperseing and the best of performance pesticide activity component is renderd a service.Though insecticides adjuvant does not possess pesticide activity, can improve the physics and the chemical behavior of agricultural chemicals, be indispensable important component in the pesticidal preparations.Wherein dispersant can impel solid-state former medicine insoluble or that be insoluble in water to be scattered in equably in the water with fine particles, forms the aqueous dispersions with certain stability.The screening of dispersant is to influence one of principal element of preparation performance.

Dispersant commonly used in the pesticidal preparations has: naphthalenesulfonic acid-formaldehyde condensate, alkylphenol ethoxylate, polyaryl phenol ethoxylated phosphate esters, EO-PO block copolymer, polycarboxylate etc.Most of raw material sources not only consumed a large amount of petrochemical industry resources in the production process, and cost are often higher, raw material is harmful in petrochemical, can not satisfy the growth requirement of environmentally friendly agricultural chemicals.Along with being on the rise of the in short supply and problem of environmental pollution of petroleum resources, make full use of natural reproducible resource, produce the green product of " environmental friendliness " and focus and the forward position that green chemistry process has become current chemistry, chemical industry and cross discipline research thereof.Environmentally friendly agricultural chemicals at first requires auxiliary agent " greenization ", and the raw material sources of this agent of will seeking help are in renewable resources, production technology " greenization ", the nontoxic and easy degraded of product.

Lignin is that occurring in nature content is only second to cellulosic biomass resource, accounts for the 20%-30% of plant corpus weight, and the whole world can produce about 1,500 hundred million tons of lignin every year.Industrial lignin derives from the chemical pulping process, mainly comprises lignosulfonates in the acid polishing effluent and the alkali lignin in the alkaline pulp black liquor.Alkali lignin can be transformed into lignosulfonates by sulfonation.Lignosulfonates are to be the macromolecular compound of main hydrophilic radical with phenylpropyl alcohol alkyl hydrophobic framework with sulfonic group, it is the amphiphile, amphiphilic molecule organized assembles, solid particle had absorption, stably dispersing, wetting effect, it is one of pesticidal preparations dispersant kind commonly used, but exist shortcomings such as the dispersion stabilization of product and adaptability is relatively poor, require not match with the polymolecularity of pesticide water dispersible granules, therefore be difficult to be applied to separately prepare in the preparation of water dispersible granules.

For improving the dispersibility of lignosulfonates, be with lignosulfonates and anion or the composite dispersant that obtains of non-ionic surface active agent mostly in the pesticide patent both at home and abroad.Among " storage stable pesticidal aqueous emulsions " patent CN 1054204C as Switzerland Novannis company application, with composite dispersants that is used as pesticidal aqueous emulsions such as the salt of sodium, potassium, magnesium, calcium or the ammonium salt of lignin sulfonic acid and alkali metal, alkaline earth metal or the sulfonated polystyrene of anionic dispersing agents sulfonated naphthalene/formaldehyde condensation products, non-ionic dispersing agent polyvinyl alcohol, polyvinyl methyl ethers.The publication CN 1446047A of Germany Bayer Crop Science GmbH use more than the mixture of two kinds of surfactants (comprising the sulfuric ester, alkyl sulfonic ester of lignosulfonates, soap, higher alcohol and alkene etc.) in the agricultural chemicals float type preparation to strengthen the dispersibility of slurrying.The publication US 3 of Westvaco company, 986, a kind of preparation method of pesticidal preparations dispersant is provided in 979, be with 25%～95% lignosulfonates and 75%～5% anion surfactant such as aliphatic alcohol sulfate, olefinic sulphur acid esters etc., composite forming such as non-ionic surface active agent fatty acid one alkanolamine condensation product, fatty acid ethylene oxide adduct.Among the publication US 6,855,327 of Cognis company be 1: 9～9: 11 non-ionic surface active agent alkyl glycoside and the composite preparation pesticide dispersing agent of lignosulfonates with ratio range.Prepare Herbicidal suspension so that lignosulfonates, naphthalenesulfonate formaldehyde condensation compound, polycarboxylate, sulfonation CF condensation product etc. are composite as dispersant among the publication US 6,617,280 of BASF AG.

With lignosulfonates after the direct chemical modification as the patent of pesticide dispersing agent seldom.Among the publication CN 1209964C of Switzerland Singenta Participation AG be that 4～25 poly-aryl phenol phosphate of ethoxylation and EO are that the composition of 1～4 ethoxylation lignosulfonates is as the agricultural-chemical suspension dispersant with n.Wherein the alkoxylate lignosulfonates can buy or use alkylene oxide reagent such as oxirane that lignosulfonates are carried out the alkoxylation acquisition on market, by the mixed alkoxylated effect, the alkylene oxide unit of introducing is different or replaces between for example oxirane and expoxy propane.But the method complex process, big, the modification cost height of control difficulty also can't know its concrete technological parameter at present.

Summary of the invention

The objective of the invention is to overcome above-mentioned technological deficiency, with the renewable resources lignosulfonates of originating abundant, cheap is raw material, provide a kind of modified lignosulfonate pesticide dispersing agent and preparation method thereof by attainable modified technique, the degraded applied widely, easy of this dispersant, nontoxic, environmental friendliness; This preparation method's cost is low.

The preparation method of modified lignosulfonate pesticide dispersing agent of the present invention changes the molecular weight distribution of lignin sulfonic acid molecules of salt, leading active function groups kind and quantity by chemical modification (oxidation, sulfonation, polycondensation), change its micelle structure and surperficial physical and chemical performance by the physics compatibility, thereby carry out above-mentioned target, may further comprise the steps:

(1) is the solution of concentration 30%～50% weight with the lignosulfonates poach, system pH transferred to 8.0～10.0, add redox initiator and oxidant, be warming up to 80～100 ℃ of afterreactions 0.5～2 hour with alkaline conditioner;

(2) with alkaline conditioner system pH is transferred to 9.0～11.0, add sulfonating agent, reacted 2～4 hours down at 90～100 ℃;

(3) with acid regulator system pH is transferred to 4.0～6.0, add condensation polymerization monomer, reacted 1～3 hour down at 90～100 ℃;

(4) add modifier, at 80～90 ℃ of following insulated and stirred cooling discharge after 1～2 hour;

Above-mentioned raw materials weight portion consumption is as follows:

Lignosulfonates 1000;

Alkaline conditioner 10～30;

Acid regulator 5～20;

Redox initiator 3～10;

Oxidant 10～50;

Sulfonating agent 20～100;

Condensation polymerization monomer 30～50;

Modifier 5～20.

Described alkaline conditioner is sodium hydroxide and/or ammoniacal liquor.

Described acid regulator is HCl, H ₂SO ₄, in the acetate, citric acid one or more.

Described redox initiator is FeSO ₄, FeCl ₂, Fe ₂(SO ₄) ₃, Cu (NO ₃) ₂One or more.

Described oxidant is H ₂O ₂, KMnO ₄, K ₂Cr ₇O ₄, KIO ₃In one or more.

Described sulfonating agent is one or more in sodium hydrogensulfite, sodium sulphite, sodium pyrosulfite, the Sodium Metabisulfite.

Described condensation polymerization monomer is one or more in formaldehyde, urea, acetone, acrylic acid, the melamine.

Described modifier is one or more in silicone emulsion, n-butanol, lauryl amine, the positive tetradecylic acid.

The present invention compared with prior art has the following advantages and effect:

1. by active function groups kind and quantity in oxidation and the sulfonating reaction raising lignin sulfonic acid molecules of salt, strengthen its absorption and dispersive property on the pesticide granules surface; By the compatibility effect of modifier, change the aggregate structure of lignosulfonates, improve its surperficial physical and chemical performance, change its absorption configuration on the pesticide granules surface, reach good wetting and absorption stability.

2. improve the molecular weight of lignosulfonates by polycondensation reaction, make it be adsorbed on the pesticide granules surface after, not only have the Coulomb repulsion effect, also have sterically hindered effect, further improve dispersive property, and make pesticide granules keep dispersity for a long time.

3. the lignosulfonates raw material of the present invention's use can directly be reclaimed by acid polishing effluent, or is formed by the alkali lignin sulfonation transformation that alkaline pulp black liquor reclaims.The production process of modification is carried out under atmospheric low-temperature, easy operating control.With the pesticide dispersing agent of present use such as naphthalene system etc. relatively, have the advantage that technology is simple, efficient is high, production cost is low, the ratio of performance to price is good.Product appearance is a brown ceramic powder, and good water solubility, no strange taste, nontoxic belong to green chemical.

4. product of the present invention not only can be used as pesticide dispersing agent and uses separately, also can with composite uses such as the dispersant of other kinds such as naphthalene system.Stable performance, highly versatile.Adopt the water dispersible granules of preparation of product of the present invention to have the advantage that smooth in appearance is even, suspensibility is high, disintegration is fast, redispersibility is good.

Embodiment

Embodiment 1: take by weighing lignosulfonates 1000g, add water 1500g and mix solution into concentration 40% thoroughly, add 5g NaOH system pH is transferred to 9.0, add 1gFeSO ₄, 2gFe ₂(SO ₄) ₃And 40gKMnO ₄, be warming up to 85 ℃ of afterreactions 1.5 hours; Add 5gNaOH system pH is transferred to 10.0, add the 80g Sodium Metabisulfite, reacted 4 hours down for 90 ℃ in temperature; Add 20gH ₂SO ₄System pH is transferred to 4.0, add formaldehyde 50g, reacted 2 hours down for 95 ℃ in temperature; Add the 20g silicone emulsion, at 80 ℃ of following insulated and stirred of temperature cooling discharge after 1 hour.

Embodiment 2: take by weighing lignosulfonates 1000g, add water 1000g and mix solution into concentration 50% thoroughly, add 10gNaOH system pH is transferred to 10.0, add 10gFe ₂(SO ₄) ₃And 40gH ₂O ₂, 10g KIO ₃, be warming up to 95 ℃ of afterreactions 0.5 hour; Add 10gNaOH system pH is transferred to 11.0, add 50g sodium sulphite and 50g sodium hydrogensulfite, reacted 2 hours down for 95 ℃ in temperature; Add 10gHCl system pH is transferred to 5.0, add urea 40g, reacted 1 hour down for 90 ℃ in temperature; Add the 5g lauryl amine, at 85 ℃ of following insulated and stirred of temperature cooling discharge after 2 hours.

Embodiment 3: take by weighing lignosulfonates 1000g, add water 2333g and mix solution into concentration 30% thoroughly, add 5gNaOH and 5g ammoniacal liquor system pH is transferred to 9.5, add 3g Cu (NO ₃) ₂, 3g Fe ₂(SO ₄) ₃And 20gK ₂Cr ₇O ₄, be warming up to 80 ℃ of afterreactions 2 hours; Add 20g ammoniacal liquor system pH is transferred to 11.0, add 10g sodium hydrogensulfite, 5g sodium pyrosulfite and 5g sodium sulphite, reacted 3 hours down for 90 ℃ in temperature; Add the 15g citric acid system pH is transferred to 6.0, add 30g acrylic acid, reacted 2 hours down for 90 ℃ in temperature; Add the 15g n-butanol, at 90 ℃ of following insulated and stirred of temperature cooling discharge after 1.5 hours.

Embodiment 4: take by weighing lignosulfonates 1000g, add water 1500g and mix solution into concentration 40% thoroughly, add 5g ammoniacal liquor system pH is transferred to 8.0, add 8g Cu (NO ₃) ₂, 5gKIO ₃, 5g KMnO ₄, be warming up to 100 ℃ of afterreactions 1 hour; Adding 5g ammoniacal liquor, 5gNaOH transfer to 9.0 with system pH, add the 50g sodium sulphite, react 2.5 hours down for 95 ℃ in temperature; Add 3gH ₂SO ₄, 2g acetate transfers to 6.0 with system pH, adds acetone 45g, in the reaction 3 hours down of 100 ℃ of temperature; Add n-butanol 5g, silicone emulsion 5g, at 85 ℃ of following insulated and stirred of temperature cooling discharge after 1 hour.

Embodiment 5: take by weighing lignosulfonates 1000g, add water 1500g and mix solution into concentration 40% thoroughly, add 3gNaOH system pH is transferred to 8.0, add 7gFeSO ₄And 10gKIO ₃, be warming up to 80 ℃ of afterreactions 0.5 hour; Adding 13g ammoniacal liquor, 2gNaOH transfer to 10.0 with system pH, add the 65g sodium hydrogensulfite, react 3.5 hours down for 90 ℃ in temperature; Adding 5gHCl, 5g acetate transfer to 5.5 with system pH, add melamine 30g, react 1 hour down for 100 ℃ in temperature; Add positive tetradecylic acid 5g, n-butanol 5g, lauryl amine 5g, at 90 ℃ of following insulated and stirred of temperature cooling discharge after 2 hours.

Embodiment 6: take by weighing lignosulfonates 1000g, add water 1000g and mix solution into concentration 50% thoroughly, add 10g NaOH system pH is transferred to 10.0, add 10gFeCl ₂And 50gH ₂O ₂, be warming up to 95 ℃ of afterreactions 0.5 hour; Add 10gNaOH system pH is transferred to 11.0, add the 100g sodium sulphite, reacted 2 hours down for 95 ℃ in temperature; Adding 2gHCl, 4g acetate, 4g citric acid transfer to 5.0 with system pH, add urea 10g, melamine 30g, react 1 hour down for 90 ℃ in temperature; Add the positive tetradecylic acid of 5g, at 85 ℃ of following insulated and stirred of temperature cooling discharge after 2 hours.

Embodiment 7: take by weighing lignosulfonates 1000g, add water 1000g and mix solution into concentration 50% thoroughly, add 10gNaOH system pH is transferred to 10.0, add 10gFeCl ₂And 50gH ₂O ₂, be warming up to 95 ℃ of afterreactions 0.5 hour; Add 10gNaOH system pH is transferred to 11.0, add the 100g sodium sulphite, reacted 4 hours down for 95 ℃ in temperature; Adding 2gHCl, 8g acetate transfer to 5.0 with system pH, add urea 10g, melamine 20g, formaldehyde 10g, react 1 hour down for 90 ℃ in temperature; Add the positive tetradecylic acid of 5g, at 85 ℃ of following insulated and stirred of temperature cooling discharge after 2 hours.

Table 1 is the formula table of 80% dimethomorph water dispersion granula, prescription according to table 1, adopt modified lignosulfonate pesticide dispersing agent of the present invention to prepare 80% dimethomorph water dispersion granula, tested suspensibility, wetability, disintegrative and the dispersiveness of granula, and contrasted with the water dispersible granules performance of the refining wooden sodium preparation of the Kinsperse126 that uses unmodified lignosulfonates and Norway Bao Lige company.The results of property of 80% dimethomorph water dispersion granula is as shown in table 2, and wherein the mensuration of suspensibility is undertaken by CIPAC MT168, and wetability adopts the measuring graduates test method determination, is qualified less than 1min; Disintegrative represents that to measure disintegrative time length general provision is qualified less than 3min; Dispersed mensuration adopts the graduated cylinder bulk method, the number of reversals be lower than 10 persons it has been generally acknowledged that qualified.

Table 1

Component	Mass fraction (%)
		Dimethomorph naphthalenesulfonate formaldehyde condensation compound+K12 pesticide dispersing agent	80 12 8

Table 2

Dispersant	Suspensibility (%)	Wetability (s)	Disintegrative (s)	Dispersed (inferior)
						Before the heat storage	After the heat storage
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 unmodified wooden salt Kinsperse126 make with extra care wooden sodium	89.6 90.5 87.4 91.2 88.8 81.6 89.5	94.4 88.7 90.8 92.8 91.3 80.2 91.5	36 42 40 30 37 58 34	42 50 48 43 41 110 43	4 3 4 3 4 7 4

As seen from Table 2, when using the lignosulfonates that pass through modification not prepare 80% dimethomorph water dispersion granula, suspensibility, disintegrative etc. are all not ideal; And when using modified lignosulfonate pesticide dispersing agent of the present invention, the performance of water dispersible granules each side all near in addition surpass to use external product (Kinsperse126 makes with extra care wooden sodium), but the external product price reaches 18000 yuan/ton, and product cost of the present invention only is 6000 yuan/ton, and product comparatively speaking of the present invention has better economic benefit.

Claims (2)

1. the preparation method of a modified lignosulfonate pesticide dispersing agent is characterized in that this method may further comprise the steps:

(1) with the lignosulfonates poach is the solution of concentration 30%～50% weight, system pH transferred 8.0～10.0, add redox initiator and oxidant, be warming up to 80～100 ℃ of afterreactions 0.5～2 hour with alkaline conditioner;

(2) with alkaline conditioner system pH is transferred 9.0～11.0, add sulfonating agent, reacted 2～4 hours down at 90～100 ℃;

(3) with acid regulator system pH is transferred to 4.0～6.0, add condensation polymerization monomer, reacted 1～3 hour down at 90～100 ℃;

(4) add modifier, at 80～90 ℃ of following insulated and stirred cooling discharge after 1～2 hour;

Above-mentioned raw materials weight portion consumption is as follows:

Lignosulfonates 1000;

Alkaline conditioner 10～30;

Acid regulator 5～20;

Redox initiator 3～10;

Oxidant 10～50;

Sulfonating agent 20～100;

Condensation polymerization monomer 30～50;

Modifier 5～20;

Described alkaline conditioner is sodium hydroxide and/or ammoniacal liquor;

Described acid regulator is HCl, H ₂SO ₄, in the acetate, citric acid one or more;

Described redox initiator is FeSO ₄, FeCl ₂, Fe ₂(SO ₄) ₃, Cu (NO ₃) ₂One or more;

Described oxidant is H ₂O ₂, KMnO ₄, K ₂Cr ₇O ₄, KIO ₃In one or more;

Described sulfonating agent is one or more in sodium hydrogensulfite, sodium sulphite, sodium pyrosulfite, the Sodium Metabisulfite;

Described condensation polymerization monomer is one or more in formaldehyde, urea, acetone, acrylic acid, the melamine;

Described modifier is one or more in silicone emulsion, n-butanol, lauryl amine, the positive tetradecylic acid.

2. the modified lignosulfonate pesticide dispersing agent of the described method of claim 1 preparation.