CN102786697A - High molecular weight and moderate sulfonation degree lignin-based pesticide dispersant and its preparation method - Google Patents
High molecular weight and moderate sulfonation degree lignin-based pesticide dispersant and its preparation method Download PDFInfo
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Abstract
The invention discloses a high molecular weight and moderate sulfonation degree lignin-based pesticide dispersant and its preparation method. The preparation method consists of: first adding a NaOH solution into lignin powder to conduct swelling for 30-60min; adding benzyl chloride, and under the condition of an oil bath at 95-110DEG C, carrying out an etherification reaction for 2-4h; then adding water, sodium lignosulphonate, and a formaldehyde aqueous solution to perform a copolymerization reaction at 80-95DEG C for 1-3h; and adjusting the pH value to 5-9, thus obtaining the high molecular weight and moderate sulfonation degree lignin-based pesticide dispersant. The dispersant prepared in the invention has a weight-average molecular weight of more than 15000 and a sulfonation degree of 0.6-1.0mmol/g, is applicable to 80% dimethomorph water dispersible granules, 80% carbendazim water dispersible granules, 40% myclobutanil wettable powder, and a plurality of pesticide preparations and dosage forms, and has excellent dispersibility, stability, wettability and thermal storage performance.
Description
Technical field
The present invention relates to a kind of pesticide dispersing agent, particularly relate to sulfonation degree lignin-base pesticide dispersing agent and preparation method thereof in a kind of HMW.This pesticide dispersing agent is applicable to the dispersion of Multiple Pesticides preparations such as dimethomorph water dispersion granula, carbendazim water dispersing granule, nitrile bacterium azoles wettable powder and formulation.
Background technology
Estimate that according to Food and Argriculture OrganizationFAO (FAO) farm crop that the whole world is lost in disease and pest every year are about 10%～30% of total harvest then; Agricultural chemicals is as the important means of insect pests crop smothering, cover crop; At present pesticide preparation develops to safety, low toxicity, efficient, no dust and new formulation direction easy to use; Comprise the use that reduces organic solvent, water dispersible granules, wettable powder, suspension agent etc. have demonstrated great potential and wide prospect.Because most of agricultural chemicals is lyophobic dust, give full play to its drug effect, must add dispersant with high efficiency preventing the gathering of solid in the system or liquid particle, and make it keep homodisperse and the best effectiveness of bringing into play pesticide activity component in a long time.
The pesticide dispersing agent that uses at present mainly contains sulfonated lignin, naphthalenesulfonate polycondensate and poly carboxylic acid three major types.The dispersion effect of poly carboxylic acid good but cost an arm and a leg (reach 90,000 yuan/t), because lighter color, be used for light pesticide preparation on a small quantity; The dispersing property of naphthalenesulfonate polycondensate is better, but wettability and less stable, and large usage quantity, price are also higher at present.The dispersing property and the wettability of sulfonated lignin are better, and unique properties has irreplaceable effect in pesticide dispersing agent.Homemade sulfonated lignin do not carry out modification to agricultural chemicals, and the product dispersing property is general, though price is lower, consumption is less; Market is mainly occupied by the modified lignin mahogany sulfonate of companies such as U.S. MeadWestvaco and Norway Borregaard.Therefore, be that feedstock production agricultural chemicals dispersant with high efficiency is significant for reduction pesticide preparation cost, raising pesticide efficacy with the industrial lignin.
Xylogen is that occurring in nature content is only second to cellulosic biomass resource, accounts for 20 ~ 30% of plant materials weight, and the whole world can produce about 1,500 hundred million tons of xylogen every year.Industrial lignin is mainly derived from the boiling waste water of paper-making pulping industry and chemical fibre pulp industry, and according to the difference of fibrous material, pulping process and process for extracting etc., their physicochemical property differ greatly.Industrial lignin is divided into four types usually: 1. sulfonated lignin (LS): sulfonated lignin (LS) come from spentsulfiteliquor, and it has well water-soluble and application prospects.2. alkali lignin: alkali lignin mainly comes from alkaline pulp black liquors (being black liquid) such as sulphate process, contains more sugar part, inorganic salt and alkali, and application is restricted, and in alkali recovery process, is used as fuel.Can extract xylogen wherein through methods such as acid out or flocculations, water insoluble under the neutrallty condition, need through could being used as dispersion agent after the sulfonation, but owing to molecular weight and sulfonation degree are all on the low side, poor-performing.3. enzymolysis xylogen: enzymolysis xylogen is the xylogen for preparing the cellulose fermentation in the plant material (corn straw etc.) separation and Extraction in the residue of alcohol.4. other xylogen: the xylogen of pulping process gained such as the slurrying of solvent-applied method, SEP, like formic acid xylogen, acetic acid lignin, high-boiling alcohol lignin etc.
China's paper-making pulping industry can produce more than 1,000 ten thousand tons of industrial lignins every year, is main with the sulfonated lignin in the acid polishing effluent with the alkali lignin that remains in the alkaline pulping black liquor.Contain 50% ~ 60% sulfonated lignin, 10% ~ 20% reducing sugar and 20% ~ 30% inorganic salt in the acid polishing effluent, output is less; Contain 30% ~ 50% alkali lignin, 20% ~ 30% alkali, 8% ~ 15% inorganic salt and 20% ~ 30% sugar part etc. in the alkaline pulping black liquor, output is bigger, accounts for 90% of industrial lignin.The sulfonated lignin that present home market buys mainly contain two kinds, and the one, directly obtain from the acid polishing effluent concentrate drying, because without purification, the content of sulfonated lignin is about 50%, and fluctuation is bigger, its dispersing property is general; Another kind is that the alkali lignin that alkaline process black liquor acid out extracts obtains through sulfonation reaction, and purity is higher, but molecular weight and sulfonation degree are all lower, and dispersing property is general, and acid out technology environmental pollution is very big.
Because the dispersing property of sulfonated lignin is general; Domestic and international many patents adopt and the compound use of naphthalenesulfonate polycondensate; Like the Chinese invention patent CN1054204C of Switzerland Novannis company application, with composite dispersion agents that is used as pesticidal aqueous emulsions such as sulfonated lignin and sulfonated naphthalene/formaldehyde condensation products or sulfonated polystyrene salt, Z 150PH, polyvinyl methyl ethers; Prepare Herbicidal suspension so that sulfonated lignin, naphthalenesulfonate formaldehyde condensation compound, polycarboxylate, sulfonation cresoform condenses etc. are composite as dispersion agent among the publication USP6617280 of BASF AG; Patent USP6274156B1 with sulfonated lignin, polypropylene hydrochlorate, sulfonated alkyl naphathalene formaldehyde condensation products etc. as dispersion agent; The patent (USP6620421B1) of inventions such as Shugo Nishi is that dispersion agent prepares WG (water dispersible granules) with naphthalene system and sodium lignosulfonate, and consumption is less than 10%; People such as Narayanan (USP5714157) carry out calcium dodecylbenzene sulphonate, wooden salt and naphthalenesulfonate formaldehyde condensation compound composite as dispersion agent; The patent of Masahiro (USP20040057971A1) is a dispersion agent with naphthalene system and sodium lignosulfonate.Sulfonated lignin also can be composite as dispersion agent with other negatively charged ion or nonionogenic tenside, as the Chinese invention patent CN1446047A of German Baeyer application use more than the mixture of two kinds of tensio-active agents (comprising the sulfuric ester, alkyl sulfonic ester of sulfonated lignin, soap, higher alcohols and alkene etc.) in the agricultural chemicals floated preparation to strengthen dispersive ability; Patent USP3986979 is main with wooden salt, adds a spot of negatively charged ion or nonionic wetting agent, is used for the processing of multiple water-insoluble agricultural chemicals; A kind of preparation method of pesticide preparation dispersion agent is provided among the patent USP3986979 of Westvaco company; Be with 25% ~ 95% sulfonated lignin and 75% ~ 5% AS such as aliphatic alcohol sulfate, olefinic sulphur acid esters etc., composite forming such as nonionogenic tenside lipid acid-alkanolamine condenses, lipid acid ethylene oxide adduct.Be nonionogenic tenside APG and the composite preparation pesticide dispersing agent of sulfonated lignin of 1:9 ~ 9:11 with ratio range among the publication USP6855327 of Cognis company.Patent USP7338920 develops a kind of compound herbicide that contains plurality of active ingredients, and its dispersion agent adopts wooden salt, sodium lauryl sulphate, polyoxyethylene glycol octyl group sulfonated ester etc. composite.The composite sulfonated lignin that make of physics can be used in the part formulation of pesticide, but can not fundamentally improve the application performance of sulfonated lignin.
Some progress have also been obtained through chemical modification development sulfonated lignin pesticide dispersing agent.Chinese invention patent CN1603514 adds steaming-boiling agent, properties-correcting agent and lignin molecule amount adjusting control agent in the lump in the paper-making pulping cooking process; Boiling is after purification, concentrated, twice-modified; The spray-dried again modified lignin resin product that obtains high added value can be used as pesticide dispersing agent; Patent EP1586237 is used for WG after with sulfonated lignin and formaldehyde condensation; Meadwestvaco company (USP4751247) separates xylogen acid out from black liquor, carries out hydroxymethylation with formaldehyde, regulates pH to 2 ~ 3 acidifyings, and inorganic salt and other impurity are removed in washing, again with organic amine and oxygen sulfur compound (like SO
2) reaction, generate the sulfomethylation lignin amine, again as pesticide dispersing agent; Patent US P6855327 obtains a kind of neutral sodium lignosulfonate based on high sulfonic group content and low-molecular-weight lignin modification, and it is composite to mix a spot of alkyl glucose of gathering, and not only is applicable to solid preparation, also is applicable to liquid preparation.
Sulfonated lignin are to be the amphiphilic polymer of main hydrophilic radical with phenylpropyl alcohol alkane hydrophobic framework with sulfonate radical; Mainly on hydrophobicity agricultural chemicals (major part has benzene ring structure) particle, adsorb through π-π effect and hydrogen bond action; The absorption back relies on the negative charge of sulfonate radical and macromolecular sterically hindered making between particle to repel each other; Be scattered in equably in the water, form aqueous dispersions with certain stability.Discover that molecular weight and sulfonation degree are the key factors of decision lignosulfonic acid salt pair pesticide granules absorption dispersing property.Benzene ring structure is more in the lignosulfonic acid molecules of salt, molecular weight is big more, and then the adsorption site on pesticide granules is more, absorption is strong more, sterically hindered big more after the absorption, and dispersing property is strong more; Sulfonation degree is high more, absorption back form particle with negative charge many more, electrostatic repulsion is big more, but because of wetting ability strengthens, adsorptive capacity descends.Therefore sulfonation degree is the desired characteristics of sulfonated lignin agricultural chemicals dispersant with high efficiency in the HMW.
On the other hand, hydrophilic group (sulfonate radical, carboxyl, hydroxyl etc.) and oleophilic group (C in the commercially available lignosulfonic acid molecules of salt
6-C
3Structure) distribution uniform, make its oleophilicity a little less than, cause adsorptive power and adsorption strength on the hydrophobicity pesticide granules lower, this has directly influenced the performance of its dissemination.
Summary of the invention
The objective of the invention is, hydrophilic group less and oleophilic group distributes too evenly, the relatively poor deficiency of dispersing property to existing sulfonated lignin pesticide dispersing agent molecular weight; Abundant to originate, cheap, reproducible xylogen is a raw material; Provide that sulfonation degree is a sulfonated lignin agricultural chemicals dispersant with high efficiency in a kind of HMW, the weight-average molecular weight of dispersion agent greater than 15000, sulfonation degree is 0.6～1.0mmol/g.This dispersion agent is applicable to the water dispersible granules and the wettable powder of Multiple Pesticides, has good dispersiveness, stability, wettability and heat storage performance.
Another object of the present invention is to provide the preparation method of said sulfonated lignin agricultural chemicals dispersant with high efficiency.
It is that etherifying agent is introduced benzyl in xylogen powder (comprising alkaline pulping black liquor powder, acid out alkali lignin and enzymolysis xylogen, high-boiling alcohol lignin etc.) that the inventive method at first adopts Benzyl Chloride, increases the benzene ring structure in the lignin molecule; Add sulfonated lignin then, formaldehyde carries out copolyreaction; Can improve the molecular weight of sulfonated lignin on the one hand; Can make the hydrophilic group and the oleophilic group of product more be tending towards the two ends distribution on the other hand; Thereby prepare the sulfonated lignin of sulfonation degree in the HMW, use the used as pesticides dispersant with high efficiency.
The object of the invention is realized through following technical scheme:
The preparation method of sulfonation degree lignin-base pesticide dispersing agent in a kind of HMW may further comprise the steps:
(1) in the xylogen powder, adds NaOH solution swelling 30 ~ 60min;
(2) add Benzyl Chloride, at 95 ~ 110 ℃ of following etherification reaction 2 ~ 4h of oil bath;
(3) add entry, sodium lignosulfonate, formalin then, 80 ~ 95 ℃ of following copolyreaction 1 ~ 3h;
(4) regulate pH value to 5 ~ 9, obtain sulfonation degree lignin-base pesticide dispersing agent in the HMW; The weight-average molecular weight of said dispersion agent greater than 15000, sulfonation degree is 0.6 ~ 1.0mmol/g.
In parts by weight, the consumption of composition of raw materials is:
Said xylogen powder is selected from the pulvis that one or more dryings in pulp black liquor, bamboo pulp black liquor, wheat straw black liquor, reed pulp black liquor, bagasse black liquor, Herba Poae Sphondylodis slurry black liquor, cotton stalk pulp black liquor and the cotton pulp black liquor form, or said xylogen powder is selected from the pulvis that enzymolysis xylogen or lignin by acid separation drying form; Or said xylogen powder is selected from the pulvis that one or more dryings in formic acid xylogen, acetic acid lignin and the high-boiling alcohol lignin form;
The mass concentration of said formalin is 35-40%.
For further realizing the object of the invention, the mass concentration of said formalin is preferably 37%.
Said adjusting pH value to 5 ~ 9th regulated through adding acidic substance; Said acidic substance preferentially are selected from one or both in sulfuric acid, nitric acid or the hydrochloric acid.
Sulfonation degree lignin-base pesticide dispersing agent in a kind of HMW, the weight-average molecular weight of this dispersion agent greater than 15000, sulfonation degree is 0.6 ~ 1.0mmol/g.
Said dispersion agent preferably adopts spraying drying to obtain powder product.
The weight-average molecular weight of sulfonation degree lignin-base pesticide dispersing agent is preferably 15200-18600 in the said HMW.
In the present invention, described pulp black liquor, bamboo pulp black liquor, wheat straw black liquor, reed pulp black liquor, bagasse black liquor, Herba Poae Sphondylodis slurry black liquor, cotton stalk pulp black liquor or cotton pulp black liquor are that alkaline process obtains black digestion liquid in paper industry and the chemical fibre industry.For example, the pulp black liquor that obtains of Nan Ping, Fujian paper industry Pinus massoniana Lamb alkaline process; Yibin, Sichuan paper industry bamboo alkaline process obtains bamboo pulp black liquor; The wheat straw black liquor that Shandong spring woods paper industry wheat straw alkaline process obtains; Hebei Jigao Fiber Co.,Ltd's linters alkaline process is produced in the cotton pulp dregs of rice and is obtained cotton pulp black liquor.
In the present invention, described enzymolysis xylogen is the xylogen for preparing the cellulose fermentation in the plant material (corn straw etc.) separation and Extraction in the residue of alcohol.For example, the xylogen that extracts in Jilin a small bay in a river board development of agricultural products company " ethanol is produced in the pre-treatment of the corn straw wet oxidation " residue.
In the present invention, described lignin by acid separation is the xylogen that black liquor obtains through acid-precipitation method.For example, Hunan Tag woods group Yongzhou Xiang River paper industrial limited company adopts the sulfuric acid acid-precipitation method to handle the wood pulp xylogen that black liquor obtains.
In the present invention, described formic acid xylogen, acetic acid lignin, high-boiling alcohol lignin are to adopt formic acid, acetate or the high alcohol that boils to carry out the xylogen that slurrying is extracted as cooking liquor.For example, the high-boiling alcohol lignin sold of the gloomy luxuriant fine chemistry industry auxiliary agent in Nan Ping ltd.
Sodium lignosulfonate of the present invention is the commercially available prod, can be from the sodium lignosulfonate of acid polishing effluent, or from the alkali lignin of alkaline process through sulfonation reaction and the sulfonation alkali lignin.
The present invention compared with prior art has the following advantages and effect:
(1) the lignin-base agricultural chemicals dispersant with high efficiency of the present invention preparation has the characteristics of sulfonation degree in the HMW, the sulfonated lignin weight-average molecular weight greater than 15000, sulfonation degree is 0.6～1.0mmol/g.
(2) method of the introducing of benzyl of the present invention and employing xylogen and sulfonated lignin copolymerization makes that the product hydrophilic group of preparation and oleophilic group distribution are more obvious, on the hydrophobicity pesticide granules, has adsorptive power and absorption stability by force.
(3) the lignin-base agricultural chemicals dispersant with high efficiency of the present invention's preparation has good dispersiveness, stability and heat storage performance.With common sodium lignosulfonate contrast, the suspensibility of 80% dimethomorph water dispersion granula improves 10 percentage points; Heat storage back is improved more than 5 percentage points.
(4) the lignin-base agricultural chemicals dispersant with high efficiency of the present invention's preparation is applicable to Multiple Pesticides formulations such as water dispersible granules and wettable powder.For example 80% HSDB 6915,80% derosal, 40% acetamiprid water dispersible granules and 40% nitrile bacterium azoles wettable powder, 40% isoprocarb wettable powder etc.
Embodiment
Below in conjunction with embodiment the present invention is further described, need to prove, embodiment does not constitute the restriction that the present invention is required protection domain.
Embodiment 1: take by weighing 50g wood pulp papermaking black liquor powder, the NaOH solution of adding 50mL, 10mol/L is swelling 30min at normal temperatures; After adding the 20g Benzyl Chloride then, stir and carry out etherification reaction 3h after oil bath is warmed up to 100 ℃; Add entry 300g, sodium lignosulfonate 100g, formalin (the formaldehyde mass content is 37%) 25g, at 85 ℃ of following copolyreaction 3h.Adopting mass concentration at last is that 20% sulphuric acid soln is regulated pH to 7, again product is cooled to room temperature and can obtains lignin-base agricultural chemicals dispersant with high efficiency liquid product.
Embodiment 2: take by weighing 50g bamboo pulp black liquor powder, the NaOH solution of adding 50mL, 10mol/L is swelling 60min at normal temperatures; After adding the 30g Benzyl Chloride then, stir and carry out etherification reaction 2h after oil bath is warmed up to 95 ℃; Add entry 200g, sodium lignosulfonate 60g, formalin (the formaldehyde mass content is 37%) 40g, at 95 ℃ of following copolyreaction 2h.Adopting concentration at last is the salpeter solution adjusting pH to 7 of 20wt%, again product is cooled to room temperature and can obtains lignin-base agricultural chemicals dispersant with high efficiency liquid product.
Embodiment 3: take by weighing 50g wheat straw black liquor powder, the NaOH solution of adding 50mL, 10mol/L is swelling 40min at normal temperatures; After adding the 20g Benzyl Chloride then, stir and carry out etherification reaction 4h after oil bath is warmed up to 110 ℃; Add entry 300g, sodium lignosulfonate 70g, formalin (the formaldehyde mass content is 37%) 50g, at 95 ℃ of following copolyreaction 2h.Adopting concentration at last is the hydrochloric acid soln adjusting pH to 8 of 20wt%, again product is cooled to room temperature and can obtains lignin-base agricultural chemicals dispersant with high efficiency liquid product.
Embodiment 4: take by weighing 20g cotton stalk pulp black liquor powder and 30g pulp black liquor powder, the NaOH solution of adding 50mL, 10mol/L is swelling 30min at normal temperatures; After adding the 40g Benzyl Chloride then, stir and carry out etherification reaction 1h after oil bath is warmed up to 105 ℃; Add entry 250g, sodium lignosulfonate 80g, formalin (the formaldehyde mass content is 37%) 30g, at 80 ℃ of following copolyreaction 1h.Adopting concentration at last is the hydrochloric acid soln adjusting pH to 7 of 20wt%, again product is cooled to room temperature and can obtains lignin-base agricultural chemicals dispersant with high efficiency liquid product.
Embodiment 5: take by weighing 10g enzymolysis xylogen powder, 10g wood pulp lignin by acid separation powder and 30g bamboo pulp black liquor powder, the NaOH solution of adding 50mL, 10mol/L is swelling 50min at normal temperatures; After adding the 35g Benzyl Chloride then, stir and carry out etherification reaction 3h after oil bath is warmed up to 105 ℃; Add entry 300g, sodium lignosulfonate 50g, formalin (the formaldehyde mass content is 40%) 45g, at 85 ℃ of following copolyreaction 2h.Adopting concentration at last is the sulphuric acid soln adjusting pH to 9 of 20wt%, again product is cooled to room temperature and can obtains lignin-base agricultural chemicals dispersant with high efficiency liquid product.
Embodiment 6: take by weighing 20g enzymolysis xylogen powder, 20g wheat straw black liquor powder and 10g cotton pulp black liquor powder, the NaOH solution of adding 50mL 10mol/L is swelling 30min at normal temperatures; After adding the 25g Benzyl Chloride then, stir and carry out etherification reaction 2h after oil bath is warmed up to 110 ℃; Add entry 300g, sodium lignosulfonate 90g, formalin (the formaldehyde mass content is 35%) 30g, at 90 ℃ of following copolyreaction 2h.Adopting concentration at last is the salpeter solution adjusting pH to 9 of 20wt%, again product is cooled to room temperature and can obtains lignin-base agricultural chemicals dispersant with high efficiency liquid product.
The explanation of embodiment effect:
Measuring molecular weight, sulfonation degree and the performance when being used for pesticide preparation of dispersant with high efficiency of the foregoing description preparation, the result sees table 1.
The structure and the performance of table 1 different sorts lignin-base pesticide dispersing agent
Table 1 explanation:
(1) mensuration of weight-average molecular weight adopts gel permeation chromatography, and standard specimen is a PS sulfonation sodium; Sulfonation degree is to adopt automatic potentiometric titration to measure; Sample is all through negatively charged ion, resin cation(R.C.) purifying;
(2) sodium lignosulfonate (wood pulp) is to be the product of raw material through the acid polishing explained hereafter by Jilin stone Xian paper industry with timber;
(3) WG is a pesticide water dispersible granules, and the prescription of 80% HSDB 6915 WG is m (HSDB 6915): m (naphthalenesulfonate formaldehyde condensation compound): m (sodium lauryl sulphate): m (wooden salt)=80:9:3:8; Pesticide dispersing agent WP is a pesticide wettable, and the prescription of 40% nitrile bacterium azoles WP is m (a nitrile bacterium azoles): m (naphthalenesulfonate formaldehyde condensation compound): m (wooden salt): m (kaolin)=40:9:6:45; The prescription of 40% isoprocarb WP is m (isoprocarb): m (drawing back powder): m (a wooden salt): m (zeyssatite)=40:9:6:45.
(4) storage of the heat of pesticide preparation is meant and in 54 ± 2 ℃ electric drying oven with forced convection, places sample sealing back 14 days.
(5) pesticide preparation suspensibility measuring method is with reference to CIPAC MT168.
Visible from table 1; The product content of the present invention preparation greater than 75%, weight-average molecular weight greater than 5000, sulfonation degree is 1.0～2.0mmol/g; Purity and molecular weight are greater than sodium lignosulfonate (wood pulp); Sulfonation degree is close with it, can reach the purpose of synthetic middle sulfonation degree HMW lignin-base pesticide dispersing agent.Also can see from table 1, adopt suspensibility after the pesticide preparation heat storage of product prepn of the present invention, explain that dispersing property is better all than adopting the high five more than the per-cent of wood pulp sodium lignosulfonate preparation.
It is that etherifying agent is introduced benzyl in the xylogen powder that the present invention at first adopts Benzyl Chloride, increases the benzene ring structure in the lignin molecule, makes it form π-pi-conjugated absorption more easily at hydrophobicity agricultural chemicals (major part has benzene ring structure) particle surface.Modified-reaction further adds sulfonated lignin, formaldehyde carries out copolyreaction, can improve on the one hand sulfonated lignin molecular weight, its oleophilicity is strengthened, thereby the adsorptive capacity on the hydrophobicity agricultural chemicals is more; On the other hand; Connection between xylogen and the sulfonated lignin can make the hydrophilic group of product and oleophilic group more be tending towards the two ends distribution; Sterically hindered effect that the dispersion agent product of feasible preparation forms after the pesticide granules surface adsorption and Coulomb repulsion effect are concentrated with obvious more, thereby Multiple Pesticides is all had efficient dissemination.And the stability of its absorption and difficult drop-off property, being it also has the immediate cause of same excellent dispersion properties to the pesticide preparation after the heat storage.Visible by table 1, the dispersion agent of the present invention's preparation is applicable to the water dispersible granules and the wettable powder of Multiple Pesticides, has good dispersiveness, stability, wettability and heat storage performance.
Being raw material development pesticide dispersing agent with industrial lignin (alkali lignin or sulfonated lignin) in the prior art, generally is to adopt physical purification methods such as ultrafiltration, desugar, or chemical modification methods such as oxidation, sulfonation, carboxylated, condensation.And the present invention is at the physicochemical characteristic of having analyzed pesticide granules itself; Set about from the absorption matching that improves modified lignin resin product and pesticide granules; Propose the employing Benzyl Chloride and in xylogen, introduced benzyl; And carry out copolymerization through xylogen and sulfonated lignin, and finally having obtained sulfonation degree sulfonated lignin in the HMW that strong and oleophilicity of oleophilicity and wetting ability two ends distribute, principle of the present invention and prior art have bigger different.
Claims (6)
1. the preparation method of sulfonation degree lignin-base pesticide dispersing agent in the HMW is characterized in that may further comprise the steps:
(1) in the xylogen powder, adds NaOH solution swelling 30 ~ 60min;
(2) add Benzyl Chloride, at 95 ~ 110 ℃ of following etherification reaction 2 ~ 4h of oil bath;
(3) add entry, sodium lignosulfonate, formalin then, 80 ~ 95 ℃ of following copolyreaction 1 ~ 3h;
(4) regulate pH value to 5 ~ 9, obtain sulfonation degree lignin-base pesticide dispersing agent in the HMW; The weight-average molecular weight of said dispersion agent greater than 15000, sulfonation degree is 0.6 ~ 1.0mmol/g.
In parts by weight, the consumption of composition of raw materials is:
Said xylogen powder is selected from the pulvis that one or more dryings in pulp black liquor, bamboo pulp black liquor, wheat straw black liquor, reed pulp black liquor, bagasse black liquor, Herba Poae Sphondylodis slurry black liquor, cotton stalk pulp black liquor and the cotton pulp black liquor form, or said xylogen powder is selected from the pulvis that enzymolysis xylogen or lignin by acid separation drying form; Or said xylogen powder is selected from the pulvis that one or more dryings in formic acid xylogen, acetic acid lignin and the high-boiling alcohol lignin form;
The mass concentration of said formalin is 35-40%.
2. preparation method according to claim 1 is characterized in that, the mass concentration of said formalin is 37%.
3. preparation method according to claim 1 is characterized in that, said adjusting pH value to 5 ~ 9th regulated through adding acidic substance; Said acidic substance are selected from one or both in sulfuric acid, nitric acid or the hydrochloric acid.
4. sulfonation degree lignin-base pesticide dispersing agent in the HMW of each said method preparation in the claim 1 to 3, the weight-average molecular weight that it is characterized in that this dispersion agent greater than 15000, sulfonation degree is 0.6 ~ 1.0mmol/g.
5. according to sulfonation degree lignin-base agricultural chemicals dispersant with high efficiency in the said HMW of claim 4, it is characterized in that said dispersion agent adopts spraying drying to obtain powder product.
6. according to sulfonation degree lignin-base agricultural chemicals dispersant with high efficiency in the said HMW of claim 4, it is characterized in that the weight-average molecular weight of sulfonation degree lignin-base pesticide dispersing agent is 15200-18600 in the said HMW.
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| CN105504308A (en) * | 2015-12-18 | 2016-04-20 | 华南理工大学 | High-molecular-weight lignin pesticide dispersant with high carboxyl group content and preparing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751247A (en) * | 1985-10-03 | 1988-06-14 | Westvaco Corporation | Amine salts of lignosulfonates |
| CN101147480A (en) * | 2007-09-13 | 2008-03-26 | 华南理工大学 | Modified lignosulfonate pesticide dispersing agent and its preparation method |
| CN102146146A (en) * | 2010-02-10 | 2011-08-10 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
-
2012
- 2012-07-17 CN CN201210248430.6A patent/CN102786697B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751247A (en) * | 1985-10-03 | 1988-06-14 | Westvaco Corporation | Amine salts of lignosulfonates |
| CN101147480A (en) * | 2007-09-13 | 2008-03-26 | 华南理工大学 | Modified lignosulfonate pesticide dispersing agent and its preparation method |
| CN102146146A (en) * | 2010-02-10 | 2011-08-10 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李晓娜等: "相对分子质量和磺化度对木质素磺酸钠农药分散剂性能的影响", 《精细化工》, vol. 26, no. 8, 30 August 2009 (2009-08-30), pages 755 - 759 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504308A (en) * | 2015-12-18 | 2016-04-20 | 华南理工大学 | High-molecular-weight lignin pesticide dispersant with high carboxyl group content and preparing method thereof |
| CN105504308B (en) * | 2015-12-18 | 2017-11-07 | 华南理工大学 | Lignins pesticide dispersing agent with high-carboxyl-content HMW and preparation method thereof |
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| CN102786697B (en) | 2014-02-12 |
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