CN114685211B - Pesticide-fertilizer composition and application thereof - Google Patents
Pesticide-fertilizer composition and application thereof Download PDFInfo
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- CN114685211B CN114685211B CN202011457127.8A CN202011457127A CN114685211B CN 114685211 B CN114685211 B CN 114685211B CN 202011457127 A CN202011457127 A CN 202011457127A CN 114685211 B CN114685211 B CN 114685211B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C21/00—Methods of fertilising, sowing or planting
- A01C21/005—Following a specific plan, e.g. pattern
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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Abstract
The invention relates to the field of pesticides and fertilizers, in particular to a pesticide-fertilizer composition and application thereof. The composition comprises an active component A and an active component B, wherein the dosage of the active component A is 0.25-250 g/mu, and the dosage of the trace element fertilizer of the active component B is 1000-2000 g/mu; wherein the active component A is 1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-alcohol, and the active component B is a trace element fertilizer. The composition has the biological activities of promoting flower and fruit growth and increasing yield, and the combination of the two has more obvious effect.
Description
Technical Field
The invention relates to the field of pesticides and fertilizers, in particular to a pesticide-fertilizer composition and application thereof.
Background
Paclobutrazol (chemical name: 2RS, 3RS) -1- (4-chlorphenyl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentan-3-ol), also called chlorobutazone, is a triazole compound successfully developed in 80 th of 20 th century in British empire chemical industry, has the physiological effects of delaying the longitudinal growth of plants, inhibiting the elongation of stem nodes, increasing stem thickness, promoting tillering (or branching), being beneficial to rooting, flowering and fruit setting, increasing chlorophyll content, influencing the photosynthesis and respiration of plants, delaying the senescence of plants and the like. However, paclobutrazol runs and degrades slowly in plants, so the duration of drug action is long; the paclobutrazol has good stability and long residual time in soil, and causes phytotoxicity such as excessive inhibition, growth stagnation, incapability of plant growth recovery and the like when the paclobutrazol is used repeatedly for many times in a short period when the paclobutrazol is prepared at too high concentration and too large dosage.
Uniconazole (chemical name: (E) -1-p-chlorophenyl-2 (1,2,4-triazol-1-yl) -4,4-dimethyl-1-penten-3-ol), also called as high-efficiency oxazole, is a triazole plant growth retardant developed in 90 years of the 20 th century, and has the biological activities of delaying the development process of crops, promoting roots and tillers, controlling growth and strengthening seedlings, resisting lodging, enhancing stress resistance, improving chlorophyll content, delaying senescence and increasing of plants. However, strict control is required in the administration period and the administration dose in order to prevent the occurrence of phytotoxicity.
Disclosure of Invention
In view of the above, the present invention aims to provide a pesticide-fertilizer composition and an application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a pesticide-fertilizer composition comprises an active component A and an active component B, wherein the dosage of the active component A is 0.25-250 g/mu, and the dosage of the trace element fertilizer of the active component B is 1000-2000 g/mu; wherein the active component A is 1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-alcohol, and the active component B is a trace element fertilizer.
The active component A is 1- (2-chlorothiazole-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-alcohol with the structure shown in formula 1,
the active component B microelement fertilizer comprises, by weight, 15-20% of zinc sulfate, 15-20% of manganese sulfate, 15-20% of boric acid, 10-20% of magnesium sulfate, 10-15% of ferrous sulfate and the balance fulvic acid.
Preferably, the trace element fertilizer of the active component B is 20% of zinc sulfate, 20% of manganese sulfate, 20% of boric acid, 15% of magnesium sulfate, 15% of ferrous sulfate and 10% of fulvic acid.
The dosage of the active component A is 2.5-150 g/mu, and the dosage of the active component B microelement fertilizer is 1000-2000 g/mu.
The dosage of the active component A is 25-50 g/mu, and the dosage of the active component B microelement fertilizer is 1500-2000 g/mu.
The pesticide-fertilizer composition is applied as a fertilizer in delaying the development process of crops, promoting roots and tillering, controlling growth and strengthening seedlings, improving the content of chlorophyll, increasing flowers and fruits and improving the yield of crops.
A pesticide fertilizer preparation consists of the pesticide fertilizer composition and pharmaceutically acceptable auxiliary materials.
The application of the medicinal fertilizer preparation is the application of the medicinal fertilizer preparation as a fertilizer in delaying the development process of crops, promoting roots and tillering, controlling the growth and strengthening seedlings, improving the content of chlorophyll, increasing flowers and fruits and improving the yield of the crops.
The invention has the following advantages and beneficial effects:
the active component in the pesticide-fertilizer composition is A (1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-alcohol), which can delay the development process of crops, promote roots and tillering, control growth and strengthen seedlings; the biological activity superior to those of uniconazole and paclobutrazol can be achieved in the aspects of increasing the chlorophyll content, increasing the flower and fruit, increasing the crop yield and the like, the degradation rate is equivalent to that of the uniconazole and is obviously higher than that of the paclobutrazol; and no obvious phytotoxicity or yield reduction can be caused when the preparation concentration is too high and the dosage is too large. Meanwhile, the components A and B of the composition can synergistically promote the flower and fruit growth and increase the yield of the biological activity, and the effect is more obvious.
Drawings
FIG. 1 is a graph showing the degradation of component A, paclobutrazol and uniconazole in indoor soil provided by the embodiment of the invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The pesticide-fertilizer composition can achieve biological activity superior to paclobutrazol and uniconazole, has low residue and high degradation rate, and does not generate phytotoxicity when the preparation concentration is too high and the dosage is too large; furthermore, the invention also provides the application of the pesticide-fertilizer composition in the aspects of delaying the development process of crops, promoting roots and tillering, controlling growth and strengthening seedlings, improving the content of chlorophyll, increasing flowers and fruits, improving the yield of crops and the like.
Example 1
Combination A: preparation and nuclear magnetic data of 1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazol-1-yl) pentan-3-ol:
step A:
1- (1,2,4-triazol-1-yl) -3,3-dimethyl-2-butanone 3.3g, DMF 50mL, sodium hydride 1.0g are added into a 100mL flask, stirred at room temperature for 0.5 hour, and 2-chloro-5- (chloromethyl) thiazole 3.3g are stirred and heated at 80 ℃ for 2 hours, after the TLC detection reaction is finished, water 300mL is added, ethyl acetate 80mL is extracted by 3, organic phases are combined, anhydrous sodium sulfate is dried, and column chromatography (eluent is ethyl acetate and petroleum ether (boiling range is 60-90 ℃) and the volume ratio is 1:2) is carried out to purify to obtain 0.83g of the compound 1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazol-1-yl) pentan-3-one and white solid.
And B, step B:
a100 mL flask is added with 0.83g of 1- (6-chloropyridin-3-yl) 2- (1,2,4-triazole-1-yl) -4,4-dimethyl-3-pentanone prepared in the step A and 30mL of methanol, slowly added with 0.33g of sodium borohydride in batches under ice-bath cooling and stirring, the temperature is controlled not to exceed 25 ℃, after the addition is finished, the mixture is stirred and reacted for 4 hours at room temperature, after the TLC detection reaction is finished, decompression and desolventization are carried out, 100mL of water is added, the pH is adjusted to =7 by concentrated hydrochloric acid, ethyl acetate 50mL multiplied by 3 is extracted, organic phases are combined, dried by anhydrous sodium sulfate, and the mixture is purified by column chromatography (eluent is ethyl acetate and petroleum ether (boiling range is 60-90 ℃) and the volume ratio is 1:1) to obtain 0.51g of the compound 1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-ol and white solid.
1 H NMR(600MHz,DMSO)δ8.57(s,1H),7.87(s,1H),7.30(s,1H),5.56(d,J＝6.5Hz,1H),4.74(dd,J＝11.1,3.5Hz,1H),3.57(dd,J＝15.1,11.1Hz,1H),3.47(dd,J＝6.5,1.2Hz,1H),3.35(dd,J＝15.6,4.7Hz,1H),0.63(s,9H).
Example 2 dosage design for pharmaceutical treatment
And (2) component A:1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazol-1-yl) pentan-3-ol with uniconazole and paclobutrazol as positive controls and a blank control without any agent added. The dose design is shown in table 1.
Table 1 dosage design for treatment of drugs
Example 3 Effect of component A on different growth periods of potted indoor cucumber
Test subjects (varieties): cucumber (open field No. 2).
Medicament treatment: the dosing schedule of the agent treatments in example 2 was followed with 12 replicates of each treatment.
The time and frequency of application: the application is carried out 1 time in the 5-leaf stage of cucumber.
The influence of different medicament treatments on the growth of indoor potted cucumber seedlings is investigated, and the influence of different medicament treatments on the yield of indoor potted cucumber is investigated in the mature period.
The calculation formula is as follows:
plant height dwarfing rate (%) = (blank control plant height-treated plant height)/blank control plant height 100
Stem thickness increase (%) = (treated stem thickness-blank control stem thickness)/blank control stem thickness 100
Yield increase (%) = (treatment yield-blank yield)/blank yield 100
The test results are shown in tables 2 and 3
TABLE 2 Effect of different treatments on the growth and development of indoor potted cucumber in seedling stage
TABLE 3 influence of different treatments on the number and yield of potted cucumber fruits in a house
As can be seen from table 2, the components A, the uniconazole and the paclobutrazol have certain growth control effect on cucumber seedlings, the component A has obvious amplification on stem thickness, the uniconazole and the paclobutrazol have no obvious amplification on the stem thickness of the cucumber seedlings, the dwarfing of the cucumber seedlings treated by the uniconazole and the paclobutrazol is serious when the pesticide dosage is 25 g/mu and 250 g/mu, and the component A has no obvious pesticide damage under the same dosage. The crossing of the component A on the uniconazole and the paclobutrazol has better effect of controlling strong cucumber seedlings.
As can be seen from Table 3, the cucumber yield is improved to a certain extent by the components A, the uniconazole and the paclobutrazol, the yield improvement effect of the component A is more obvious, the cucumber yield is obviously reduced by the uniconazole and the paclobutrazol when the dosage of the agent is 25 g/mu and 250 g/mu, and the cucumber yield is not reduced by the component A under the same dosage.
Example 4 Effect of component A on different growth periods of potted indoor soybeans
Test subjects (varieties): soybean (reclamation of farmers 18).
Medicament treatment: the dosing schedule of the agent treatments in example 2 was followed with 12 replicates of each treatment.
The time and frequency of application: the medicine is applied once when the fourth compound leaf of the soybean is unfolded.
The influence of different medicament treatments on the growth of indoor potted soybean seedlings is investigated, and the influence of different medicament treatments on the growth and yield of indoor potted soybeans is investigated in the mature period.
The calculation formula is as follows:
the plant height dwarfing rate and stem thickness increase were the same as in example 2.
Pod number increase (%) = (number of pod treated-number of pod treated in blank control)/number of pod treated in blank control 100
Pod weight gain (%) = (weight of pod treated-weight of pod of blank control)/weight of pod of blank control 100
TABLE 4 Effect of different agents on the growth and development of potted indoor soybean seedlings
TABLE 5 Effect of different Agents treatment on growth and yield of potted soybeans indoors
As can be seen from tables 4 and 5, component A has significant promoting effects on dwarfing of soybean plants, stout of stems, shortening of internodes and improvement of yield, and compared with uniconazole and paclobutrazol, component A has more significant effects on promoting stout of soybean stems, and does not cause significant phytotoxicity and yield reduction at high dose.
Example 5 Effect of component A on the growth of potted indoor peanuts at different stages
Test subjects (varieties): peanut (winding flower No. 2).
Treating a medicament: the dosing schedule of the agent treatments in example 2 was followed with 12 replicates of each treatment.
The time and frequency of application: the application is carried out 1 time in the seedling stage (before flowering) of the peanut.
The influence of different medicament treatments on the growth of indoor potted peanut seedlings is investigated from the early flowering stage to the flowering stage, and the influence of different medicament treatments on the growth and yield of indoor potted peanuts is investigated at the maturity stage.
The calculation formula is as follows:
the plant height dwarfing rate was the same as in example 3.
Chlorophyll content increase (%) = (treated chlorophyll content-placebo chlorophyll content)/placebo chlorophyll content 100
Fruit number increase (%) = (real number of processed fruit-real number of blank control fruit)/real number of blank control fruit 100
Fresh fruit weight increase (%) = (treated fresh fruit weight-blank control fresh fruit weight)/blank control fresh fruit weight 100
TABLE 6 influence of different treatments on the growth and development of the seedling stage (from early flowering to flowering needle stage) of potted peanuts indoors
TABLE 7 Effect of different Agents treatment on growth and yield of potted peanuts indoors
As can be seen from tables 6 and 7, component A has obvious promoting effects on dwarfing of the peanut plants, increasing of chlorophyll content, increasing of flowers and fruits and improving of yield, and compared with uniconazole and paclobutrazol, component A does not generate obvious phytotoxicity and yield reduction at high dose.
Example 6 Effect of component A on the growth of potted indoor corn at different stages
Test subjects (varieties): corn (zhengdan 958).
Medicament treatment: the dosing schedule of the pharmaceutical treatments in example 2 was followed, with 12 replicates of each treatment.
The application time and times are as follows: the medicine is applied once in the 4-5 leaf stage of the corn.
The influence of different medicament treatments on the growth of indoor potted corn seedlings is investigated, and the influence of different medicament treatments on the growth and yield of indoor potted corn is investigated in the maturation period.
The calculation formula is as follows:
the plant height dwarfing rate and stem thickness increase were the same as in example 3.
Dry weight gain (%) = (dry weight under treatment-dry weight under blank)/dry weight under blank 100
Ear weight gain (%) = (treated ear weight-blank control ear weight)/blank control ear weight 100
TABLE 8 Effect of different treatments on seedling growth of potted indoor maize
TABLE 9 Effect of different Agents treatment on growth and yield of potted indoor maize
As can be seen from tables 8 and 9, component A has significant promoting effects on dwarfing of maize plants, stout stems, developed root systems, and increased yield, and compared with uniconazole and paclobutrazol, component A does not cause significant phytotoxicity and yield reduction at high doses.
Example 7 degradation Effect of component A, uniconazole, paclobutrazol in indoor soil
Experimental materials: taking 3 parts of dry soil which is sieved by a 40-mesh sieve, respectively adding the component A, the uniconazole and the paclobutrazol (the initial adding concentrations are all 100 mg/kg), sampling at 0, 1,2, 3, 5, 7, 10, 15, 20, 25 and 30d, and measuring the content of each medicament in the soil (see figure 1).
The determination method comprises the following steps: weighing 5g of soil after adding the medicine, adding 25ml of acetonitrile, oscillating for 1min, performing ultrasonic treatment for 30min, quickly freezing at low temperature for 10min, centrifuging at 10000rpm/min for 5min, filtering with a 0.22 mu m filter membrane, and detecting by a liquid chromatography analyzer.
As can be seen from FIG. 1, the half-life of component A is significantly shorter than that of paclobutrazol, approaching that of uniconazole, but also shorter than that of uniconazole. The component A has better degradation effect in soil than both paclobutrazol and uniconazole.
Example 8 field efficacy results of the insecticide-fertilizer composition on peanuts
From examples 2 to 6, it can be known that the component A (1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-ol) has obvious promotion effects on aspects of delaying the development process of crops, promoting roots and tillering, controlling growth and strong seedlings, improving the content of chlorophyll, increasing flowers and fruits, improving the yield and the like of cucumbers, soybeans, peanuts and corns, and particularly has a more remarkable effect when the dosage is 25 g/mu, so that the component A and the component B (trace element fertilizer) with the dosage of 25 g/mu are selected to form a pesticide-fertilizer composition, and the field pesticide result of the pesticide-fertilizer composition on peanuts is determined.
Test subjects (varieties): peanut (winding flower No. 2).
Test reagents: the component A (1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazol-1-yl) pentane-3-alcohol) and the component B (zinc sulfate 20%, manganese sulfate 20%, boric acid 20%, magnesium sulfate 15%, ferrous sulfate 15%, fulvic acid 10%) are mixed together.
Test site: province of Henan Kai province Kai city Hai Hill village Li Baixia village.
The application time and times are as follows: the medicine is applied once from the initial florescence to the needle-bearing period of 6-20 days in 2020.
And (3) experimental design: adopting single-factor random block design, each treatment is repeated for 4 times, and the area of each repeated cell is 20m 2 The treatment dosage regimen was performed according to the dosage regimen of table 10.
TABLE 10 treatment dosage design for medicaments
Index and method for investigation and determination
Peanut growth investigation: 20 peanuts without diseases and insect pests in a random area of each cell are measured for the height of a main stem and the number of branches 20d (25 days in 8 months) before harvest, and the chlorophyll content is measured by using a chlorophyll meter.
Plant stunting rate (%) = (blank control stem height-treated stem height)/blank control stem height 100
Chlorophyll content increase (%) = (treated chlorophyll content-placebo chlorophyll content)/placebo chlorophyll content 100
And (4) measuring yield in the residential area, measuring the number of full peanuts, the weight of all peanuts and the weight of all kernels, and calculating the kernel yield and the yield increase.
Production increase (%) = (treatment production-blank control production)/blank control production 100
The results of the examination are shown in tables 11 and 12:
TABLE 11 Effect of different agent treatments on growth of peanuts in the field
TABLE 12 Effect of different Agents treatment on field peanut yield
As can be seen from tables 11 and 12, component B promotes the growth of peanut plants because component B is a trace element fertilizer, but after being compounded with component A, the component B can also delay the growth of peanuts. The component B with different dosages has certain promotion effect on the improvement of the flower production, and the promotion effect is more obvious after the component A is added.
Because the biological activity of the component B is similar when the dosage is 1500 g/mu and 2000 g/mu, the optimal proportion of the pesticide-fertilizer composition is as follows in consideration of the cost problem: 25 g/mu of active component A and 1500 g/mu of active component B.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. The pesticide fertilizer composition is characterized in that: the composition comprises an active component A and an active component B, wherein the dosage of the active component A is 0.25-250 g/mu, and the dosage of the trace element fertilizer of the active component B is 1000-2000 g/mu; wherein the active component A is 1- (2-chlorothiazol-5-yl) -4,4-dimethyl-2- (1H-1,2,4-triazole-1-yl) pentane-3-alcohol, and the active component B is a trace element fertilizer.
2. The insecticide-fertilizer composition of claim 1, wherein: the active component B trace element fertilizer comprises, by weight, 15-20% of zinc sulfate, 15-20% of manganese sulfate, 15-20% of boric acid, 10-20% of magnesium sulfate, 10-15% of ferrous sulfate and the balance of fulvic acid.
3. The insecticide-fertilizer composition of claim 1, wherein: the dosage of the active component A is 2.5-150 g/mu, and the dosage of the active component B microelement fertilizer is 1000-2000 g/mu.
4. The insecticide-fertilizer composition of claim 1, wherein: the dosage of the active component A is 25-50 g/mu, and the dosage of the active component B microelement fertilizer is 1500-2000 g/mu.
5. A pesticide fertilizer preparation is characterized in that: consists of the pesticide-fertilizer composition of any one of claims 1-4 and pharmaceutically acceptable auxiliary materials.
6. The use of the insecticide-fertilizer formulation of claim 5, wherein: the pesticide-fertilizer preparation is applied as a fertilizer in delaying the development process of crops, promoting roots and tillering, controlling growth and strengthening seedlings, improving the chlorophyll content, increasing flowers and fruits and improving the yield of crops.
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| IE45765B1 (en) * | 1976-08-19 | 1982-11-17 | Ici Ltd | Triazoles and imidazoles useful as plant fungicides and growth regulating agents |
| DE2756269A1 (en) * | 1977-12-16 | 1979-06-21 | Bayer Ag | AZOLYLALKYL-PYRIDINYL-AETHER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| JPS5594384A (en) * | 1979-01-12 | 1980-07-17 | Sumitomo Chem Co Ltd | Thiophene furan compound, its preparation, and fungicide, herbicide, and growth retardant of plant comprising it active ingredient |
| CN101734978A (en) * | 2008-11-07 | 2010-06-16 | 孙立华 | Flower dwarfing controlled release fertilizer |
| CN101423442A (en) * | 2008-11-20 | 2009-05-06 | 孙立民 | Flower dwarfing controlled release fertilizer |
| CN102303990B (en) * | 2010-10-13 | 2014-06-18 | 四川国光农化股份有限公司 | Medicinal fertilizer composition |
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