CN101720779A - Organic silicon pesticide synergist and preparation method thereof - Google Patents
Organic silicon pesticide synergist and preparation method thereof Download PDFInfo
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- CN101720779A CN101720779A CN200910185397A CN200910185397A CN101720779A CN 101720779 A CN101720779 A CN 101720779A CN 200910185397 A CN200910185397 A CN 200910185397A CN 200910185397 A CN200910185397 A CN 200910185397A CN 101720779 A CN101720779 A CN 101720779A
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Abstract
The invention discloses an organic silicon pesticide synergist and a preparation method thereof, the structural formula of the synergist is as follows, wherein a is equal to 5-50, b is equal to 0-25; the structural formula of R1 is that R1 is equal to -CH3, -H; and the structural formula of R2 is that R2 is equal to -H3, -CH3; -C4H9; -O(O)CCH3. The organic silicon pesticide synergist has the advantages of very low liquid surface tension which is about 20-22mN/m, capability of being used as a super extender, a penetrating agent and an emulsifying dispersant, good stability within an extensive pH value range, no toxicity or harm, good physiological safety performance, being applicable to a variety of herbicides, insecticides, fungicides, plant growth regulators, bio-pesticides and foliar fertilizers, saving the pesticide consumption by more than 40% and saving the water consumption by more than one third; and the preparation method of the organic silicon pesticide synergist has the advantages of fewer side effects and high yield.
Description
Technical field
The present invention relates to a kind of organic silicon pesticide synergist, relate to its preparation method simultaneously, particularly the preparation method of polyether-modified trisiloxanes.
Background technology
As everyone knows, at present the most of agricultural chemicals that use in the world comprise that weed killer herbicide, insecticide, bactericide, plant growth regulator etc. all have toxicity in various degree, the public hazards that become international of the residue of pesticide in the agricultural product.And along with pest and the drug-fast raising of mushroom, require the usage amount of all kinds of agricultural chemicals increasing, human beings'health in serious threat, in order to improve drug effect, reduce pesticide dosage, the mankind are exploring always and are using various pesticide synergistic agents, use maximum organic surface active agents that is, bleeding agent, wetting agent or the like, and since the surface tension of these organic class surfactants mostly more than 25mN/m, its synergistic effect is not fairly obvious, it should be noted that organic silicon surfactant until the seventies, the eighties is very active as the research of pesticide synergistic agent to the organosilicon surface-active, abroad bring into use the nineties, finds that organic silicon pesticide synergist is a kind of efficient, nontoxic, the exsertile pesticide synergistic agent of superficiality.Wherein be based on alkoxy-modified poly-trisiloxanes and its compound mostly, its method for making is as follows:
Method 1
Reaction:
In the following formula: Me=CH
3X=0～10; Y=1～20.
From above reaction as can be known, though this method can be produced hydrogen containing siloxane, also contain the hydrogen siloxane ring body simultaneously, both are difficult to separate.
Method 2
Reaction:
In the following formula: Me=CH
3X=0～10; Y=1～20.
From above-mentioned reaction as can be known, synthetic hydrogen-containing siloxane must be with pure tetramethyl-ring tetrasiloxane (D
4 -H, (MeHSiO)
4), and D
4 -HNot only cost an arm and a leg, and be difficult to from mixed methylcyclosiloxane, separate.
The Si-H addition catalyst:
Normally used Si-H addition catalyst mostly is chloroplatinic acid, and this noble metal catalyst costs an arm and a leg, and is difficult to separate from product, and a large amount of heat releases when carrying out the Si-H addition reaction, causes taking place side reaction and dashes material.
The end alkenyl polyether:
Be used for the used allyl-terminated polyether of synthesizing organo-silicon pesticide synergistic agent, a series of side reaction can take place in this allyl-terminated polyether when carrying out the Si-H addition reaction:
This intramolecular rearrangement reaction causes delay of response, even might stop the carrying out of Si-H addition reaction.Cause productive rate to reduce.
Summary of the invention
First technical problem to be solved by this invention provides a kind of have extremely low surface tension of liquid, the fairly obvious organic silicon pesticide synergist of synergistic effect.
Second technical problem to be solved by this invention provides the preparation method of above-mentioned organic silicon pesticide synergist.
The technical scheme of technical solution problem of the present invention is: described organic silicon pesticide synergist is the organic silicon modified by polyether azane, and its chemical structural formula is:
Wherein: a=5～50; B=0～25;
R
1Structural formula be: R
1=-CH
3,-H,
R
2Structural formula be: R
2=-H
3,-CH
3-C
4H
9-O (O) CCH
3
Preferably: a=5～15, b=0～5;
Preferred R
1Structural formula be :-CH
3
Preferred R
2Structural formula be :-CH
3,-H.
For solving above-mentioned second problem, the technical solution used in the present invention is: the preparation method of described organic silicon pesticide synergist comprises the steps:
Synthesizing of a, extraordinary polyethers:
1.1 sodium alkoxide is added in the autoclave pressure, add the stirring of sufficient amount of solvent alcohol again and make it abundant dissolving, add oxirane, high-speed stirred is warming up to 105～110 ℃, the still internal pressure rises to 1.8～2.0atm, reacted 2～4 hours, when pressure is reduced to normal pressure, when temperature is reduced to room temperature, obtain the epoxy radicals polyethers sodium salt of end socket, steam solvent alcohol and but can;
1.2
The epoxy radicals polyethers sodium salt of end socket is added in the reaction bulb, and dichloroethane of Jia Ruing or carrene add hot reflux again, react 2～4 hours, obtain extraordinary polyethers,
The mol ratio of sodium alkoxide, oxirane, dichloroethane or carrene is 1: 6～10: 0.8～1.0; Described 1.1 operations also can be:
Sodium alkoxide is added in the autoclave pressure, add the stirring of sufficient amount of solvent alcohol again and make it abundant dissolving, add expoxy propane, high-speed stirred, be warming up to 100～110 ℃, the still internal pressure rises to 1.7～2.0atm, reacts 2～4 hours, when pressure is reduced to normal pressure, when temperature is reduced to room temperature, add oxirane again, be warming up to 105～110 ℃, the still internal pressure is 1.8～2.0atm, reacted 2～4 hours, when the still internal pressure is reduced to normal pressure, with the still temperature drop to room temperature, obtain the epoxy radicals polyethers sodium salt of end socket, steam solvent alcohol and but can; The mol ratio of described oxirane and expoxy propane is: 60～99.5: 0.5～40;
Described sodium alkoxide is sodium methoxide, caustic alcohol, sodium butoxide is a kind of or several mixture.
Described solvent alcohol is methyl alcohol, ethanol, butanols.
The reaction equation of above-mentioned building-up process is as follows:
Synthesizing of b, organic silicon pesticide synergist
The extraordinary polyethers of a operation and HMDS are added in the reaction bulb, dissolve, stir, at N with the organic solvent of capacity
2Protection down; be warming up to 90～120 ℃; the catalyzer cesium fluoride that adds 10～60ppm; stir fast; reaction system gradually becomes transparent by muddiness, and continuing to add after 2～5 hour time of reaction mass concentration and be 20～50% the sodium bicarbonate solution pH value that neutralizes is 6.5～7.5, filters; get final product, the mol ratio of extraordinary polyethers, HMDS is 1: 1.0～1.2.
Described organic solvent is isopropyl alcohol, chloroform, acetone is a kind of or several mixture.
Reaction equation is as follows:
Owing to the hydrolysis reason and the purity problem of HMDS, therefore, described HMDS preferably is prepared by following method:
The preparation of C, HMDS:
In reactor, add solvent and (CH
3)
3SiCl, and both volume ratios are 1～4: 1; Under agitation feed dry NH
3Temperature is controlled at 10～50 ℃, when escaping gas is alkalescence, stops to feed NH
3, use N instead
2Stop reaction after reacting 0～3h again; The dropping mass concentration is 10～60%NaOH aqueous solution in the downhill reaction liquid fully stirring, make the solid complete obiteration in the solution, move into again and tell supernatant liquor in the separatory funnel, again supernatant liquor is carried out rectifying, collect 126-127 ℃ of product, i.e. HMDS.
Described solvent is n-hexane, normal butane, isopentane, benzene is a kind of or several mixture.
The reaction equation of above-mentioned building-up process is as follows:
2(CH
3)
3SiCl+3NH
3→(CH
3)
3SiNHSi(CH
3)
3+2NH
4Cl↑
NH
4Cl+NaOH→NH
3H
2O+NaCl
The invention has the beneficial effects as follows: this organic silicon pesticide synergist has extremely low surface tension of liquid, be about 20～22mN/m, can be used as super spreading agent, bleeding agent and emulsifying dispersant, in the pH value scope good stability is being arranged widely, nonhazardous, the physiological safety performance is good, is applicable to all kinds of weed killer herbicides, insecticide, bactericide, plant growth regulator, biopesticide and foliage fertilizer, can save pesticide dosage more than 40%, reduce water consumption is more than 1/3rd; And the preparation method of this organic silicon pesticide synergist has the advantage that side reaction is few, yield is high.
Embodiment
Below in conjunction with embodiment the present invention is done detailed explanation, but the present invention should not only limit to these embodiment.
Embodiment 1:
Synthesizing of a, extraordinary polyethers:
1.1
With sodium methoxide and the 162g methyl alcohol of 81g, drop in the stainless steel cauldron of 1L, its sodium methoxide is dissolved fully, add 550g oxirane again, high-speed stirred is warming up to 100 ℃, and autoclave pressure pressure is 1～2.0atm.Along with the carrying out of reaction, pressure descends gradually, when the still internal pressure is 1.2atm, is cooled to normal temperature, obtains the APEO sodium salt with the methoxyl group end-blocking:
1.2 the APEO sodium salt that makes is moved in the normal-pressure reaction kettle, steam methyl alcohol after, in still, add the dichloroethane of 160g, high-speed stirred is warming up to reflux temperature, react 2.5 hours, steams unreacted dichloroethane, decolouring, filtration, must hold the chloro polyethers:
Synthesizing of C, HMDS:
The 1000ml four-hole boiling flask that frozen water condensing unit, stirring, inlet duct and thermometer are housed is placed the frozen water cooler, add 300ml n-hexane and 150ml (CH
3)
3SiCl; Under agitation feed dry NH
3(about 14L); NH
3Flow is 140ml/min, and the time is 90min (is alkaline to escaping gas); Maintain the temperature at during reaction below 30 ℃, stop logical NH
3, use N instead
2Stop reaction after reacting 1h again; After reaction finished, dripping mass concentration in abundant stirring downhill reaction liquid was the 25%NaOH aqueous solution, and making the solid complete obiteration in the solution (is NH
4The Cl complete reaction), moves into again and tell supernatant liquor in the separatory funnel, again supernatant liquor is carried out rectifying and collect (126-127 ℃ of product), i.e. HMDS;
b、
Synthesizing of organic silicon pesticide synergist:
Take by weighing 354g chlorine end capped polyether (a step) and 161g HMDS (c step) and add in the reactor and stir, at N
2Protection down; be warming up to 90 ℃; the cesium fluoride catalyzer that adds 30ppm, solution are muddy, after 3 hours; reactant gradually becomes transparent by muddiness; continue reaction after 4 hours, it is 7.5 that the aqueous solution of the sodium bicarbonate of adding 8.5g, mass concentration 50% is neutralized to pH value, filters; obtain organic silicon pesticide synergist 450g, its surface tension is 21.0mN/m (0.1% the aqueous solution).
Its structural formula is:
Embodiment 2:
Synthesizing of a1, extraordinary polyethers:
1.1 the 27g sodium methoxide is added in the autoclave pressure, add the stirring of 60g methyl alcohol again and make it abundant dissolving, add the 210g expoxy propane, high-speed stirred is warming up to about 105 ℃, and the still internal pressure rises to 1.7atm.Along with the carrying out of reaction, pressure reduces gradually, when pressure is reduced to 1.1～1.2atm, reduces to room temperature, adds oxirane 201g again, is warming up to about 110 ℃, and the still internal pressure is 1.8～2.0atm.When the still internal pressure is reduced to 1.1～1.2atm, with the still temperature drop to room temperature, steam methyl alcohol after, obtain the methanol solution of the epoxy radicals polyethers sodium salt of methoxyl group end-blocking:
1.2 the epoxy radicals polyethers sodium salt (390g) of the methoxyl group end-blocking that makes is moved in the normal-pressure reaction kettle, steam methyl alcohol after, in still, add the dichloroethane of 55g, high-speed stirred, be warming up to reflux temperature, reacted 2.5 hours, steam unreacted dichloroethane, decolouring is filtered, and must hold the chloro polyethers:
Synthesizing of b1, organic silicon pesticide synergist:
Take by weighing 101g chlorine end capped polyether (a1 step) and 32.5g HMDS (c step) and add in the reactor and stir, at N
2Protection down; be warming up to 90 ℃, add the cesium fluoride catalyzer of 30ppm, solution is muddy; after 3 hours; reactant gradually becomes transparent by muddiness, continues reaction after 2 hours, and it is 6.5 that the sodium bicarbonate aqueous solution of adding 4g, mass concentration 30% is neutralized to pH value; filter; obtain organic silicon pesticide synergist 97g, its surface tension is 20.6mN/m (0.1% the aqueous solution), and its structural formula is:
Claims (9)
1. organic silicon pesticide synergist, it is characterized in that: its chemical structural formula is:
Wherein: a=5～50; B=0～25;
R
1Structural formula be: R
1=-CH
3,-H,
R
2Structural formula be: R
2=-H
3,-CH
3-C
4H
9-O (O) CCH
3
2. a kind of organic silicon pesticide synergist according to claim 1 is characterized in that:
Described: a=5～15, b=0～5; R
1Structural formula be :-CH
3R
2Structural formula be :-CH
3,-H.
3. the preparation method of the described organic silicon pesticide synergist of claim 1 comprises the steps:
Synthesizing of a, extraordinary polyethers:
1.1 sodium alkoxide is added in the autoclave pressure, add the stirring of sufficient amount of solvent alcohol again and make it abundant dissolving, add oxirane, high-speed stirred is warming up to 105～110 ℃, the still internal pressure rises to 1.8～2.0atm, reacted 2～4 hours, when pressure is reduced to normal pressure, when temperature is reduced to room temperature, obtain the epoxy radicals polyethers sodium salt of end socket, steam solvent alcohol and but can;
1.2
The epoxy radicals polyethers sodium salt of end socket is added in the reaction bulb, and dichloroethane of Jia Ruing or carrene add hot reflux again, react 2～4 hours, obtain extraordinary polyethers,
The mol ratio of sodium alkoxide, oxirane, dichloroethane or carrene is 1: 6～10: 0.8～1.0;
Synthesizing of b, organic silicon pesticide synergist
The extraordinary polyethers of a operation and HMDS are added in the reaction bulb, dissolve, stir, at N with the organic solvent of capacity
2Protection down; be warming up to 90～120 ℃; the catalyzer cesium fluoride that adds 10～60ppm; stir fast; reaction system gradually becomes transparent by muddiness, and continuing to add after 2～5 hour time of reaction mass concentration and be 20～50% the sodium bicarbonate solution pH value that neutralizes is 6.5～7.5, filters; get final product, the mol ratio of extraordinary polyethers, HMDS is 1: 1.0～1.2.
4. the preparation method of organic silicon pesticide synergist according to claim 3, it is characterized in that: described 1.1 operations are:
Sodium alkoxide is added in the autoclave pressure, add the stirring of sufficient amount of solvent alcohol again and make it abundant dissolving, add expoxy propane, high-speed stirred, be warming up to 100～110 ℃, the still internal pressure rises to 1.7～2.0atm, reacts 2～4 hours, when pressure is reduced to normal pressure, when temperature is reduced to room temperature, add oxirane again, be warming up to 105～110 ℃, the still internal pressure is 1.8～2.0atm, reacted 2～4 hours, when the still internal pressure is reduced to normal pressure, with the still temperature drop to room temperature, obtain the epoxy radicals polyethers sodium salt of end socket, steam solvent alcohol and but can; The mol ratio of described oxirane and expoxy propane is: 60～99.5: 0.5～40.
5. according to the preparation method of claim 3 or 4 described organic silicon pesticide synergists, it is characterized in that: described sodium alkoxide is a kind of of sodium methoxide, caustic alcohol, sodium butoxide etc. or several mixture.
6. according to the preparation method of claim 3 or 4 described organic silicon pesticide synergists, it is characterized in that: described solvent alcohol is methyl alcohol, ethanol, butanols.
7. the preparation method of organic silicon pesticide synergist according to claim 3, it is characterized in that: described organic solvent is isopropyl alcohol, chloroform, acetone is a kind of or several mixture.
8. the preparation method of organic silicon pesticide synergist according to claim 3, it is characterized in that: described HMDS prepares by the following method:
In reactor, add solvent and (CH
3)
3SiCl, and both volume ratios are 1～4: 1; Under agitation feed dry NH
3Temperature is controlled at 10～50 ℃, when escaping gas is alkalescence, stops to feed NH
3, use N instead
2Stop reaction after reacting 0～3h again; The dropping mass concentration is 10～60%NaOH aqueous solution in the downhill reaction liquid fully stirring, make the solid complete obiteration in the solution, move into again and tell supernatant liquor in the separatory funnel, again supernatant liquor is carried out rectifying, collect 126-127 ℃ of product, i.e. HMDS.
9. the preparation method of organic silicon pesticide synergist according to claim 8, it is characterized in that: described solvent is n-hexane, normal butane, isopentane, benzene is a kind of or several mixture.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102919060A (en) * | 2012-11-08 | 2013-02-13 | 云南省农业科学院热带亚热带经济作物研究所 | Novel method for rainproof grafting of mango saplings or seedlings |
| CN109400344A (en) * | 2018-10-29 | 2019-03-01 | 佛山市铁人环保科技有限公司 | A kind of control accurate type blade face barrier and its preparation method and application |
| CN110283316A (en) * | 2018-12-28 | 2019-09-27 | 杭州师范大学 | A kind of preparation method of organosilicon synergist |
| CN111713493A (en) * | 2020-07-23 | 2020-09-29 | 陕西农塔生物数据研究有限公司 | Synergistic insecticidal auxiliary agent |
| US11066430B2 (en) * | 2014-12-04 | 2021-07-20 | Shin-Etsu Chemical Co., Ltd. | Method for producing polyalkylene glycol derivative having amino group at end |
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2009
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| DD255737A1 (en) * | 1986-10-31 | 1988-04-13 | Akad Wissenschaften Ddr | METHOD FOR PRODUCING SILOXYL SALKENDIYL-BIS-OMEGA HYDROXYPOLYOXYALKYLENEES |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102919060A (en) * | 2012-11-08 | 2013-02-13 | 云南省农业科学院热带亚热带经济作物研究所 | Novel method for rainproof grafting of mango saplings or seedlings |
| US11066430B2 (en) * | 2014-12-04 | 2021-07-20 | Shin-Etsu Chemical Co., Ltd. | Method for producing polyalkylene glycol derivative having amino group at end |
| CN109400344A (en) * | 2018-10-29 | 2019-03-01 | 佛山市铁人环保科技有限公司 | A kind of control accurate type blade face barrier and its preparation method and application |
| CN110283316A (en) * | 2018-12-28 | 2019-09-27 | 杭州师范大学 | A kind of preparation method of organosilicon synergist |
| CN110283316B (en) * | 2018-12-28 | 2021-05-18 | 杭州师范大学 | Preparation method of organic silicon synergist |
| CN111713493A (en) * | 2020-07-23 | 2020-09-29 | 陕西农塔生物数据研究有限公司 | Synergistic insecticidal auxiliary agent |
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