CN101810173A - Agricultural effervescing agent and preparation method thereof - Google Patents
Agricultural effervescing agent and preparation method thereof Download PDFInfo
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- CN101810173A CN101810173A CN200910108117A CN200910108117A CN101810173A CN 101810173 A CN101810173 A CN 101810173A CN 200910108117 A CN200910108117 A CN 200910108117A CN 200910108117 A CN200910108117 A CN 200910108117A CN 101810173 A CN101810173 A CN 101810173A
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Abstract
The invention belongs to a novel agricultural effervescing agent and relates to a chitosan or oligosaccharide effervescing agent and a preparation method thereof. The chitosan or oligosaccharide effervescing agent comprises a chitosan or oligosaccharide derivant and one or more compounds capable of generating gas when contacting with water. The chemical name of the chitosan is beta-1,4-poly-D-glucosamine; and the molecular formula of the chitosan is (C6H11O4N)n. The invention has an optimized scheme that: the chitosan is chitosan oligosaccharide, which is also named oligosaccharins, oligomerized chitosan, oligosaccharide, chitooligosaccharide, chitin oligosaccharide and the like, the chemical name of the chitosan is belt-1,4-oligo-D-glucosamine, and the molecular formula of the chitosan is (C6H11O4N)n, wherein n is between 2 and 20. The preparation method of the invention comprises the steps of weighing, mixing, crushing, pelleting and drying formula materials. The agricultural effervescing agent of the invention has high disintegration speed in water and full dissolution (dispersion), does not block a spray head and an irrigation pipeline, does not need heating during use, has difficult absorption of moisture and low packaging, storage, transportation, metering and use cost, is widely applied to grain crops, cash crops, gardening, lawns and urban landscaping, and has wide market application prospect.
Description
Technical field
The invention belongs to the novel agricultural effervescent agent, relate to a kind of shitosan or oligosaccharide effervescent agent and preparation method thereof.
Background technology
The object of the present invention is to provide a kind of efficient, quick (dispersion), stable high agricultural shitosan or oligosaccharide effervescent agent of dissolving.Another object of the present invention is to provide the preparation method of above-mentioned agricultural effervescing agent.
Shitosan (Chitosan) is the product behind chitin (Chitin) deacetylation, and chemical name is: β-1,4-gathers-D-glucosamine, molecular formula: (C
6H
11O
4N) n is the most basic, the most important derivative of chitin.Chitin has another name called chitin, chitin, and chemical name is: (1,4)-2-acetamide-2-deoxidation-callose, molecular formula is: (C
8H
13O
5N) n, its structure is similar to cellulose.Mainly be present in the cell wall of animal shells such as shrimp, crab, pupa and insect and mushroom, algae.The biosynthesis amount of annual chitin is billions of tons on the earth, is that output is only second to cellulosic natural polymer.
Be the structure of chitin and chitosan molecule below:
Pure chitin and shitosan are white plates or powdery solid, have strong hydrogen bond action between the chitin molecule, make chitin form the crystalline texture of height, thereby chitin molecule height indissoluble.Water insoluble and the most organic solvents of chitin also are insoluble to diluted acid, rare concentrated base, only are dissolved in concentrated acid and some solvent, but main chain is degraded simultaneously.The insoluble range of application that limited of chitin is used so be processed into shitosan mostly.
The active group of chitosan molecule is amino rather than acetyl group, thereby chemical property and dissolubility make moderate progress than chitin, dissolves in diluted acid, formic acid, acetate, but also water insoluble and most organic solvent.Because amino and hydroxyl are more active, the chemical property of shitosan is active than chitin, and the number of chemical reaction can take place, and such as alkylation, acylation reaction or the like, can produce many chitosan derivatives in view of the above, as CMC or the like.
Shitosan and derivative thereof are because its recyclability, various active group in biocompatibility and the structure, has multiple good character, to be that natural world is unique be with cationic natural activity polysaccharide to shitosan, be described as and remove carbohydrate, protein, fat, vitamin, human body the 6th vital principle outside the mineral matter, be confirmed as the unique health food that can propagate curative effect in Japan, in the last few years, along with improving constantly with the further in-depth of application study the understanding of shitosan, various countries carry out, shitosan has been applied in many fields, at cosmetics, health products, food industry, medicine, chemical industry, papermaking, agricultural, environmental protection, be widely used in the fields such as light textile.
But, restricted the further expansion of its range of application because shitosan can not be directly water-soluble.Therefore, people have developed chitosan oligosaccharide again, and chitosan oligosaccharide is to be raw material with the shitosan, the low molecular weight product that good water solubility, function are big, biologically active is high that forms through biotechnologys such as acid-hydrolysis method or enzyme hydrolysis method degradeds.
Chitosan oligosaccharide also claims amino-oligosaccharide, chitosan oligomer, chitin oligosaccharide, shell oligosaccharide, chitin oligo saccharide etc., and chemical name is: β-1,4-oligomerization-D-glucosamine, molecular formula: (C
6H
11O
4N) n, wherein n is 2-20.Compare with high molecular shitosan, molecular weight is lower than 10,000 low molecular chitosan and has better dissolubility, higher biologically active, more physiological function, be more conducive to digesting and assimilating of human body intestinal canal, chitosan oligosaccharide is nearly 100% in the human body internal absorption factor, and its effect is tens of times of shitosan.
Below be the present situation that shitosan or chitosan oligosaccharide are used on agricultural, studies have shown that:
But the disease resistance of 1 inducing plant, multiple fungi, bacterium and virus are produced immunity and killing action, can be widely used in the diseases such as virus, bacterium, fungus-caused mosaic disease, little leaf, spot disease, anthracnose, downy mildew, eqpidemic disease, climing rot, yellow dwarf, rice blast, bacterial wilt, soft rot of control fruit tree, vegetables, underground rhizome, tobacco, traditional Chinese medicine and grain and cotton crop.
2, chitosan oligosaccharide (particularly four, five, six sugar) but stimulating plant growth, effectively improve crops and fruit and vegetable output, prevention and elimination of disease and pests, the beneficial bacterium of propagation soil and bio-bacterial manure, be described as the agricultural chemicals that is not agricultural chemicals, be not the chemical fertilizer of chemical fertilizer, the special role of the fertile economic benefits and social benefits of this medicine of chitosan oligosaccharide has determined its extensive use at agriculture field.
3, can change soil microflora, the promotion beneficial microorganism is grown and is suppressed some phytopathogens.
4, the various plants pathogen had to a certain degree direct repression, influence fungus spore germination, bring out that the mycelia form morphs, biochemistry changes etc. in the spore, it is remarkable to suppress the putrefying bacteria impact of performance, have both multiple function, when being natural fruit, the food preservative freshness retaining agent of function admirable.
5, on food, can be used as preservative film.Its aqueous solution is applied to fruit and vegetable surfaces, can artificially forms the closed environment of a hypoxemia high carbon dioxide at fruit and vegetable surfaces, suppress fruits and vegetables and breathe, antibacterial breeding simultaneously improves the fruits and vegetables glossiness, improves the organoleptic quality of fruit tree.
6, can excite the plant vivo gene, produce and to have chitinase, dextranase, guarantor's element and the PR albumen etc. of resistant effect, and have the cell activation effect, the recovery of the plant that helps to be injured strengthens the resistance of crop at short root strong sprout, promotes growth and development of plants.
7, chitosan oligosaccharide is used characteristics such as have trace (PPM level), efficient, low-cost, nuisanceless on agricultural, and is significant to China's agricultural sustainability development.
The problem that exists during shitosan or chitosan oligosaccharide are used on agricultural:
1, poorly soluble.Shitosan generally need be dissolved in 1% the acetum, and chitosan solution is nondispensable too dense, also can only be mixed with concentration less than 5% solution for moderately viscous shitosan.Can be converted into colloid when concentration is too big, even form the swelling thing.Even dissolubility is chitosan oligosaccharide preferably, also need to be heated to about 40 ℃, same solvability is little, and the content of commercially available prod is between 0.5-2%.Bring very big inconvenience for like this peasant's use, because the content of fluid product is too low, cause the significant wastage of packing, accumulating simultaneously.
2, the solid product hygroscopicity is strong.Shitosan has very strong hygroscopicity, is only second to glycerine, is higher than polyethylene glycol, sorbierite.In moisture absorption process, the hydroxyl in the molecule, amido isopolarity group and hydrone effect and hydration, strand expands gradually, the change of physical property and chemical property takes place, to packing, the accumulating conditional request height of product.
3, fluid product poor stability.Shitosan is deposited as solution and when using, need be in the sour environment.Because it has ethylidene ether structure, in acid solution degradation of chitosan will take place, solution viscosity also descends thereupon.
At the problems referred to above, the applicant has developed agricultural shitosan or chitosan oligosaccharide effervescent agent.When used in the field, described agricultural effervescing agent was after entry, and disintegration rapidly is dissolved in the water active ingredient fast.
Effervescent agent is a kind of novel formulation, be mainly used in the exploitation of human medicine, the effervescent agent of Initial Public Offering is the vitamin C effervescent tablet that Roche Holding Ag produces in the world, after this, Beyer Co., Ltd's Development and Production goes out the aspirin effervescent tablet, from then on worldwide starts effervescent agent and is applied to tide in medicine and the health-care preparation.Especially in recent years, obtained high speed development in fields such as vitamins, Amino-Cerv, flu medication, health products, Chinese herbal medicines.
Compare with other formulation products of shitosan or chitosan oligosaccharide, agricultural effervescing agent of the present invention is easy to use except having, cost is low, also has the following advantages:
The disintegration rate of particle is fast;
Uniform dissolubility fast;
There is not bulky grain after the dissolving, not blocking sprayer and drip irrigation facility;
Excellent storage stability;
Good fluidity, the packing, the storing cost low;
There is not dust, environmentally friendly;
The liquid of preparation has good wetability, and permeability and plate-out ability have improved the availability of active ingredient, has reduced waste and to the pollution of environment.
The present invention is with shitosan or chitosan oligosaccharide, be processed into novel form--effervescent agent, disintegration rate is fast in water, dissolving fully, do not stop up shower nozzle and drip irrigation pipeline, do not need heating during use, the active constituent content height, packing, storing, metering, use cost is low, owing to added wetting dispersing agent, soup after the preparation has good wetability, permeability and plate-out ability, improved the availability of active ingredient, reduced waste and, had a tangible performance the pollution of environment, cost and environment-friendly advantage, be widely used in cereal crops, economic crops, gardening, lawn and urban afforestation, its market application foreground is very wide.
Summary of the invention
The objective of the invention is to be achieved through the following technical solutions: a kind of agricultural effervescing agent, it is characterized in that, comprise that shitosan and/or chitosan derivatives and one or more contact the compound that produces gas with water, the chemical name of described shitosan is β-1,4-gathers-D-glucosamine, and molecular formula is: (C
6H
11O
4N) n.
Shitosan of the present invention is included on the chitosan molecule structure by modifying the chitosan derivatives that produces.
The present invention accelerates shitosan or disintegration, dissolving (refer to water-soluble good chitosan oligosaccharide), the dispersion (refer to water-soluble relatively poor shitosan) of chitosan oligosaccharide in water by auxiliary agents such as blowing agent, dispersants, reaches the purpose that solves traditional shell glycan or chitosan oligosaccharide product shortcoming with this.
In the present invention, the described compound that produces gas that contacts with water can be the metal dust that can react with water, aqueous slkali or acid solution, as Zn, and Fe etc.Also can be alkali metal or alkaline earth metal.
At one of preferred version of the present invention be, contact the compound that produces gas with water and be selected from carbonate or bicarbonate, or the mixture of the two, described carbonate and bicarbonate include but not limited to Li
2CO
3, Na
2CO
3, K
2CO
3, (NH
4)
2CO
3, MgCO
3, CaCO
3, Ca (HCO
3)
2, LiHCO
3, NaHCO
3, KHCO
3And NH
4HCO
3
Preferred version of the present invention is: described agricultural effervescing agent is mixed with by the raw material of following parts by weight:
0.1～95 part of shitosan and/or chitosan derivatives
5～50 parts of carbonate and/or bicarbonates
0～94.9 part of auxiliary agent.
One of preferred version of the present invention, described shitosan are chitosan oligosaccharide, also claim amino-oligosaccharide, chitosan oligomer, chitin oligosaccharide, shell oligosaccharide, chitin oligo saccharide etc., and chemical name is: β-1,4-oligomerization-D-glucosamine, molecular formula: (C
6H
11O
4N) n, wherein n is 2-20.
Chitosan oligosaccharide of the present invention is included on the chitosan oligosaccharide molecular structure by modifying the chitosan oligosaccharide derivative that produces.
One of preferred version of the present invention, described chitosan oligosaccharide agricultural effervescing agent is characterized in that, is mixed with by the raw material of following parts by weight:
0.1～95 part in chitosan oligosaccharide and/or chitosan oligosaccharide derivative
5～50 parts of carbonate and/or bicarbonates
0～94.9 part of auxiliary agent.
Auxiliary agent of the present invention is mixed with by the raw material of following parts by weight:
Acid agent 0～50
Wetting dispersing agent 0～50
Disintegrant 0～40
Binder 0～15
Filler 0～90
Dyestuff 0～5
Lubricant 0～5
Described sour agent comprises at least a or multiple acid, includes but not limited to that formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid, malonic acid, phosphoric acid, condensed phosphoric acid, polyphosphoric acids, pyrophosphoric acid, tartaric acid, fumaric acid, malic acid, grape acid, maleic acid, boric acid, succinic acid, adipic acid, amino acid, humic acid, butene dioic acid, ascorbic acid, citric acid (citric acid) and other can provide hydrionic acid source.
Described wetting dispersing agent comprises ethanol, saponin, lignosulfite, the hydrolysate of animal waste, molasses, natural gum, silkworm excrement, alkyl or aryl phosphate, sulfated castor oil, the castor oil ethylene oxide adduct, the rosin acid ethylene oxide adduct, Span and ethylene oxide adduct thereof, glycerin polyoxyethylene polyoxypropylene ether fatty acid ester, aliphatic alcohol sulfate, alkylsulfonate, the dialkyl succinylsuccinate sulfonated ester, alkyl diphenyl ether sulfonate, alkylbenzenesulfonate, alkyl sulfate, alkene sulfonate, alkylphenol-polyethenoxy base sulphate, alkylphenol polyoxyethylene succinate sulfonate, the alkylphenol polyoxyethylene formaldehyde condensation products, the fatty acid amide APEO, aliphatic amine polyoxyethylene ether, succinic acid half ester sulfonate fatty acid amide, N-methyl fatty acid amide taurate, fatty alcohol polyoxyethylene ether sulfate, phenethyl phenol polyethenoxy ether sulfate, Sodium Polyacrylate, polyacrylamide, xanthan gum, carboxymethyl cellulose, polyoxy alkane allyl diglycol ether, alkyl phenol or aryl phenol formaldehyde condensation products APEO, the chlorination benzylamine, the bromination benzylamine, quaternary ammonium salt, polyvinyl alcohol, lignosulfonates, naphthalene sulfonic acid-formaldehyde condensation product, alkylphenol polyoxyethylene sulphate, alkylnaphthalene sulfonate, petroleum sodium sulfonate, the alkyl biphenyl sodium naphthalene sulfonate, naphtholsulfonic acid formaldehyde condensation products sodium salt, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, the benzylphenol APEO, the phenethyl phenol polyethenoxy ether, phenethyl phenol polyethenoxy polyethenoxy ether, the aliphatic alcohol polyethenoxy polyethenoxy ether, the Fluhyzon formaldehyde condensation products, polycarboxylate, the dibutyl naphthalene sulfonate, alkylphenol polyoxyethylene phosphate, alkyl polyoxyethylene ether phosphate, aralkyl phenol polyethenoxy ether phosphate, aliphatic acid polyethenoxy ether phosphate, in the alkyl polyoxyethylene ether phosphite one or more;
Described disintegrant comprises one or more in sulphur ammonium, calcium chloride, alginic acid, sodium chloride, magnesium chloride, urea, bentonite, aluminium chloride, sodium sulphate, attapulgite, white carbon, polyvinyl pyrrolidone, hydroxypropyl cellulose, microcrystalline cellulose, starch, modified starch, Explotab, carboxyrnethyl starch sodium, crosslinked carboxyrnethyl starch sodium, the super carboxyrnethyl starch sodium;
Described binder comprises carboxymethyl cellulose, polyvinyl alcohol, ethylene-vinyl acetate copolymer, starch, dextrin, sucrose, syrup, maltose, glucose, polyvinylpyrrolidone, gum Arabic, soybean protein, the arm protein, gelatine, gelatin, sodium silicate, gypsum, shellac, pitch, paraffin, wood is fragrant, polyvinyl acetate, rosin, denaturated sodium polyacrylate, polyethylene glycol, lignosulfonates, lignin, methylcellulose, ethyl cellulose, polyacrylamide, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene azoxy ketone, Hydroxypropylcelliloxe, low-substituted hydroxypropyl cellulose, in the sodium carboxymethylcellulose one or more;
Described filler comprises one or more in mineral salt, kaolin, corncob cellulose, soybean, tobacco, rice husk, sulphur, acorn, bentonite, atlapulgite, diatomite, white carbon, concavo-convex rod, clay, montmorillonite, float stone, potter's clay, quicklime, magnesium lime, phosphorus lime, pyrophillite, calcite, dolomite, gypsum, sepiolite, silica, mica, talcum, mud coal, silica gel, starch, dextrin, glucose, mannitol, lactose, the sucrose;
Described dyestuff comprises one or more in direct red brown, direct light yellow, Indian yellow, lemon yellow, sunset yellow, famille rose, acid yellowish-brown, disperse blue, reactive blue, reactive scarlet, Congo red, the amaranth;
Described lubricant comprises one or more in stearic acid, stearate, hydrogenated vegetable oil, polyoxyl 40 stearate, light mineral oil, polyethylene glycol, boric acid, sodium chloride, Sodium Benzoate, sodium acetate, enuatrol, sldium lauryl sulfate, magnesium laurylsulfate, polyoxyethylene lauryl alcohol sodium sulphate, adipic acid, fumaric acid, triacetyl glycerine, sodium carboxymethyl starch, the talcum powder.
Add sour agent and be in order to produce chemical reaction with carbonate or bicarbonate, generate carbon dioxide, if adopt acid shitosan or chitosan oligosaccharide raw material, sour agent can not add or add less.
Add wetting dispersing agent and be in order to make the fast and active ingredient of effervescent agent disintegration dissolve (dispersion) Yu Shuizhong fast, to adapt to the requirement of modernized high-efficiency agriculture, and at water-soluble relatively poor active ingredient, make active ingredient in hard water, still keep good dispersity, make soup have good wetability, permeability and plate-out ability simultaneously, increase the contact of soup, improved the availability of active ingredient, reduced waste and the pollution of environment to crop surface.
That surfactant among the present invention mainly plays is wetting, dispersion and hydrotropy effect, and suitable anion surfactant and/or non-ionic surface active agent or dispersing aid are for can be used for all the type materials of agrochemical composition usually.
Disintegrant among the present invention makes water become swelling action to infiltrate in the effervescent agent particle by wicking, accelerates the disintegration of particle.Among the present invention, according to the character of effervescent agent active ingredient, if suitable, some situation need be added disintegrant.Suitable disintegrants is for being used for all substances of agrochemical composition usually for this purpose.
Binder among the present invention is for active ingredient and auxiliary agent are bonded together, and the intensity of finished product avoids broken in transporting procedures after making things convenient for granulation and guaranteeing granulation, among the present invention, according to the character of effervescent agent active ingredient, if suitable, some situation need be added binder.Suitable binder is for being used for all substances of agrochemical composition usually for this purpose.
Filler among the present invention mainly is in order to adsorb the physical behavior of active ingredient and maintenance effervescent agent, as intensity, hygroscopicity etc.The present invention can add different fillers according to the character and the instructions for use of active ingredient, if suitable, some situation will be added filler.Appropriate filler is for being used for all substances of agrochemical composition usually for this purpose.
Agricultural effervescing agent of the present invention can be processed into shades of colour, and the purpose that adds colouring agent is in order to change the appearance color of product, to increase the commodity of products energy, and is little to other performance impact of product.Suitable colouring agent is for being used for all substances of agrochemical composition usually for this purpose.
Lubricant among the present invention is granulation for convenience, enhances productivity, and according to the physical property of raw material, some situation can not add.
More than all auxiliary agents all are known substances, also be material commonly used and that know in the pesticidal preparations processing, those skilled in the art can add at the different qualities and the different purposes of shitosan or chitosan oligosaccharide.In addition, though disclose the option of various auxiliary agents among the present invention, those skilled in the art know that the disclosed auxiliary agent, the auxiliary agent that other those skilled in the art use always also can be used for the present invention in the present invention, and falls into protection scope of the present invention.
One of preferred version of the present invention can also add other agricultural chemicals, is mixed with by the raw material of following parts by weight:
0.1～94.9 part of shitosan or chitosan oligosaccharide
Other agricultural chemicals 0.1-90 part
5～50 parts of carbonate and/or bicarbonates
0～94.8 part of auxiliary agent.
Wherein agricultural chemicals comprises insecticide, miticide, bactericide, weed killer herbicide, plant growth regulator etc., particularly bactericide and plant growth regulator, shitosan or chitosan oligosaccharide are by composite with other bactericide and/or plant growth regulator, as jinggangmeisu, middle living rhzomorph, many antibiotic, pesticide corrosion 120, kasugarnycin, dimethomorph, carbendazim, tmtd, Fluoxastrobin, brassin lactones, the basic element of cell division, gibberellin etc., can produce synergistic function, input-output ratio is higher.
One of preferred version of the present invention can also add other fertilizer, is mixed with by the raw material of following parts by weight:
0.1～94.9 part of shitosan or chitosan oligosaccharide
Other fertilizer 0.1-90 part
5～50 parts of carbonate and/or bicarbonates
0～94.8 part of auxiliary agent.
Wherein fertilizer comprises the material of plant nutrients such as containing C, H, O, N, P, K, Ga, Mg, S, Cu, Fe, Mn, Zn, Mo, B, Cl, Si, Na, Co, Se, V, Ni, Ge or beneficial element.Shitosan or chitosan oligosaccharide and above-mentioned nutriment are composite, can produce the effect of Synergistic, improve input-output ratio.
Agricultural effervescing agent of the present invention can be processed into arbitrary polygon sheet, sphere, cylindric, ellipse or arbitrary polyhedron granula, does not influence its result of use.
The present invention solves another technical scheme that its technical problem adopts, and constructs a kind of method for preparing above-mentioned agricultural effervescing agent, comprises following processing step and process: with formulation material weighing, mixing, pulverizing, granulation, be drying to obtain.
The equipment that the preparation of agricultural effervescing agent of the present invention is used all be widely apply on the market, be known to the technical staff in effervescent agent field, granulation adopts conventional prilling to realize that these technologies include but not limited to spray drying granulation, freeze drying granulation, extruder grain, cylinder granulation, fluidized bed granulation, fluidized bed prilling, rotary table granulation etc.
Implement agricultural effervescing agent of the present invention and preparation method, have following advantage:
Agricultural effervescing agent of the present invention disintegration rate in water is fast, dissolving (dispersion) is complete, do not stop up shower nozzle and drip irrigation pipeline, do not need heating during use, be difficult for the moisture absorption, packing, storing, metering, use cost is low, owing to added wetting dispersing agent, soup after the preparation has good wetability, permeability and plate-out ability, improved the availability of active ingredient, reduced waste and, had a tangible performance the pollution of environment, cost and environment-friendly advantage, be widely used in cereal crops, economic crops, gardening, lawn and urban afforestation, its market application foreground is very wide.
Concrete embodiment
In order to understand the present invention better, describe the technology contents of invention below in detail with example, but embodiment of the present invention are not limited to these examples.
Embodiment 1
Take by weighing each component raw material according to following proportioning
0.1 part of shitosan
5 parts of sodium bicarbonates
2.9 parts in tartaric acid
2 parts of alkylphenol polyoxyethylene formaldehyde condensation products
90 parts of starch
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out extruder grain then, dry, analytical control warehouse-in obtains the shitosan effervescent agent.
Embodiment 2
Take by weighing each component raw material according to following proportioning
95 parts of shitosans
5 parts of saleratus
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out extruder grain then, dry, analytical control warehouse-in obtains the shitosan effervescent agent.
Embodiment 3
Take by weighing each component raw material according to following proportioning
0.1 part of oligosaccharide
50 parts of sodium bicarbonates
40 parts of citric acids
9.9 parts in alkylphenol polyoxyethylene succinate sulfonate
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out extruder grain then, dry, analytical control warehouse-in obtains the oligosaccharide effervescent agent.
Embodiment 4
Take by weighing each component raw material according to following proportioning
95 parts of oligosaccharides
5 parts of sodium bicarbonates
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain the oligosaccharide effervescent agent.
Embodiment 5
Take by weighing each component raw material according to following proportioning
80 parts of CMCs
9 parts in amino acid
8 parts of sodium bicarbonates
3 parts of polyvinylpyrrolidones
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain CMC and amino acid effervescing agent.
Embodiment 6
Take by weighing each component raw material according to following proportioning
55 parts of sulfonation oligosaccharides
15 parts of polyethylene glycol
11 parts of saleratus
12 parts of humus
3 parts of EDTA-Fe
4 parts of neopelexes
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain sulfonation oligosaccharide and humus effervescent agent.
Embodiment 7
Take by weighing each component raw material according to following proportioning
25 parts of shitosans
3.5 parts of naphtholsulfonic acid formaldehyde condensation products sodium salts
0.5 part of polyacrylamide
21 parts in carbonic hydroammonium
50 parts in ascorbic acid
With above-mentioned component mixing except that polyacrylamide, through pulverizing the female powder of preparation, the binder polyacrylamide alcoholic solution of female powder and 10% is mixed, carry out extruder grain then, drying, screening, analytical control are put in storage and are obtained the shitosan effervescent agent.
Embodiment 8
Take by weighing each component raw material according to following proportioning
5 parts of oligosaccharides
35 parts in molasses
15 parts of rosin acid ethylene oxide adducts
9.5 parts of boric acid
11 parts in magnesium carbonate
10 parts of phenethyl phenol polyethenoxy polyethenoxy ethers
13 parts of low-substituted hydroxypropyl celluloses
1.5 parts of sodium carboxymethylcelluloses
With above-mentioned component mixing except that sodium carboxymethylcellulose, through pulverizing the female powder of preparation, the binder sodium carboxymethylcellulose alcoholic solution of female powder and 10% is mixed, carry out extruder grain then, drying, screening, analytical control warehouse-in obtain the effervescent agent of oligosaccharide and boric acid.
Embodiment 9
Take by weighing each component raw material according to following proportioning
32 parts of shitosans
30 parts of sulfated chitosans
12 parts of zinc powders
5 parts of N-methyl fatty acid amide taurates
2 parts of hydroxypropyl celluloses
9 parts of calcium bicarbonates
10 parts of fumaric acid
With above-mentioned component mixing except that hydroxypropyl cellulose, through pulverizing the female powder of preparation, the binder hydroxypropyl cellulose alcoholic solution of female powder and 10% is mixed, carry out the cylinder granulation then, drying, screening, analytical control warehouse-in obtain the effervescent agent of shitosan and sulfated chitosan.
Embodiment 10
Take by weighing each component raw material according to following proportioning
18 parts of oligosaccharides
17 parts of sulfonation oligosaccharides
5.95 parts in dextrin
12 parts of polyphosphoric acids
33 parts of lactose
14 parts of ammonium carbonates
Lemon yellow 0.05 part
Will be except that dextrin, said components mixing lemon yellow, through pulverizing the female powder of preparation, dextrin is configured to 20% binder dextrin alcoholic solution, in the lemon yellow again adding dextrin alcoholic solution, female powder and the solution that contains colouring agent and dextrin are mixed, carry out rotary table granulation then, drying, screening, analytical control warehouse-in obtain the effervescent agent of yellow oligosaccharide and sulfonation oligosaccharide.
Embodiment 11
Take by weighing each component raw material according to following proportioning
10 parts of oligosaccharides
5 parts of pesticide corrosion 120s
36 parts in sulphur
13 parts of boric acid
16 parts in carbonic hydroammonium
18.5 parts of naphtholsulfonic acid formaldehyde condensation products sodium salts
1 part of gum Arabic
0.5 part of dolomol
With above-mentioned component mixing except that gum Arabic, through pulverizing the female powder of preparation, with mixing of the binder gum Arabic alcoholic solution of female powder and 10%, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain the effervescent agent of oligosaccharide and pesticide corrosion 120.
Embodiment 12
Take by weighing each component raw material according to following proportioning
25 parts of shitosans
45 parts of oligosaccharides
12 parts of citric acids
11 parts of saleratus
7 parts of aliphatic acid polyethenoxy ether phosphate
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain shitosan and oligosaccharide effervescent agent.
Embodiment 13
Take by weighing each component raw material according to following proportioning
35 parts of oligosaccharides
10 parts of dimethomorphs
20 parts of fumaric acid
18 parts of sodium bicarbonates
8 parts of hydroxypropyl methylcelluloses
9 parts of anhydrous sodium sulfates
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain oligosaccharide and dimethomorph effervescent agent.
Embodiment 14
Take by weighing each component raw material according to following proportioning
15 parts of oligosaccharides
30 parts of calcium bicarbonates
26 parts of citric acids
11 parts of calcium lignosulfonates
9 parts of glycerin polyoxyethylene polyoxypropylene ether fatty acid esters
4 parts of glucose
5 parts of direct red browns
Will be except that the said components mixing glucose, the direct red brown, through pulverizing the female powder of preparation, glucose is configured to 20% binder dextrin alcoholic solution, direct red brown adds in the glucitol solution again, female powder and the solution that contains colouring agent and glucose are mixed, carry out rotary table granulation then, drying, screening, analytical control warehouse-in obtain rufous oligosaccharide effervescent agent.
Embodiment 15
Take by weighing each component raw material according to following proportioning
60 parts of shitosans
11 parts of sodium bicarbonates
11 parts in tartaric acid
7 parts of succinic acid half ester sulfonate fatty acid amides
5 parts of magnesium laurylsulfates
6 parts in ammonium sulfate
With the said components mixing, through pulverizing the female powder of preparation, female powder and an amount of alcoholic solution are mixed, carry out fluidized bed prilling then, drying, screening, analytical control warehouse-in obtain the shitosan effervescent agent.
Embodiment 16
Present embodiment is disintegrative, dispersiveness, the stability experiment of above-mentioned part embodiment.Because agricultural effervescing agent is an innovative product, there is not ripe product standard, therefore check with reference to national medical effervescent agent standard, for active ingredient is water miscible product, no longer carry out the mensuration of dispersive property, the sample that the foregoing description is made has carried out following detection, and concrete detection method is as follows:
Dispersed and redispersibility is measured: adopt the graduated cylinder bulk method to carry out, its step is as follows: (1) adds 98ml deionized water (100ml scale) in tool plug graduated cylinder; (2) claim the 2g sample to add graduated cylinder; (3) turn upside down and leave standstill behind the graduated cylinder 10 times, each 2 seconds, the precipitation capacity when record 30,60min; (4) put upside down graduated cylinder behind the 24h, write down the number of times that sediments is disperseed again and put upside down, the number of reversals is lower than 10 persons and thinks qualified.
Disintegrative is measured: represent to measure disintegration time length, general provision is qualified less than 3min, method is as follows: to the 100ml tool plug graduated cylinder that fills 90ml distilled water (the high 22.5cm of tube, internal diameter 28mm) adds sample particle 0.5g down in 25 ℃ in, clamp the graduated cylinder middle part, at the uniform velocity rotate along the center with 8r/min speed, up to sample in water fully till the disintegration, writing time.This time is disintegration time.
Heat storage stability: will check the sample behind the active constituent content to be respectively charged in the ampoule bottle, and put into constant temperature oven, 54 ± 2 ℃ of heat storages 14 days, sample analysis heat storage back content of effective was calculated its active ingredient resolution ratio then.
Result such as following table:
The assay of table 2: part embodiment
The result shows, the agricultural effervescing agent that the present invention makes, and excellent performances such as the disintegrative of product, dispersiveness, stability have been realized purpose of the present invention.
Though more than described various embodiment of the present invention, should be appreciated that its purpose only is to illustrate, and do not have restricted.Those skilled in the art knows, not leaving under the spirit and scope of the present invention situation, also can make various changes in the form and details.Therefore, protection scope of the present invention is improper only to be confined to arbitrary embodiment described above, limits and should and be equal to according to claim.
Claims (10)
1. an agricultural effervescing agent is characterized in that, comprises that shitosan and/or chitosan derivatives and one or more contact the compound that produces gas with water, and the chemical name of described shitosan is β-1, and 4-gathers-D-glucosamine, and molecular formula is: (C
6H
11O
4N) n.
2. according to the described agricultural effervescing agent of claim 1, it is characterized in that, contact the compound that produces gas with water and be selected from carbonate or bicarbonate, or the mixture of the two, described carbonate and bicarbonate include but not limited to Li
2CO
3, Na
2CO
3, K
2CO
3, (NH
4)
2CO
3, MgCO
3, CaCO
3, Ca (HCO
3)
2, LiHCO
3, NaHCO
3, KHCO
3And NH
4HCO
3
3. agricultural effervescing agent according to claim 1 is characterized in that, is mixed with by the raw material of following parts by weight:
0.1～95 part of shitosan and/or chitosan derivatives
5～50 parts of carbonate and/or bicarbonates
0～94.9 part of auxiliary agent.
4. agricultural effervescing agent according to claim 1, it is characterized in that, described shitosan and/or chitosan derivatives are chitosan oligosaccharide and/or chitosan oligosaccharide derivative, also claim amino-oligosaccharide, chitosan oligomer, chitin oligosaccharide, shell oligosaccharide, chitin oligo saccharide etc., chemical name is: β-1,4-oligomerization-D-glucosamine, molecular formula: (C
6H
11O
4N) n, wherein n is 2-20.
5. agricultural effervescing agent according to claim 4 is characterized in that, is mixed with by the raw material of following parts by weight: 0.1～95 part in chitosan oligosaccharide and/or chitosan oligosaccharide derivative
5～50 parts of carbonate and/or bicarbonates
0～94.9 part of auxiliary agent.
6. according to the agricultural effervescing agent of claim 3 or 5, it is characterized in that described auxiliary agent is mixed with by the raw material of following parts by weight:
Acid agent 0～50
Wetting dispersing agent 0～50
Disintegrant 0～40
Binder 0～15
Filler 0～90
Dyestuff 0～5
Lubricant 0～5
Described sour agent comprises at least a or multiple acid, includes but not limited to that formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid, malonic acid, phosphoric acid, condensed phosphoric acid, polyphosphoric acids, pyrophosphoric acid, tartaric acid, fumaric acid, malic acid, grape acid, maleic acid, boric acid, succinic acid, adipic acid, amino acid, humic acid, butene dioic acid, ascorbic acid, citric acid (citric acid) and other can provide hydrionic acid source.
Described wetting dispersing agent comprises ethanol, saponin, lignosulfite, the hydrolysate of animal waste, molasses, natural gum, silkworm excrement, alkyl or aryl phosphate, sulfated castor oil, the castor oil ethylene oxide adduct, the rosin acid ethylene oxide adduct, Span and ethylene oxide adduct thereof, glycerin polyoxyethylene polyoxypropylene ether fatty acid ester, aliphatic alcohol sulfate, alkylsulfonate, the dialkyl succinylsuccinate sulfonated ester, alkyl diphenyl ether sulfonate, alkylbenzenesulfonate, alkyl sulfate, alkene sulfonate, alkylphenol-polyethenoxy base sulphate, alkylphenol polyoxyethylene succinate sulfonate, the alkylphenol polyoxyethylene formaldehyde condensation products, the fatty acid amide APEO, aliphatic amine polyoxyethylene ether, succinic acid half ester sulfonate fatty acid amide, N-methyl fatty acid amide taurate, fatty alcohol polyoxyethylene ether sulfate, phenethyl phenol polyethenoxy ether sulfate, Sodium Polyacrylate, polyacrylamide, xanthan gum, carboxymethyl cellulose, polyoxy alkane allyl diglycol ether, alkyl phenol or aryl phenol formaldehyde condensation products APEO, the chlorination benzylamine, the bromination benzylamine, quaternary ammonium salt, polyvinyl alcohol, lignosulfonates, naphthalene sulfonic acid-formaldehyde condensation product, alkylphenol polyoxyethylene sulphate, alkylnaphthalene sulfonate, petroleum sodium sulfonate, the alkyl biphenyl sodium naphthalene sulfonate, naphtholsulfonic acid formaldehyde condensation products sodium salt, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, the benzylphenol APEO, the phenethyl phenol polyethenoxy ether, phenethyl phenol polyethenoxy polyethenoxy ether, the aliphatic alcohol polyethenoxy polyethenoxy ether, the Fluhyzon formaldehyde condensation products, polycarboxylate, the dibutyl naphthalene sulfonate, alkylphenol polyoxyethylene phosphate, alkyl polyoxyethylene ether phosphate, aralkyl phenol polyethenoxy ether phosphate, aliphatic acid polyethenoxy ether phosphate, in the alkyl polyoxyethylene ether phosphite one or more;
Described disintegrant comprises one or more in ammonium sulfate, calcium chloride, alginic acid, sodium chloride, magnesium chloride, urea, bentonite, aluminium chloride, sodium sulphate, attapulgite, white carbon, polyvinyl pyrrolidone, hydroxypropyl cellulose, microcrystalline cellulose, starch, modified starch, Explotab, carboxyrnethyl starch sodium, crosslinked carboxyrnethyl starch sodium, the super carboxyrnethyl starch sodium;
Described binder comprises carboxymethyl cellulose, polyvinyl alcohol, ethylene-vinyl acetate copolymer, starch, dextrin, sucrose, syrup, maltose, glucose, polyvinylpyrrolidone, gum Arabic, soybean protein, the arm protein, gelatine, gelatin, sodium silicate, gypsum, shellac, pitch, paraffin, wood is fragrant, polyvinyl acetate, rosin, denaturated sodium polyacrylate, polyethylene glycol, lignosulfonates, lignin, methylcellulose, ethyl cellulose, polyacrylamide, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene azoxy ketone, Hydroxypropylcelliloxe, low-substituted hydroxypropyl cellulose, in the sodium carboxymethylcellulose one or more;
Described filler comprises one or more in mineral salt, kaolin, corncob cellulose, soybean, tobacco, rice husk, sulphur, acorn, bentonite, atlapulgite, diatomite, white carbon, concavo-convex rod, clay, montmorillonite, float stone, potter's clay, quicklime, magnesium lime, phosphorus lime, pyrophillite, calcite, dolomite, gypsum, sepiolite, silica, mica, talcum, mud coal, silica gel, starch, dextrin, glucose, mannitol, lactose, the sucrose;
Described dyestuff comprises one or more in direct red brown, direct light yellow, Indian yellow, lemon yellow, sunset yellow, famille rose, acid yellowish-brown, disperse blue, reactive blue, reactive scarlet, Congo red, the amaranth;
Described lubricant comprises one or more in stearic acid, stearate, hydrogenated vegetable oil, polyoxyl 40 stearate, light mineral oil, polyethylene glycol, boric acid, sodium chloride, Sodium Benzoate, sodium acetate, enuatrol, sldium lauryl sulfate, magnesium laurylsulfate, polyoxyethylene lauryl alcohol sodium sulphate, adipic acid, fumaric acid, triacetyl glycerine, sodium carboxymethyl starch, the talcum powder.
7. according to the described agricultural effervescing agent of claim 1-6, it is characterized in that, can also add other agricultural chemicals, be mixed with by the raw material of following parts by weight:
0.1～94.9 part of shitosan or chitosan oligosaccharide
Other agricultural chemicals 0.1-90 part
5～50 parts of carbonate and/or bicarbonates
0～94.8 part of auxiliary agent.
8. according to the described agricultural effervescing agent of claim 1-6, it is characterized in that, can also add other fertilizer, be mixed with by the raw material of following parts by weight:
0.1～94.9 part of shitosan or chitosan oligosaccharide
Other fertilizer 0.1-90 part
5～50 parts of carbonate and/or bicarbonates
0～94.8 part of auxiliary agent.
9. according to the described agricultural effervescing agent of arbitrary claim among the claim 1-8, it is characterized in that described agricultural effervescing agent can be processed into arbitrary polygon sheet, sphere, cylindric, ellipse or arbitrary polyhedron granula.
10. according to the preparation method of arbitrary described agricultural effervescing agent among the claim 1-9, it is characterized in that, comprise following processing step and process: with formulation material weighing, mixing, pulverizing, granulation, be drying to obtain.
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|---|---|---|---|
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|---|---|---|---|
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