CN109619103A - A kind of ionic macromolecule cotton topping agent and preparation method thereof - Google Patents
A kind of ionic macromolecule cotton topping agent and preparation method thereof Download PDFInfo
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- CN109619103A CN109619103A CN201811281749.2A CN201811281749A CN109619103A CN 109619103 A CN109619103 A CN 109619103A CN 201811281749 A CN201811281749 A CN 201811281749A CN 109619103 A CN109619103 A CN 109619103A
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- piperazine
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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Abstract
The invention discloses a kind of ionic macromolecule cotton chemistry topping agent for belonging to preparation technique of pesticide field and preparation method thereof.The topping agent is to generate first piperazine alkali by reacting first piperazine in a solvent with inorganic base, removes inorganic salts, then the solution is directly carried out acid-base neutralization reaction with anionic high molecular material and is prepared；Or ion-exchange reactions is carried out by the inorganic salts of anionic high molecular material and first piperazine in a solvent and is made.Ionic macromolecule cotton topping agent of the invention is pinched with conventional chemical compared with agent, preparation is simple, property is stablized, with preferable Environmental compatibility, lasting period and resistance of rainwater washing against ability, the utilization rate of pesticide active ingredient can be improved, reduce the risk that phytotoxicity occurs.
Description
Technical field
The invention belongs to preparation technique of pesticide field, in particular to a kind of ionic macromolecule cotton topping agent and its preparation
Method.
Background technique
Cotton has indeterminate growth habit, in a certain temperature conditions, top continuous growth elongation, and constantly differentiate
New cauline leaf and fruit branch.If being allowed to grow, due to the presence of apical dominance, moisture and nutrient are top by priority of supply, cause
Cotton plant constantly increases, so that vegetative growth phase is elongated, it is mature later, influence the quality and yield of cotton, it is therefore desirable to cotton
It pinches.Topping generally carries out before the flowering stage and hot weather in cotton growth stage are arrived, and predominantly releases top
Advantage reduces later period fruit abscission rate phenomenon, reaches and cotton is promoted to shift to an earlier date maturation and improve yield and other effects.Furthermore pinching also has
It adjusts the transport of cotton plants nutriment, promote that conversion of the cotton plants from nutrient growth to reproductive growth, to improve cotton field penetrating
Property and reduce nutrient growth and cause nutrient unnecessary consumption, improve efficiency of light energy utilization and other effects, to prevent cotton overgrowing, to fill
The nutrition of foot is transported to cotton buds and bolls.
During current cotton culture, topping mode mainly has two kinds of artificial topping and chemistry topping.Artificial topping compared with
It is common, but time-consuming for this method, amount of labour demanded is big, and business efficiency is low, especially the feelings in Cold region apple schema size
Under condition, the disadvantage manually pinched is increasingly apparent, has seriously affected the development and expansion of Cotton Industry.Sharply along with labour
It reduces and the quick rise of labour cost, simplification, mechanization, scale and high benefit is necessarily becoming for Cotton Production development
Gesture.
In order to substitute traditional topping mode, existing research person carries out the test of chemical agent control cotton apical dominance.
Li Xin in 2001 is abundant equal to have carried out long-staple cotton chemistry using first piperazine single dose and has bound the test for replacing and manually pinching, the results showed that uses
Chemistry, which binds, replaces artificial topping to can reduce labor intensity, improves operating efficiency, but be applied alone the first piperazine lasting period too it is short simultaneously
Production requirement cannot be met well.Zhejiang Hetian Chemical Co., Ltd. in 2010 has invented a kind of multiple with flumetralim and first piperazine
The cotton topping agent matched keeps plant compact, but lasting effect is shorter, Yi Zao by spraying the growth of control cotton stem and side shoot
It turns green at the cotton later period, postpones blow-of-cottons.A small amount of ethephon (CEPHA),2-(chloroethyl) phosphonic acid is added in Zhao Qiang in 2013 etc. in first piperazine, by spraying control cotton
Apical growth, but cotton plant type is loose, is unfavorable for picking, and is affected to caping peach, yield is unstable.
Inventor for first piperazine lasting effect it is short, not resistance of rainwater washing against the problems such as have made intensive studies, with ionic height
Molecular material reacts preparation first piperazine macromolecule polymeric material with first piperazine, achievees the purpose that slow release and anti-rain drop erosion.
The sustained release agent manufacture craft is simple, compared with conventional microcapsule sustained release preparation, shows better Environmental compatibility, agriculture can be improved
The utilization rate of pharmaceutically active ingredient extends the lasting period, reduces the risk that phytotoxicity occurs
Summary of the invention
The purpose of the present invention is to provide a kind of ionic macromolecule cotton topping agent preparation methods, which is characterized in that
The structural formula of the ionic macromolecule cotton topping agent is as follows:
The ionic macromolecule cotton topping agent the preparation method is as follows: first piperazine is generated in a solvent with inorganic base
First piperazine alkali removes inorganic salts；The solution and anionic high molecular material are directly subjected to acid-base neutralization reaction；
The preparation method or are as follows: by the soluble salt of anionic high molecular material and first piperazine carry out in a solvent from
Sub- exchange reaction.
Anionic high molecular material therein is polyacrylic acid, polymethylacrylic acid, alginic acid and its sodium salt, molecule
Amount size is 2000-4000.
The molar ratio of anionic high molecular material therein and first piperazine is 1:0.3~3.0.
The molar ratio of anionic high molecular material therein and first piperazine is preferably 1:0.6~1.0.
First piperazine therein and inorganic base generate first piperazine alkali in a solvent, remove after inorganic salts with anionic macromolecule
Material directly carries out the inorganic salts of acid-base neutralization reaction or anionic high molecular material and first piperazine carry out in a solvent from
The time of sub- exchange reaction is 1~4 hour, preferably 2~3 hours；Reaction temperature is 0~60 DEG C, preferably 20~40 DEG C.
Reaction dissolvent therein is water, in methanol, ethyl alcohol, isopropanol, tetrahydrofuran, acetone, acetonitrile, glycol monoethyl ether
One or more of mixtures.
The chemical equation and structural formula of the preparation method are following (by taking polyacrylic acid as an example):
Acid-base neutralization reaction:
Ion exchange:
Polymethylacrylic acid, alginic acid are identical as polyacrylic acid reaction mechanism.
A kind of ionic macromolecule cotton topping agent controls its excessive growth applied to cotton growth period, using sprinkling side
Formula application, per hectare dosage are 1500~2000g.
The invention has the benefit that compared with conventional chemical pinches agent, ionic macromolecule cotton topping of the invention
Agent preparation is simple, property is stable, Environmental compatibility is good, has good lasting period and resistance of rainwater washing against ability, can be improved agriculture
The utilization rate of pharmaceutically active ingredient reduces the risk that phytotoxicity occurs, and improves Cotton Production benefit.
Specific embodiment
The present invention provides a kind of ionic macromolecule cotton topping agents and preparation method thereof, below with reference to embodiment to this
Invention is described further.
Embodiment 1:
(1) 11.5 gram of 98% first piperazine raw medicine (0.1mol), 5.6g potassium hydroxide preparation method: are dissolved in 50 grams of second
Alcohol is added in 250ml there-necked flask after mixing, filters out precipitating after 2h is stirred at room temperature.It is water-soluble to add 24 gram of 30% polyacrylic acid
Liquid (0.1mol) detects stopping reaction when the first piperazine content dissociated in solution is lower than 20mg/L after 2h is stirred at room temperature, is glued
Degree is the high molecular polymer of 126 centipoises, the piperazine of first containing effective component 12%, pH value 5.7.Specific chemical reaction equation
Formula is as follows:
(2) compliance test result:
12% first piperazine soluble liquid is to cotton the effectiveness of roof control test method:
It is spraying to be watered 8L progress unmanned plane by present invention topping agent per hectare dosage 1500g.Dosage presses GB/
T8321.1-2000 requires operation, and medicament uses after need to carrying out secondary dilution.The specific method is as follows: first is that getting out 1 before making up a prescription
A bucket, 1 measuring cup, to guarantee the accuracy made up a prescription；Second is that first add half water into application case, the medicine needed for being weighed with measuring cup
Agent dose pours into bucket and is configured to mother liquor, application case then is added in mother liquor, while carrying out return water stirring, finally remaining water
It is added and stirs evenly.
Comparison medicament selects 10% first piperazine soluble powder, and specific test sample information is as shown in table 1 below.
1 test sample information of table
Practice ground is located at city, Aksu of Xinjiang (42 ° of 23 ' N, 86 ° of 24 ' E), and experimental plot soil is loam, and preceding stubble is cotton
Flower, the topsoil soils content of organic matter are 17.9gkg-1, alkali-hydrolyzable nitrogen 26.7mgkg-1, rapid available phosphorus 24.6mgkg-1, available potassium
188.0mg·kg-1.Cotton variety is to be covered using wide film, 1 film, 4 row 75 in new land, and theoretical strain number is 210,000 plants of hm-2, remove
Artificial topping link is carried out according to high-yield field Routine Management mode by other other than chemistry topping substitution.
12% first piperazine soluble liquid resistance of rainwater washing against test method:
2mg rhodamine B is added separately in 10mL reagent agent, is diluted with water 6.33 times.Take clean cotton leaf
Several, each blade drops evenly 0.5mg reagent agent dilution, dries at room temperature.It is washed and is dried with 0.5g deionized water,
Fluorescence area M on blade is calculated using ImageJ software by Stereo fluorescence microscopei, fluorescence area is M before washingo, calculate back
Percentage F is received,
Using effect to illustrate the invention is beaten using cotton topping agent of the invention, conventional chemical topping agent and manually
Top carries out cotton topping respectively, and concrete outcome is as shown in table 2.As shown in Table 2, after using cotton topping agent of the invention, with
10% first piperazine soluble powder is compared, and significantly enhances first piperazine to the lasting effect and the effectiveness of roof control on cotton control top；With it is artificial
Topping is compared, and labor intensity is significantly reduced, and improves mechanical work level, and cost input reduces by 400 yuan of hm-2, rate of growth
Up to 0.05%.Therefore the present invention has extensive promotional value.
The topping agent of table 2 handles the influence to cotton plant height and yield
Note: different letters indicate upper significant difference (Duncan method) horizontal in P < 0.05 after same column data, similarly hereinafter.
Resistance of rainwater washing against test effect is as shown in table 3 below, by the visible 12% first piperazine soluble liquid resistance of rainwater washing against of table
Ability is substantially better than comparison medicament.
3 resistance of rainwater washing against test effect of table
Embodiment 2:
(1) preparation method: 11.5 gram of 98% first piperazine raw medicine (0.1mol) is used into deionized water dissolving, adds 24 grams
30% aqueous sodium polyacrylate (0.1mol) stirs at 40 DEG C and detects the first piperazine content dissociated in solution after 2h and be lower than
Stop reaction when 50mg/L, obtains the high molecular polymer that viscosity is 126 centipoises, the piperazine of first containing effective component 12%, pH value
It is 5.7.Specific chemical equation is as follows:
(2) compliance test result:
12% first piperazine soluble liquid is to cotton the effectiveness of roof control test method: solvable with 12% first piperazine in embodiment 1
Property liquor test method is consistent.
12% first piperazine soluble liquid resistance of rainwater washing against test method: with 12% first piperazine solubility liquid in embodiment 1
Agent test method is consistent.
Cotton topping is carried out using cotton topping agent of the invention, conventional chemical topping agent and artificial topping respectively, is had
Body result is as shown in table 4 below.As shown in Table 4, after using cotton topping agent of the invention, with 10% first piperazine soluble powder phase
Than significantly enhancing first piperazine to the lasting effect and the effectiveness of roof control on cotton control top；Compared with artificial topping, cost input is reduced
400 yuan of hm-2, rate of growth is up to 0.03%.By taking Xinjiang as an example, using cotton topping agent of the present invention, then it can increase unginned cotton every year
0.36 hundred million kilograms of yield, RMB is increased income up to 2.7 hundred million, save the cost puts into RMB 600,000,000 (400 yuan × 1,500,000 hectares), because
This present invention has extensive promotional value.
The topping agent of table 4 handles the influence to cotton plant height and yield
Resistance of rainwater washing against test effect is as shown in table 5 below, by the visible 12% first piperazine soluble liquid resistance of rainwater washing against of table
Ability is substantially better than to be compareed in medicament.
5 resistance of rainwater washing against test effect of table
Embodiment 3:
(1) preparation method: 11.5 gram of 98% first piperazine raw medicine (0.1mol) is dissolved with 5.6g potassium hydroxide with methanol, is mixed
It closes and is added in 250ml there-necked flask, filter out precipitating after 2h is stirred at room temperature, add 29 gram of 30% polymethyl aqueous acid
(0.1mol), 20 DEG C stirring 2h after detect solution in dissociate first piperazine content be lower than 50mg/L when stop reaction, obtain viscosity
For 126 centipoises, the high molecular polymer of the piperazine of first containing effective component 12%, pH value 5.7.Specific chemical equation
It is as follows:
(2) compliance test result
12% first piperazine soluble liquid is to cotton the effectiveness of roof control test method: solvable with 12% first piperazine in embodiment 1
Property liquor test method is consistent.
12% first piperazine soluble liquid resistance of rainwater washing against test method: with 12% first piperazine solubility liquid in embodiment 1
Agent test method is consistent.
Cotton topping is carried out using cotton topping agent of the invention, conventional chemical topping agent and artificial topping respectively, is had
Body result is as shown in table 6 below.As shown in Table 6, after the first piperazine soluble liquid of this method preparation carries out cotton topping, with 10%
First piperazine soluble powder is compared, and significantly enhances first piperazine to the lasting effect on cotton control top；Compared with artificial topping, subtract significantly
Light labor intensity, improves mechanical work level, cost input reduces by 400 yuan of hm-2, rate of growth is up to 0.02%.As it can be seen that
Cotton topping agent preparation process of the invention is simple, and progress cotton topping the effectiveness of roof control is good, and input cost is low, has and preferably pushes away
Wide value.
The topping agent of table 6 handles the influence to cotton plant height and yield
Resistance of rainwater washing against test effect is as shown in table 7 below, by the visible 12% first piperazine soluble liquid resistance of rainwater washing against of table 7
Ability is substantially better than medicament control.
Table 7: resistance of rainwater washing against test effect
Claims (8)
1. a kind of ionic macromolecule cotton topping agent, which is characterized in that the structure of the ionic macromolecule cotton topping agent
Formula is as follows:
2. a kind of preparation method of ionic macromolecule cotton topping agent, which is characterized in that described the preparation method is as follows: by first piperazine
It generates first piperazine alkali in a solvent with inorganic base, removes inorganic salts；By the solution and anionic high molecular material directly into
Row acid-base neutralization reaction；
The preparation method or for the soluble salt of anionic high molecular material and first piperazine are carried out ion friendship in a solvent
Change reaction.
3. a kind of preparation method of ionic macromolecule cotton topping agent according to claim 2, which is characterized in that described
Anionic high molecular material is polyacrylic acid, polymethylacrylic acid, alginic acid and its sodium salt, ammonium salt, sylvite.
4. a kind of preparation method of ionic macromolecule cotton topping agent according to claim 2, which is characterized in that described
The molar ratio of anionic high molecular material and first piperazine is 1:0.3~3.0.
5. a kind of preparation method of ionic macromolecule cotton topping agent according to claim 2, which is characterized in that described
The molar ratio of anionic high molecular material and first piperazine is preferably 1:0.6~1.0.
6. a kind of preparation method of ionic macromolecule cotton topping agent according to claim 2, which is characterized in that described
First piperazine and inorganic base generate first piperazine alkali in a solvent, remove and directly carry out acid with anionic high molecular material after inorganic salts
Alkali neutralization reaction or anionic high molecular material inorganic salts and first piperazine carry out in a solvent ion-exchange reactions when
Between be 1~4 hour, the temperature of reaction is 0~60 DEG C.
7. a kind of preparation method of ionic macromolecule cotton topping agent according to claim 2, which is characterized in that described
First piperazine and inorganic base generate first piperazine alkali in a solvent, remove and directly carry out acid with anionic high molecular material after inorganic salts
Alkali neutralization reaction or anionic high molecular material inorganic salts and first piperazine carry out in a solvent ion-exchange reactions when
Between preferably 2~3 hours, the temperature of reaction is preferably 20~40 DEG C.
8. a kind of preparation method of ionic macromolecule cotton topping agent according to claim 2, which is characterized in that described
Reaction dissolvent is one or more of water, methanol, ethyl alcohol, isopropanol, tetrahydrofuran, acetone, acetonitrile, glycol monoethyl ether
Mixture.
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2018
- 2018-10-31 CN CN201811281749.2A patent/CN109619103B/en active Active
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| US20150126363A1 (en) * | 2012-04-16 | 2015-05-07 | Basf Se | Agroformulation comprising copolymer of acrylic acid, poly(alkylene glycol) (meth)acrylate, and alkyl (meth)acrylate |
| US20160106092A1 (en) * | 2013-05-27 | 2016-04-21 | Lamberti Spa | Water soluble polymers for agrochemical compositions |
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