CN105432602A - Application of gamma-PGA (poly-gamma-glutamic acid) as pesticide adhesive - Google Patents
Application of gamma-PGA (poly-gamma-glutamic acid) as pesticide adhesive Download PDFInfo
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- CN105432602A CN105432602A CN201510852377.4A CN201510852377A CN105432602A CN 105432602 A CN105432602 A CN 105432602A CN 201510852377 A CN201510852377 A CN 201510852377A CN 105432602 A CN105432602 A CN 105432602A
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Abstract
The invention discloses an application of gamma-PGA (poly-gamma-glutamic acid) as a pesticide adhesive. Gamma-PGA is mixed with phoxim, abamectin or carbendazim for use. As the pesticide adhesive, gamma-PGA can reduce higher than 20% of pesticide degradation under the condition of 3 h of ultraviolet radiation and can reduce higher than 25% of pesticide degradation under the condition of water spraying. Therefore, gamma-PGA has the functions of ultraviolet resistance and rain wash resistance, so that the efficacy period of a pesticide is prolonged, the use times and amount of the pesticide are reduced, and sustainable development of ecological agriculture is promoted.
Description
Technical field
The present invention relates to pesticide field, be specifically related to the application of Polyurethane-epoxy resin as agricultural chemicals adhesive.
Background technology
China be pesticide producing use big country, conventional agricultural chemicals as organophosphorous pesticide phoxim, insecticide Avermectin, kill the disease-resistant comprehensive microbial inoculum carbendazim of mite etc., long-term use agricultural chemicals brings the residual problem of serious agriculture, the health problem of the serious harm people.Reducing the use of agricultural chemicals, is the Important Action concerning national economy.Common agricultural chemicals protectant has the macromolecular compound of chemosynthesis, and as triethanolamine, isocyanates, betain, these compou nd synthesis costs are higher, and have certain pollution to environment.In addition, conventional agricultural chemicals stabilizing agent or auxiliary agent have soybean oil, solvent wet goods, and these material extraction costs are high, also limit widely using of agricultural chemicals.
Polyurethane-epoxy resin (γ-PGA), be a kind of macromolecule extracellular polymeric by Microbe synthesis, be the same polyamide be connected to form by L-and D-Glu, mean molecule quantity is generally between 10-1000kD.Each monomer of composition Polyurethane-epoxy resin has a free anionic carboxyl, and therefore, it can be combined with various metals cation; Because a large amount of hydrophily carboxyl forms hydrogen bond between intramolecule or molecule, the existence of hydrogen bond enhances the water-soluble of Polyurethane-epoxy resin greatly; Polyurethane-epoxy resin molecule exists a large amount of peptide bond, can be decomposed by various hydrolase, catabolite is glutamic acid, can be absorbed by organism, therefore, Polyurethane-epoxy resin has excellent biological degradability, and nontoxic, harmless, noresidue (Kunioka, 1997).
Polyurethane-epoxy resin has water-soluble, the multiple excellent feature such as film forming, edibility, biological degradability, can be widely used in the fields (BuescherandMargaritis, 2007) such as medicine, food, light industry, environmental protection and agricultural.In agriculture application aspect, Polyurethane-epoxy resin can be used as wall material (Chen Shouwen etc., 2006 of the agent of fertilizer penetration enhancement, biopesticide microcapsules; Tian Chunhua, 2008; Wangetal., 2008).In food applications, Polyurethane-epoxy resin can as Mineral Nutrition Absorption promoter, stabilizing agent, thickener and cryoprotector (Suginoetal., 2008; Sakaietal., 2000; ShihandVan, 2001).In cosmetics, can be used as skin lubrication agent, hairspray, humectant etc.In medical, Polyurethane-epoxy resin and derivative thereof can as drug delivery carrier (Guanetal., 2008; ManochaandMargaritis, 2008), gene delivery vector (Kurosakietal., 2009), the bio-medical materials such as adhesive (Hirooetal., 1998).In environmental protection, Polyurethane-epoxy resin can be used as heavy metal absorbent and flocculant (Yuanetal., 2014).
Summary of the invention
The object of this invention is to provide the application of a kind of Polyurethane-epoxy resin as agricultural chemicals adhesive.
The technical solution used in the present invention is:
Polyurethane-epoxy resin is as the application of agricultural chemicals adhesive.
Further, Polyurethane-epoxy resin is as the application of agricultural chemicals adhesive and weed killer herbicide, insecticide or bactericide.
Further, Polyurethane-epoxy resin is mixed with phoxim pesticide.
Further, the mass ratio of described Polyurethane-epoxy resin and described phoxim is 1:1 ~ 5.
Further, Polyurethane-epoxy resin and Avermectin combined use of pesticides.
Further, the mass ratio of described Polyurethane-epoxy resin and described Avermectin is 1:0.25 ~ 1.
Further, Polyurethane-epoxy resin and carbendazim combined use of pesticides.
Further, the mass ratio of described Polyurethane-epoxy resin and described carbendazim is 1:1 ~ 5.
Polyurethane-epoxy resin provided by the invention is as the application of agricultural chemicals adhesive, mainly utilize film forming and the slow release of Polyurethane-epoxy resin, it is combined with Multiple Pesticides, comprise water soluble pesticide weed killer herbicide, insecticide, bactericide etc., pulvis weed killer herbicide, insecticide, bactericide etc., can not with cupric combined use of pesticides, Polyurethane-epoxy resin, as agricultural chemicals adhesive, can reduce degradation of pesticide and reach more than 20% under ultraviolet irradiation 3h condition; Under water pouring condition, degradation of pesticide can be reduced and reach more than 25%.Illustrate that Polyurethane-epoxy resin has the effect of uvioresistant, anti-rain drop erosion, the drug effect cycle of agricultural chemicals can be extended, reduce agricultural chemicals and run off, thus reduce access times and the usage amount of agricultural chemicals, promote the sustainable development of the ecological agriculture.Involved Polyurethane-epoxy resin is the polymer substance that Microbe synthesis metabolism produces, with short production cycle, and environmentally safe.
Embodiment
Now the present invention will be described in detail in conjunction with the embodiments.
Under embodiment 1 ultraviolet irradiation condition, Polyurethane-epoxy resin is on the impact of phoxim half life period
Step 1 solution allocation
With acetone: the mother liquor (separately adding Tween 80, is ten thousand/to final concentration) of the phoxim pesticide of water=1:1 volume ratio preparation 800ppm, and the Polyurethane-epoxy resin solution mother liquor preparing 400ppm is stand-by.Mixed with mass ratio 1:1 with Polyurethane-epoxy resin mother liquor by phoxim mother liquor, namely in mixed liquor, phoxim concentration is 400ppm, and Polyurethane-epoxy resin concentration is 200ppm, and wherein control group is phoxim mother liquor and equal quality clear water mixed liquor.
Step 2 ultraviolet irradiation
Being added by the mixed solution configured in culture dish to liquid height is 1cm, is positioned over and irradiates 3h under uviol lamp distance 30cm, and to be sampled in colorimetric cylinder and constant volume (10mL), vibration mixing, leaves standstill 3min.Add isopyknic benzinum in accurate absorption 3mL to colorimetric cylinder, vibration mixing leaves standstill 30min, draws in upper solution to 1.5mL centrifuge tube to be measured.
Step 3 detects
Vapor detection:
Instrument: Japanese Shimadzu GC-16A gas chromatograph, FPD detector.
Reagent: acetone, it is pure that carrene is analysis.
Chromatographic condition: chromatographic column is: 3mm × 1.1m glass column, 3.6%OV-101 fixer, ChromosorbW.AW.DMCS80-100 order carrier.Temperature: column temperature 175 DEG C, sensing chamber and temperature of vaporization chamber 210 DEG C.Carrier gas: nitrogen 60mlmin
-1, air: lkgcm
-2, hydrogen: lkgcm
-2.As can be seen from Table 1, add 200ppm Polyurethane-epoxy resin, under ultraviolet irradiation 3h condition, phoxim degraded can be reduced and reach 22.28%, illustrate that Polyurethane-epoxy resin can slow down the loss of phoxim, extend drug effect.
Under table 1 ultraviolet irradiation 3h condition, 200ppm Polyurethane-epoxy resin is on the impact of Determination of Phoxim Residues rate
Under embodiment 2 ultraviolet irradiation condition, Polyurethane-epoxy resin is on the impact of Avermectin half life period
Step 1 solution allocation
By Avermectin dissolution of crystals in methyl alcohol, be made into the concentration of 400ppm, and stand-by with the Polyurethane-epoxy resin solution mother liquor of distilled water preparation 400ppm.By Avermectin mother liquor and Polyurethane-epoxy resin mother liquor with volume ratio 1:1 mix all with, namely in mixed liquor, Avermectin concentration is 200ppm, and Polyurethane-epoxy resin concentration is 200ppm, and wherein control group is Avermectin mother liquor and equal quality clear water mixed liquor.
Step 2 ultraviolet irradiation
Being added by the mixed solution configured in culture dish to liquid height is 1cm, is positioned over and irradiates 3h under uviol lamp distance 30cm, and to be sampled in colorimetric cylinder and constant volume (10mL), vibration mixing, leaves standstill 3min.Add isopyknic acetonitrile in accurate absorption 3mL to colorimetric cylinder, move to vibration mixing in 10mL brown bottle and leave standstill 30min, draw in upper solution to 1.5mL centrifuge tube to be measured.
Step 3 detects
Liquid phase detects:
Instrument: high performance liquid chromatograph Agilent1260, ultraviolet-visible detector.
Reagent: Avermectin crystal (B component 1>96%, wherein component B1a<80%, component B1b>16%), acetonitrile, methyl alcohol (chromatographically pure), it is pure that acetone, carrene are analysis, anhydrous sodium sulfate, alkali alumina.
Chromatographic condition: chromatographic column is: SymmetryC18 stainless steel chromatographic column (75mm × 4.6mm, 5 μm), mobile phase: V (methyl alcohol): V (water)=85:15; Flow velocity 1.5mL/min; Sampling volume is 10 μ L; Determined wavelength is 245nm, column temperature 40 DEG C.
As can be seen from Table 2, add 200ppm Polyurethane-epoxy resin, under ultraviolet irradiation 3h condition, Avermectin degraded can be reduced and reach 25.42%, illustrate that Polyurethane-epoxy resin can slow down the loss of Avermectin, extend drug effect.
Under table 2 ultraviolet irradiation 3h condition, 200ppm Polyurethane-epoxy resin is on the impact of Avermectin residual rate
Under embodiment 3 water pouring condition, Polyurethane-epoxy resin is on the impact of Determination of Phoxim Residues rate
Step 1 solution allocation
Phoxim and the 400ppm Polyurethane-epoxy resin mother liquor of preparation 800ppm are stand-by, add the Tween 80 emulsifier of 2 ‰ when wherein preparing phoxim mother liquor.Respectively by mass mixings such as Polyurethane-epoxy resin mother liquor, water and phoxim mother liquors, be 400ppm to phoxim concentration, Polyurethane-epoxy resin concentration is 200ppm, and wherein processed group is 400ppm phoxim+200ppm Polyurethane-epoxy resin mixed liquor, and control group is 400ppm phoxim solution.
Step 2 sprays, water drenches and sampling
Afternoon, 15:00 carried out spray medicine to Chinese cabbage, and 1h sampling after spray medicine, sample quality is greatly about 25-40g.
Carry out carrying out second time sampling after water drenches 12h to cabbage leaf after sampling, after leaf natural is dried, carry out the mensuration of pesticide concentration.
Step 3 sample pre-treatments
The sample fetched is shredded mixing, take respectively in the centrifuge tube of 5g to 50mL, add benzinum: acetone=1:1 solution 10mL soaked overnight, add the active carbon vibration mixing 30min of 0.1-0.3g next day, at the centrifugal 15min of 12000r/min, get supernatant solution and filter that to carry out gas phase to be measured.
Step 4 detects
Method is with the step 3 of embodiment 1.
Result is as shown in table 3, and as can be seen from the table, 12h after water drenches, comparatively clear water control group is low by 29.03% for the phoxim degradation rate of Polyurethane-epoxy resin processed group, and namely under water pouring condition, Polyurethane-epoxy resin can slow down the loss of phoxim, extends drug effect.
Under table 3 water pouring condition, 200ppm Polyurethane-epoxy resin is on the impact of phoxim degradation rate
Under embodiment 4 water pouring condition, Polyurethane-epoxy resin is on the impact of Avermectin residual rate
Step 1 solution allocation
By Avermectin dissolution of crystals in methyl alcohol, be made into the concentration of 400ppm, and stand-by with the Polyurethane-epoxy resin solution mother liquor of distilled water preparation 400ppm.By Avermectin mother liquor and Polyurethane-epoxy resin mother liquor with volume ratio 1:1 mix all with, namely in mixed liquor, Avermectin concentration is 200ppm, and Polyurethane-epoxy resin concentration is 200ppm, and wherein control group is Avermectin mother liquor and equal quality clear water mixed liquor.
Step 2 sprays, water drenches and sampling
Afternoon, 15:00 carried out spray medicine to Chinese cabbage, and 1h sampling after spray medicine, sample quality is greatly about 25-40g.
Carry out carrying out second time sampling after water drenches 12h to cabbage leaf after sampling, after leaf natural is dried, carry out the mensuration of pesticide concentration.
Step 3 sample pre-treatments
The sample fetched is shredded mixing, take respectively in the centrifuge tube of 5g to 50mL, add benzinum: acetone=1:1 solution 10mL soaked overnight, add the active carbon vibration mixing 30min of 0.1-0.3g next day, at the centrifugal 15min of 12000r/min, get supernatant solution and filter that to carry out liquid phase to be measured.
Step 4 detects
Method is with the step 3 of embodiment 2.
Result is as shown in table 4, and as can be seen from the table, 12h after water drenches, comparatively clear water control group is high by 28.93% for the Determination of Abamectin Residue of Polyurethane-epoxy resin processed group, and namely under water pouring condition, Polyurethane-epoxy resin can slow down the loss of Avermectin, extends drug effect.
Under table 4 water pouring condition, 200ppm Polyurethane-epoxy resin is on the impact of Avermectin degradation rate
Under embodiment 5 water pouring condition, Polyurethane-epoxy resin is on the impact of carbendazim degradation rate
Step 1 solution allocation
With the carbendazim solution of distilled water configuration 400ppm, first use a small amount of dissolving with hydrochloric acid carbendazim, then be settled to scale with distilled water.Dissolving Polyurethane-epoxy resin configuration concentration with distilled water is that the Polyurethane-epoxy resin mother liquor of 400ppm is stand-by.Polyurethane-epoxy resin mother liquor is mixed with carbendazim mother liquor equal-volume, be 200ppm to carbendazim concentration, Polyurethane-epoxy resin concentration is 200ppm, wherein processed group 200ppm carbendazim solution+200ppm Polyurethane-epoxy resin mixed liquor, and control group is 200ppm carbendazim solution.
Step 2 sprays and sampling
Afternoon, 15:00 carried out spray medicine to Chinese cabbage, and 1h sampling after spray medicine, sample quality is greatly about 25-40g.
Carry out carrying out second time sampling after water drenches 12h to cabbage leaf after sampling, after leaf natural is dried, carry out the mensuration of pesticide concentration.
Step 3 sample treatment
The sample fetched is shredded mixing, take respectively in the centrifuge tube of 10g to 50mL, add 50mL methyl alcohol to smash to pieces, transfer in wide-mouth bottle, add 20mL washed with methanol, ultrasonic extracts 10min, suction filtration 3 times, merge extract, extract proceeds in flask through anhydrous sodium sulfate water suction filtration, is evaporated near dry.Each sample treatment repeats 3 times.
Clean flask with the 0.2mol/L hydrochloric acid of 50ml and 5%NaCl mixed solution (V/V=1/4), be transferred in separatory funnel by cleaning fluid, then add 30mL carrene thermal agitation 1min, stratification, discards dichloromethane layer.The NaOH of aqueous phase 0.2mol/L regulates solution ph to 7.0, uses dichloromethane extraction (20mL × 3), and through anhydrous sodium sulfate drying, combined dichloromethane layer, is evaporated near dry, adds methanol constant volume to 5mL, filter, treat liquid-phase chromatographic analysis.
Step 4 detects
Chromatograph: high performance liquid chromatograph Agilent1260, ultraviolet-visible detector.
Reagent: carbendazim (99%), anhydrous sodium sulfate, carrene, methyl alcohol, hydrochloric acid, NaOH, NaCl, NH
4ac (AR), methyl alcohol (chromatographic grade).
Chromatographic condition: chromatographic column is HypersilODSC18 (250mm × 4.6mm, 5 μm), and column temperature is room temperature, mobile phase: methyl alcohol-2%NH
4the Ac aqueous solution (V/V=45/55), flow velocity is 1.0mL/min, determined wavelength 284nm, and sample size is 10 μ L.
Result is as shown in table 5, as can be seen from the table, sprays rear 48h, and comparatively clear water control group is low by 30.32% for the carbendazim degradation rate of Polyurethane-epoxy resin processed group, and namely under water pouring condition, Polyurethane-epoxy resin can slow down the loss of carbendazim, extends drug effect.
Under table 5 water pouring condition, 200ppm Polyurethane-epoxy resin is on the impact of carbendazim degradation rate
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to example to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (8)
1. Polyurethane-epoxy resin is as the application of agricultural chemicals adhesive.
2. apply as claimed in claim 1, it is characterized in that: Polyurethane-epoxy resin is as the application of agricultural chemicals adhesive and weed killer herbicide, insecticide or bactericide.
3. apply as claimed in claim 2, it is characterized in that: Polyurethane-epoxy resin is mixed with phoxim pesticide.
4. apply as claimed in claim 3, it is characterized in that: the mass ratio of described Polyurethane-epoxy resin and described phoxim is 1:1 ~ 5.
5. apply as claimed in claim 2, it is characterized in that: Polyurethane-epoxy resin and Avermectin combined use of pesticides.
6. apply as claimed in claim 5, it is characterized in that: the mass ratio of described Polyurethane-epoxy resin and described Avermectin is 1:0.25 ~ 1.
7. apply as claimed in claim 2, it is characterized in that: Polyurethane-epoxy resin and carbendazim combined use of pesticides.
8. apply as claimed in claim 7, it is characterized in that: the mass ratio of described Polyurethane-epoxy resin and described carbendazim is 1:1 ~ 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108546178A (en) * | 2018-03-25 | 2018-09-18 | 江苏辉丰生物农业股份有限公司 | Medicine fertilizer composition containing potassium phosphite and polyglutamic acid |
| CN108925553A (en) * | 2017-05-23 | 2018-12-04 | 沧州鸿源农化有限公司 | A kind of anti-drift builder composition |
| CN117426400A (en) * | 2023-12-20 | 2024-01-23 | 中科生物技术(山东)有限公司 | Synergistic auxiliary agent of acaricide, preparation method and application thereof |
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Cited By (4)
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| CN108925553A (en) * | 2017-05-23 | 2018-12-04 | 沧州鸿源农化有限公司 | A kind of anti-drift builder composition |
| CN108546178A (en) * | 2018-03-25 | 2018-09-18 | 江苏辉丰生物农业股份有限公司 | Medicine fertilizer composition containing potassium phosphite and polyglutamic acid |
| CN117426400A (en) * | 2023-12-20 | 2024-01-23 | 中科生物技术(山东)有限公司 | Synergistic auxiliary agent of acaricide, preparation method and application thereof |
| CN117426400B (en) * | 2023-12-20 | 2024-03-29 | 中科生物技术(山东)有限公司 | Synergistic auxiliary agent of acaricide, preparation method and application thereof |
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