CN1951195A - Plant bacteriostatic agent and preparation method thereof - Google Patents
Plant bacteriostatic agent and preparation method thereof Download PDFInfo
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- CN1951195A CN1951195A CN 200610160701 CN200610160701A CN1951195A CN 1951195 A CN1951195 A CN 1951195A CN 200610160701 CN200610160701 CN 200610160701 CN 200610160701 A CN200610160701 A CN 200610160701A CN 1951195 A CN1951195 A CN 1951195A
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- agent
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- zinc
- phosphoric acid
- plant bacteriostatic
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Abstract
The invention discloses a plant bacteria inhibitor and its preparing process, wherein the active compositions include ZnMAP and ZnDAP, and the preparing process consists of using ethanol, phosphorylation agent, ammonia and zinc salts as raw materials, reacting ethanol with phosphorylation agent to obtain reaction product containing MAP, DAP and TAP, ammonizing the reaction product with ammonia, and introducint divalent zinc ions.
Description
Technical field
The present invention relates to pesticide field.More particularly, the present invention relates to a kind of plant bacteriostatic agent and preparation method thereof.
Background technology
Aliette is a kind of plant bacteriostatic agent of domestic prolonged application, and it can be used for the inhibition of the multiple germ of plant, especially downy mildew.In recent years along with the mankind's deepening continuously to aluminium evil research in the food, people begin the intake of aluminium in the strict dietary restriction, can to be absorbed the aluminium residual quantity that causes in the fruit by plant corpus in the process of growth of crops too much owing to the aluminium element in the aliette, thereby influenced the safety of food.In addition, PCl is adopted in the aliette production of prior art mostly
3And POCl
3As raw material, at first the accessory substance HCl of these raw materials in esterification process can cause environmental pollution, and careless slightly in process of production, just causes raw material PCl easily
3And POCl
3Leakage, thereby when causing environmental pollution, also seriously endangering the healthy of operator.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of pathogenic bacteria that can not only suppress effectively in the plant, and processing and making process safety, environmental protection, can not cause the residual plant bacteriostatic agent of harmful element again to crops in the use.
Another object of the present invention also is to provide a kind of manufacture method of this plant bacteriostatic agent.
Technical scheme of the present invention at first is the design of bacteriostatic agent active component.In order to substitute the aluminium element in the aliette, we have carried out screening carefully to this compounds, through taking all factors into consideration of associate validity and two aspects of safety, finally determined to replace aluminium with zinc, promptly making a kind of is the plant bacteriostatic agent of active component with phosphate monoester zinc (ZnMAP) and phosphate diester zinc (ZnDAP).Because as you know, zinc is a kind of essential trace element in the human body, and this element still is in the state of general deficiency in present people's food supply.Trace zinc that may be residual in the plant not only can harm humans health, it is opposite that the deficiency of zinc element has very useful effect in the food for remedying; Secondly, though phosphate monoester zinc and phosphate diester zinc utilize its active component as plant bacteriostatic agent not to be reported in the prior art as the existing in the prior art report of known substance.
Next is exactly the formulation of raw material selection and synthetic route.Through conscientiously screening and scheme optimization, the concrete raw material that decision is adopted is ethanol and phosphoric acid agent, the design synthetic route of selecting is to carry out esterification by ethanol and phosphoric acid agent earlier, with ammoniacal liquor the product of esterification is carried out ammonification then, introduces divalent zinc ion at last again.
Here the concrete technical problem of first that will solve is exactly the selection of phosphoric acid agent, because the different concrete reactive modes that phosphoric acid agent was suitable for is also inequality.Phosphoric acid agent commonly used at present has PCl
3, POCl
3, pyrophosphoric acid and P
2O
5Deng.Generally speaking, these phosphoric acid agents may be used to prepare the second phosphorus zinc bacteriostatic agent of this aspect, still, because PC
L3Very strong with the reaction of POCl, and see that air pole is volatile, equipment is required comparatively harshness, and the resulting accessory substance HCl in reaction back also can cause environmental pollution.The reaction of pyrophosphoric acid then needs to carry out with the dimethylbenzene azeotropic dehydration, and course of reaction is comparatively slow, and used dimethylbenzene also is harmful raw material.Through relatively comprehensive, preferably adopt P in the present invention
2O
5Make phosphoric acid agent.This is based on the consideration of the following aspects: at first, and P
2O
5Raw material can not produce pollutant in process, reaction condition is very gentle, and raw material sources are also quite sufficient, low price; In addition, P
2O
5Have the tetrahedral structure of the key of 6 activity, use P
2O
5Carry out the mixture that esterification can generate phosphate monoester, phosphate diester and phosphotriester etc. with ethanol.Concrete preparation feedback formula is as follows:
The product that above-mentioned reaction generates is the mixture of phosphate monoester (MAP), phosphate diester (DAP) and phosphotriester (TAP), except these several compositions, also has very a spot of phosphoric acid polyester (PAP) and phosphoric acid.
Preferably by regulating the inventory of raw material, make the percentage composition of phosphate monoester (MAP) in three kinds of esters, phosphate diester (DAP) and phosphotriester (TAP) be respectively 52wt%, 34.5wt% and 13.5wt%.And through test confirmation, fungistatic effect the best of formed zinc salt in this case.
As follows, at above-mentioned P
2O
5With directly add ammoniacal liquor in the product of ethanol, in its aminate, introduce divalent zinc ion then, finally form the second phosphorus zinc salt of two kinds of different structures.
Wherein can use zinc salt, for example zinc sulphate etc. is introduced divalent zinc ion in product, but is not limited in this.
(1) monoesters reaction
(2) dibasic acid esters reaction
Above-mentioned reaction is exothermic reaction, because this course of reaction occurs in the P of powdery
2O
5Between the ethanol of solid and liquid state, so Gu initial reaction stage is liquid-heterogeneous reaction system, it is too drastic that be prone to local reaction this moment, and untimely meeting makes hydroxyl material generation dehydration that product is darkened as its heat diffusion.In addition, powdery P
2O
5The solid caking that easily absorbs water also is disadvantageous to esterification.In order to address this problem, the present invention adopts the acetone equal solvent as P
2O
5Sustained release agent, thereby Gu the reaction system that makes this reaction is become by liquid-heterogeneous system is liquid-liquid homogeneous phase system, and therefore make ethanol and P
2O
5Reaction evenly carry out.
Phosphate monoester zinc and phosphate diester zinc in the above-mentioned product all have good bacteriostasis, and its accessory substance ammonium sulfate also can be used as the fertilizer use, if therefore above-mentioned two kinds of components are separated from end product manufacturing cost is increased greatly, and not have too big necessity.Generally economic method is that this mixture integral body is directly used as the former medicine of second phosphorus zinc, if having special requirement certainly, can both be separated from product by the method for rectifying.
The intermittent operation method is adopted in the preparation of product of the present invention, needs to have calculated by reaction equation in advance the input amount of raw material before production.Because P
2O
5Want before use obtain solution,, add P again so should in enamel still, add slowly-releasing solution acetone earlier
2O
5, treat that it dissolves the back fully and adds ethanol, its reaction condition is that temperature is 15-25 ℃, pressure is normal pressure.React after 1 hour, add ammoniacal liquor, add ZnSO at last
4
Confirm that through test reactor product of the present invention is ploughed diseases such as the microbial downy mildew of spore, eqpidemic disease, rice blast for the rice of the Peronospora in the phycomycete subphylum in the plant, Phytophthora disease fungus and Deuteromycotina the obvious suppression effect.The conventional amount of application of product is every mu of ground 80-160g.
The invention has the beneficial effects as follows that not only the drug effect of product of the present invention obviously is better than existing second phosphorus zinc, and the raw material that adopts promptly environmental pollution can be do not caused, the healthy of operator can be do not damaged yet.Product of the present invention in addition in use poisonous and harmful element residual in the crops not only can not occur, also can help to solve the zinc deficiency problem in modern's food on the contrary.The cost of material that has plenty of product of the present invention again is very low, is easy to be extended and applied especially.
Preferred forms
Preparation embodiment 1
In the enamel still, add 15Kg acetone sustained-release liquid, add 5Kg P then
2O
5, treat that adding 10Kg ethanol again after it dissolves fully reacts, reaction temperature is 20 ℃, pressure is normal pressure.React after 1 hour, obtain containing the product of the mixed ester of MAP, DAP and TAP through look-matter on-line analysis, wherein the weight ratio of MAP: DAP: TAP is 52: 34.5: 13.5.In this product, add 15Kg ammoniacal liquor, add 15KgZnSO then
4Above-mentioned product (second phosphorus zinc) is directly used in following bacteriostatic test without separation.
Experimental example 1
Reagent agent: second phosphorus zinc; Aliette (contrast medicament)
For trying pathogen: graw mold of tomato, fusarium wilt, downy mildew, leaf mold, rice blast
Test method: mother liquid concentration 0.1mg/ml.By the required chemicals treatment concentration of test the bactericide mother liquor is joined respectively in the sterilising medium, pour into after mixing to make in the culture dish and contain 5ppm, 10ppm, 25ppm, 50ppm, 75ppm medicine medium, each concentration is established three repetitions.
Result of the test (after 7 days):
Table 1 second phosphorus zinc control tomato downy mildew, leaf mold, gray mold, fusarium wilt and
The rice blast result of the test
| Downy mildew second phosphorus zinc | Colony diameter cm | Colony diameter cm | Colony diameter cm |
| CK | 2.1 | 2.2 | 2.4 |
| 5 | 1.2 | 1.1 | 1.3 |
| 10 | 0.9 | 0.9 | 1 |
| 25 | 1.1 | 0.9 | 0.7 |
| 50 | 0.4 | 0.5 | 0.5 |
| 75 | 0 | 0 | 0 |
| The contrast medicament | |||
| 5 | 1.4 | 1.3 | 1.2 |
| 10 | 1 | 0.9 | 1.1 |
| 25 | 0.9 | 1 | 0.8 |
| 50 | 0.7 | 0.6 | 0.7 |
| 75 | 0 | 0 | 0 |
| Leaf mold second phosphorus zinc | |||
| CK | 8.6 | 8.6 | 8 |
| 5 | 2.9 | 2.7 | 3.3 |
| 10 | 4.3 | 3.4 | 3.3 |
| 25 | 2.3 | 3.1 | 3 |
| 50 | 2.1 | 1.7 | 2.6 |
| 75 | 1.8 | 2.1 | 1.5 |
| The contrast medicament | |||
| 5 | 8.6 | 8.6 | 8.5 |
| 10 | 8.6 | 5.8 | 6.8 |
| 25 | 4.2 | 4.5 | 5.3 |
| 50 | 1.5 | 1.6 | 1.7 |
| 75 | 1.1 | 1 | 1.2 |
| Gray mold second phosphorus zinc | |||
| CK | 9.2 | 9.2 | 9.2 |
| 5 | 4.5 | 5 | 5 |
| 10 | 5.1 | 4.4 | 4.4 |
| 25 | 2 | 2.3 | 2.3 |
| 50 | 1.2 | 1 | 1.1 |
| 75 | 0 | 0 | 0 |
| The contrast medicament | |||
| CK | 9.2 | 9.2 | 9.2 |
| 5 | 6.7 | 6 | 7.2 |
| 10 | 4.8 | 5.6 | 5.1 |
| 25 | 3.6 | 3.3 | 3.7 |
| 50 | 1.8 | 1.9 | 2.1 |
| 75 | 0.8 | 1.2 | 0.9 |
| Fusarium wilt second phosphorus zinc | |||
| CK | 5.6 | 5.2 | 5.2 |
| 5 | 4.9 | 4.9 | 4.2 |
| 10 | 4.2 | 4.5 | 4.5 |
| 25 | 3.9 | 4 | 3.8 |
| 50 | 2.7 | 2.9 | 2.2 |
| 75 | 0 | 0 | 0 |
| The contrast medicament | |||
| CK | 5.6 | 5.2 | 5.2 |
| 5 | 3.6 | 3.5 | 3.5 |
| 10 | 4.2 | 4.4 | 4.5 |
| 25 | 3.2 | 3.3 | 2.9 |
| 50 | 2 | 1.9 | 2 |
| 75 | 1.7 | 1.7 | 1.8 |
| Rice blast second phosphorus zinc | |||
| CK | 3.7 | 3.8 | 4 |
| 5 | 2.2 | 2.5 | 2.3 |
| 10 | 2.1 | 2.2 | 2.2 |
| 25 | 2 | 1.9 | 2 |
| 50 | 1.6 | 1.7 | 1.5 |
| 75 | 1.4 | 1.5 | 1.3 |
| The contrast medicament | |||
| CK | 3.7 | 3.8 | 4 |
| 5 | 3 | 3.1 | 3.3 |
| 10 | 2.9 | 3 | 3.2 |
| 25 | 2.8 | 2.7 | 2.9 |
| 50 | 2.5 | 2.6 | 2.7 |
| 75 | 2.5 | 2.3 | 2.1 |
By above-mentioned result of the test as can be known: (1) second phosphorus zinc all has the obvious suppression effect to the pathogen of five kinds of diseases; (2) second phosphorus zinc is obvious because the inhibition effect of contrast medicament aliette to the inhibitory action of rice blast.
Experimental example 2
Subjects: cucumber variety is a Chang Chun Mi Ci.
Test is handled: reagent agent is 300,400,500,600,800 times of liquid of second phosphorus zinc.With 500 times of 80% aliettes is contrast.
Table 2 second phosphorus zinc control plastic tent cucumber downy mildew effect
| Handle | Concentration (doubly) | Repeat (inferior) | Disease index | Control efficiency (%) | Output (kg/hm 2) | Than aliette rate of growth (%) | Rate of growth (%) |
| Second phosphorus zinc | 300 | 4 | 5.4 | 84.0 | 5445 | 9 | 145 |
| Second phosphorus zinc | 400 | 4 | 7.0 | 89.0 | 5680 | 14 | 156 |
| Second phosphorus zinc | 500 | 4 | 7.8 | 88.0 | 6752 | 36 | 203 |
| Second phosphorus zinc | 600 | 4 | 9.5 | 82.0 | 6320 | 27 | 184 |
| Aliette | 500 | 4 | 15.5 | 55.0 | 4979 | - | 124 |
| Blank | - | 4 | 34.3 | - | 2224 | - | - |
By above-mentioned result of the test as can be known: spray second phosphorus zinc cucumber downy mildew is had the better prevention effect, use 400-500 times and be advisable, its preventive effect all significantly is better than 500 times of 80% aliettes.At plastic tent cucumber downy mildew premorbid spray medicine, 7 days 1 time at interval, continuous four times, can effectively control this disease development.
Claims (7)
1, a kind of plant bacteriostatic agent is characterized in that it contains phosphate monoester zinc (ZnMAP) and phosphate diester zinc (ZnDAP) is made active component.
2, according to the preparation method of the described plant bacteriostatic agent of claim 1, it is characterized in that: with ethanol, phosphoric acid agent, ammoniacal liquor and zinc salt is raw material, at first form the product that contains single second phosphate (MAP), diethyl phosphate (DAP) and three second phosphates (TAP), use this product of ammoniacal liquor ammonification again, introduce divalent zinc ion at last and be prepared from by ethanol and phosphoric acid agent generation esterification.
3, according to the preparation method of the described plant bacteriostatic agent of claim 2, the temperature that it is characterized in that esterification is 15-25 ℃.
4,, it is characterized in that phosphoric acid agent is P according to the preparation method of claim 2 or 3 described plant bacteriostatic agents
2O
5
5,, it is characterized in that before ethanol and phosphoric acid agent reaction, phosphoric acid agent being dissolved in the sustained release agent according to the preparation method of claim 2 or 3 described plant bacteriostatic agents.
6,, it is characterized in that sustained release agent is an acetone according to the preparation method of the described plant bacteriostatic agent of claim 5.
7, according to the preparation method of claim 2 or 3 described plant bacteriostatic agents, it is characterized in that making that by the input amount of regulating feed ethanol, phosphoric acid agent phosphate monoester (MAP) accounts for 52wt% in the esterification products, phosphate diester (DAP) accounts for 34.5wt% and phosphotriester (TAP) accounts for 13.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610160701 CN1951195A (en) | 2006-11-29 | 2006-11-29 | Plant bacteriostatic agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610160701 CN1951195A (en) | 2006-11-29 | 2006-11-29 | Plant bacteriostatic agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1951195A true CN1951195A (en) | 2007-04-25 |
Family
ID=38057914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610160701 Pending CN1951195A (en) | 2006-11-29 | 2006-11-29 | Plant bacteriostatic agent and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1951195A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232639A (en) * | 2018-10-11 | 2019-01-18 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (bis- chloropropyl of 1,3-) ester |
-
2006
- 2006-11-29 CN CN 200610160701 patent/CN1951195A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232639A (en) * | 2018-10-11 | 2019-01-18 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (bis- chloropropyl of 1,3-) ester |
| CN109232639B (en) * | 2018-10-11 | 2021-02-09 | 山东泰和水处理科技股份有限公司 | Preparation method of tris (1, 3-dichloropropyl) phosphonate |
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