CN109699642A - A kind of pesticide micro-capsule and preparation method thereof can easily be accommodated rate of release - Google Patents
A kind of pesticide micro-capsule and preparation method thereof can easily be accommodated rate of release Download PDFInfo
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Abstract
The invention discloses a kind of pesticide micro-capsules that can easily be accommodated rate of release, including capsule-core and capsule material；Capsule material is to pass through the polyurethane that crosslinking curing obtains by isocyanates, polyurethane soft segment and chain extender, and the mass percent that capsule material accounts for pesticide micro-capsule is 2%~40%；Capsule-core includes oil-soluble pesticide and organic solvent；The mass percent that organic solvent accounts for pesticide micro-capsule is 0~45%；Using oil-soluble pesticide as capsule-core in the present invention, the pesticide micro-capsule of stable structure can be complemented each other to form with capsule material during the preparation process；The present invention obtains capsule material by isocyanates, polyurethane soft segment and chain extender curing cross-linking reaction, and reaction rate is easy to control, so as to facilitate the rate of release for adjusting pesticide micro-capsule.
Description
Technical field
The present invention designs pesticide microcapsule technology field, is in particular to design a kind of pesticide that can easily be accommodated rate of release
Microcapsule preparation method.
Background technique
Pesticide micro-capsule, which refers to, to be formed nucleocapsid structure small container using natural or synthesis high molecular material, then will
Pesticide coats the formulations of pesticide therein, effective component rate of release can be controlled with use environment according to the needs of use, to drop
Low toxicity of pesticide, phytotoxicity and environmental pollution, while having, stable effective ingredients low to environment and human body toxicity good and to crop
The advantages that highly-safe.But traditional microcapsules product causes rate of release excessively slow due to capsule material technical parameter mismatch, with
Cause release concentration lower than effective concentration, sprays bad (the especially initial stage medicine of universal drug effect so as to cause crop field is used for
Effect) in addition individual product do not embody drug effect always under the conditions of open environment.The approach to solve the above problems is mainly by softgel shell
Porosity that is thinning or increasing softgel shell, but the research and development period length, the technical difficulty that increase the porosity of softgel shell are big, therefore mesh
The preceding effect that raising rate of release is mainly realized by reducing the thickness of softgel shell.
But shell thickness is reduced at present and still has apparent defect to increase the method for release efficiency.One side capsule
It is poor that thickness of the shell reduction will lead to microcapsules stability, is particularly susceptible crystallization livering during cold storage；Another aspect softgel shell is thick
Degree, which reduces, is easy to cause the micro-capsule in field or operation to rupture too early, and capsule-core substance is caused to release immediately or even part core-clad material
Matter can crystallize in advance, go wrong so as to cause in spraying use.
Polyurethane is a kind of block polymer as made of long-chain-segment raw material and short segment polymerizable raw material, is pesticide microcapsules
In one of most common cyst material, general long chain diol constitutes soft segment, polyisocyanates and chain extender and constitutes hard section.At present
Cyst material in report for pesticide micro capsule passes through diisocyanate mostly and small molecule amine interfacial polymerization forms polyureas
Softgel shell, the degree of cross linking, molecular weight of this softgel shell etc. are easy to the technique such as reaction temperature, reaction time etc. carried out by polymerization reaction
Factor influences, and capsule material polymerization rate is caused to be not easily controlled, and polymerization reaction is too fast to will cause aggregation, polymerization reaction slowly can excessively
Capsule is caused brokenly, the micro-capsule product batches unstable quality being prepared is made；And since obtained micro-capsule product its capsule material is hard
Hard microcellular structure causes rate of release to be difficult to control.Moreover, the delivery mode for having this micro-capsule of document report is that capsule-core is effective
Ingredient spreads or overflows from cyst wall micropore, or causes cyst wall to rupture by environmental pressure, and causing can only or partial size thick by capsule
Change rate of release.Meanwhile the crop field environment of practical medication is complicated and changeable, pesticide micro-capsule controls pesticide as one kind after application
The method of release needs to adjust its rate of release according to plant growth characteristic and use environment, can just play better drug effect, but
It is to hardly result in the rate of release and delivery mode of needs by changing capsule thickness or microcapsule diameter.
Therefore it provides a kind of preparation method for the pesticide micro-capsule that can easily be accommodated rate of release is that those skilled in the art need
It solves the problems, such as.
Summary of the invention
In view of this, preparing pledge the present invention provides a kind of pesticide microcapsule preparation method that can easily be accommodated rate of release
The pesticide microcapsule suspending agent that amount is stablized, rate of release is controllable.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of pesticide micro-capsule can easily be accommodated rate of release, which is characterized in that including capsule-core and capsule material；The capsule material be by
Isocyanates, polyurethane soft segment and chain extender pass through the polyurethane that crosslinking curing obtains, and the capsule material accounts for the pesticide micro-capsule
Mass percent is 2%~40%；The capsule-core includes oil-soluble pesticide and organic solvent；The organic solvent accounts for the pesticide
The mass percent of micro-capsule is 0~45%.
The beneficial effect of above-mentioned optimal technical scheme is: using oil-soluble pesticide as capsule-core in the present invention, in preparation process
In the pesticide micro-capsule of stable structure can be complemented each other to form with capsule material；The present invention passes through isocyanates, polyurethane soft segment and expansion
Chain agent curing cross-linking reaction obtains capsule material, and reaction rate is easy to control, so as to facilitate the rate of release for adjusting pesticide micro-capsule.
Preferably, the isocyanates and the mass ratio of the polyurethane soft segment are 2~5:8~5.
The beneficial effect of above-mentioned optimal technical scheme is: isocyanates and polyurethane soft segment are in mass ratio disclosed by the invention
Under can guarantee that polyurethane is effectively prepared, thus be advantageously implemented facilitate adjust pesticide micro-capsule rate of release effect.
Preferably, the isocyanates includes aliphatic type isocyanates or aromatic type isocyanates.
Preferably, the isocyanates includes methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate
Ester, paraphenylene diisocyanate, dimethyl diphenyl diisocyanate, poly methylene poly phenyl poly isocyanate, isophorone two are different
In cyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate or cyclohexanedimethyleterephthalate diisocyanate
It is one or more.
The beneficial effect of above-mentioned optimal technical scheme is: the isocyanates that the present invention uses can be with polyurethane soft segment and expansion
Chain agent cooperates, and is conducive to adjust cross-linking and curing reaction rate, to be conducive to adjust the structure for the polyurethane being prepared
And performance, and then realize the effect of conveniently regulating and controlling pesticide micro-capsule rate of release.
Preferably, the polyurethane soft segment includes polyether polyol or polyester polyol.
Preferably, the polyether polyol is that ethylene oxide and propylene oxide have rule or a statistic copolymer, described
The structural formula of polyether polyol are as follows:
The integer that the n is 0~100, the integer that the m is 0~100, the sum of the n and m for 1~100 integer.
Preferably, the sum of the n and m for 10~50 integer.
Preferably, the sum of the n and m for 20~40 integer.
Preferably, the polyurethane soft segment includes the 210 (ring of series block polyethers of Jiangsu Zhongshang Chemical Co., Ltd.'s production
Ethylene Oxide polymer molecular weight M1000), block polyether 330 (M3000), block polyether 2802 (glycerol and epoxypropane polymer
) or block polyether 1618A (glycerol and propylene oxide, ethylene oxide block polymers M5000, ethylene oxide segment accounting M3000
6%), the polyurethane soft segment capsule material further includes polyglycol ether Series P EG200, PEG400 or PEG1000 of BASF production；
The polyurethane soft segment capsule material further includes propylene oxide epoxyethane block copolymer Pluronic series agriculture breast 400 or agriculture breast
700。
The beneficial effect of above-mentioned optimal technical scheme is: polyurethane soft segment disclosed by the invention can be with isocyanates and expansion
Chain agent cooperates, and is conducive to adjust cross-linking and curing reaction rate, to be conducive to adjust the structure for the polyurethane being prepared
And performance, and then realize the effect for facilitating and adjusting pesticide micro-capsule rate of release.
Preferably, the structural formula of the polyester polyol are as follows:
The R1For C2~C6Carbon chain compound, the R2For C2H5, the n be 1~100 integer.
Preferably, the polyurethane soft segment capsule material includes adipic acid system polyester-diol.
Preferably, the polyurethane soft segment capsule material includes PEA-1000, PEA-2000, PEA-3000, PBA-580, PBA-
1000, one or more of PBA-2000, PDA-1000, PDA-2000, PHA-1000, PHA-2000 or PHA-3000.
Wherein, PEA-1000, PEA-2000 and PEA-3000 are the polyethylene glycol adipate glycol of Yantai Hua Da chemistry
(PEA) class；PBA-580, PBA-1000, PBA-2000 are polybutylene glyool adipate (PBA) class；PDA-1000,PDA-
2000 be polyadipate diethylene glycol (DEG) esterdiol (PDA) class；PHA-1000, PHA-2000, PHA-3000 are polyadipate hexylene glycol
Esterdiol (PHA) class.
The beneficial effect of above-mentioned optimal technical scheme is: polyurethane soft segment disclosed by the invention can be with isocyanates and expansion
Chain agent cooperates, and is conducive to adjust cross-linking and curing reaction rate, to be conducive to adjust the structure for the polyurethane being prepared
And performance, and then realize the effect for facilitating and adjusting pesticide micro-capsule rate of release.
Preferably, the chain extender includes diamine, the structural formula of the diamine are as follows:
H2N-R-NH2
The R includes C1~C12Carbon chain compound；The R further includes the copolymer of propylene oxide and ethylene oxide, institute
The structural formula for stating the copolymer of propylene oxide and ethylene oxide is
Preferably, the chain extender includes ethylenediamine, hexamethylene diamine, 3, and 3 '-two chloro- 4,4 '-diphenylmethanediamiands
(MOCA), 3,5- dimethythiotoluene diamine (DMTDA), 3,5- diethyl toluene diamine (DETDA), 4,4 '-di-2-ethylhexylphosphine oxide (3-
Chloro- 2,6- diethylaniline) (M-CDEA), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- diethyl) aniline (M-DEA) or 4,4 '-methylene
One of bis- (2,6- diisopropyl) aniline (M-DIPA) are a variety of.
Preferably, the chain extender include Yangzhou morning new material CAM-2070, CAM-2005, CAED-900 or
CAED-600。
The beneficial effect of above-mentioned optimal technical scheme is: chain extender disclosed by the invention can be with isocyanates and polyurethane
Soft segment cooperates, and is conducive to adjust cross-linking and curing reaction rate, to be conducive to adjust the structure for the polyurethane being prepared
And performance, and then realize the effect for facilitating and adjusting pesticide micro-capsule rate of release.
Preferably, it is 2%~25% that the capsule material, which accounts for the mass percent of the pesticide micro-capsule,.
The beneficial effect of above-mentioned optimal technical scheme is: capsule material accounts for the mass percent of pesticide micro-capsule disclosed by the invention
In range, it may be implemented to facilitate the effect for adjusting pesticide micro-capsule rate of release.
Preferably, the oil-soluble pesticide includes chlopyrifos, phoxim, pirimiphos-methyl, lythidathion, cypermethrin, cyanogen
Valerate, Fenpropathrin, gamma cyhalothrin, decis, Biphenthrin, pyraclostrobin, carbosulfan, miaow are fresh
Amine, trefanocide, clomazone or emamectin benzoate are one such or a variety of.
The beneficial effect of above-mentioned optimal technical scheme is: oil-soluble pesticide disclosed by the invention can be with isocyanates and poly-
Urethane soft segment is mutually mixed dissolution, thereby may be ensured that the oil-soluble pesticide package complete by capsule material, stable as capsule-core, thus
Form stable pesticide microcapsule structure.
Preferably, the organic solvent includes one of dimethylbenzene, solvent naphtha, methyl oleate, vegetable oil or mineral oil
Or it is a variety of, the mass percent that the organic solvent accounts for the pesticide micro-capsule is 0~45%.
The beneficial effect of above-mentioned optimal technical scheme is: capsule-core of the present invention further includes organic solvent, and organic solvent is molten with oil
Property pesticide can be mixed uniformly, and can be mutually mixed with isocyanates and polyurethane soft segment, to be conducive to oil-soluble agriculture
Medicine comes into full contact with isocyanates and polyurethane soft segment, and then is conducive to capsule material and wraps up capsule-core wherein, and it is steady that structure is prepared
Fixed pesticide micro-capsule；The organic solvent in capsule-core is conducive to regulate and control the rate of release of pesticide micro-capsule simultaneously.
Preferably, it is 0-30% that the organic solvent, which accounts for the mass percent of the pesticide micro-capsule,.
The beneficial effect of above-mentioned optimal technical scheme is: organic solvent accounts for the mass percent of pesticide micro-capsule of the invention public
It can guarantee that the rate of release of pesticide micro-capsule is reasonable in the range of opening, be conducive to the rate of release for regulating and controlling pesticide micro-capsule.
The present invention also provides a kind of pesticide microcapsule preparation methods that can easily be accommodated rate of release, which is characterized in that specific
Include the following steps:
(1) according to a kind of pesticide micro-capsule that can easily be accommodated rate of release as described above, each raw material for standby is weighed；
(2) isocyanates, polyurethane soft segment and oiliness pestsides synthesis are formed uniformly oily mutually or by isocyanates, polyurethane
Soft segment capsule material and pesticide, which are added in organic solvent, is configured to oily phase；
(3) dispersing agent, defoaming agent are uniformly mixed with water and are configured to water phase；
(4) oil is added into water phase, forms stable O/W type lotion by emulsion process；
(5) chain extender is added into O/W type lotion, pesticide micro-capsule then is prepared by cross-linking and curing reaction.
It preferably, further include that above-mentioned pesticide micro-capsule is passed through dry or is uniformly mixed with to obtain agriculture with auxiliary agent by step (6)
Medicine microcapsules.
Preferably, the oily heat phase being prepared in the step (2) to 40-70 DEG C it is spare.
Preferably, the heated aqueous being prepared in the step (3) to 40-70 DEG C it is spare.
Preferably, the mass percent that dispersing agent accounts for the pesticide microcapsules in the step (3) is 1%-10%, defoams
The mass percent that agent accounts for the pesticide microcapsules is 0%-2%；The dispersing agent includes lignosulfonates, alkyl phenol polyoxy
Vinethene formaldehyde condensation products, polymeric carboxylic salt, the naphthalene sulfonate of modification, alkyl phenol polyoxyethylene ether or EO/PO block polyether
In any one or a few mixture；The defoaming agent is organic silicon defoaming agent or polyether antifoam agent.
Preferably, using intermittent preparation or continous way preparation in the step (4).
Preferably, the continous way preparation method based on micro passage reaction or pipeline reactor is used in the step (4).
Preferably, oil is mutually poured into water phase in the step (4), then stirs 3min under 1000r/min revolving speed and is formed
O/W type lotion；Chain extender is added dropwise under 400r/min stirring condition in the step (5), solid under then continuing under the conditions of 50 DEG C
Change 5h.This section is removed
Preferably, water phase and oil are mutually added separately to micro passage reaction according to 1:1-2 flow velocity in the step (4)
In, obtain uniform O/W lotion；Chain extender is added dropwise into O/W lotion obtained above in the step (5), it is anti-by pipeline
Answer device curing reaction 0.5-100min under the conditions of 40-70 DEG C.
The beneficial effect of above-mentioned optimal technical scheme is: preparation method integrated operation disclosed by the invention is simple, is prepared into
To pesticide micro-capsule can easily be accommodated rate of release；Wherein first by isocyanates, polyurethane soft segment and pesticide melting mixing or addition
It is mixed in organic solvent, it is ensured that isocyanates, polyurethane soft segment and oiliness pesticide uniformly contact, and guarantees to be prepared
Oil property is uniform, stablizes；Dispersing agent, defoaming agent and water are uniformly mixed with water phase, be conducive to it is oily mutually in water phase uniformly,
Stable dispersion；Oil is mutually poured into water phase and forms O/W type lotion, keeps mixed system uniform, stable, is conducive to by crosslinking curing
Reaction obtains pesticide micro-capsule.
The present invention also provides a kind of application of pesticide micro-capsule that can easily be accommodated rate of release as described above, feature exists
In the pesticide micro-capsule is for being processed as microcapsule suspending agent, microcapsule powder or microcapsulated granule.
The beneficial effect of above-mentioned optimal technical scheme is: the pesticide micro-capsule that the present invention is prepared is outstanding applied to micro-capsule is prepared
Floating agent, microcapsule powder or microcapsulated granule, can increase its application form, be easy to be extended and applied.
It can be seen via above technical scheme that compared with prior art, can easily be accommodated and release the present disclosure provides one kind
The pesticide micro-capsule and its preparation method and application for putting rate, has the following beneficial effects:
(1) present invention prepares different rates of release by adjusting the constituent of capsule material, crosslinking method, molecular weight etc.
With the micro-capsule of delivery mode；By adjusting the molecular structure of soft segment in capsule material, release can be prepared according to crop cycle
The different micro-capsule of rate；The micro-capsule of different rates of release can also be mixed in a certain ratio, optimal rate of release is provided, is reached
To best drug effect.
(2) present invention using polyether polyol soft segment as reaction raw materials, can reduce with isocyanates reactivity, make to gather
It closes that reaction is more steady, to be advantageously implemented the molecular weight and structure of polyurethane that regulation is prepared, makes to be prepared
Micro-capsule is more stable, rate of release is easy to control.Also, the ether in the polyurethane soft segment that the present invention uses is easier to rotate, tool
There is better flexibility, the elasticity of capsule material can be increased, so that the micro-capsule of preparation has superior cold thermodynamic stability；Polyethers simultaneously
Facile hydrolysis does not make micro-capsule slow release in water environment, and capsule material rupture discharges rapidly in water-less environment.
(3) for the present invention using polyester polyol soft segment as reaction raw materials, the capsule material intensity being prepared is high compared with polyether-type, and
With stronger lipophilic and thermal stability, it is easier to be adhered on crop wax coat, so as to play better drug effect；Together
When since it is with better thermal stability, such capsule material is not easy too fast release at high temperature, plays slow release effect, reaches permanent
The effect of prevention and treatment.
(4) present invention is obtained the polyurethane capsule material of varying strength, is reached using the soft segment of different molecular weight as reaction raw materials
Different rates of release.Polyester polyol molecule amount such as introducing is bigger, and structural regularity is higher, and capsule material intensity is bigger, rupture speed
Degree is slower, and rate of release is also slower.
(5) present invention is by adjusting soft and hard segments ratio in capsule material, available different elastic wall materials, is guaranteeing that micro-capsule has
While different rates of release, moreover it is possible to ensure that prepared pesticide micro-capsule has prolonged storage stability.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is the rate of release comparison diagram of Examples 1 to 3 provided by the invention；
Fig. 2 attached drawing is the rate of release comparison diagram of embodiment 1,4~6 provided by the invention；
Fig. 3 attached drawing is the rate of release comparison diagram of embodiment 1,7~8 provided by the invention.
In figure:
1, which represents embodiment 1,2, represents embodiment 2,3 and represents embodiment 3,4 and represent embodiment 4,5 and represent embodiment 5,6 generations
Table embodiment 6,7 represents embodiment 7,8 and represents embodiment 8.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a kind of pesticide micro-capsules that can easily be accommodated rate of release, including capsule-core and capsule material；Capsule material
It is that the polyurethane that crosslinking curing obtains is passed through by isocyanates, polyurethane soft segment and chain extender, capsule material accounts for the quality of pesticide micro-capsule
Percentage is 2%~40%；Capsule-core includes oil-soluble pesticide and organic solvent；Organic solvent accounts for the mass percent of pesticide micro-capsule
It is 0~45%.
For further optimisation technique scheme, isocyanates includes aliphatic type isocyanates or aromatic type isocyanic acid
Ester.
For further optimisation technique scheme, isocyanates includes methyl diphenylene diisocyanate, toluene diisocyanate
Acid esters, naphthalene diisocyanate, paraphenylene diisocyanate, dimethyl diphenyl diisocyanate, polymethylene polyphenyl polyisocyanic acid
Ester, isophorone diisocyanate, two methylene of dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate or hexamethylene
One of group diisocyanate is a variety of.
For further optimisation technique scheme, polyurethane soft segment includes polyether polyol or polyester polyol.
For further optimisation technique scheme, polyether polyol is that ethylene oxide and propylene oxide have a rule or random embedding
Section copolymer, the structural formula of polyether polyol are as follows:
The integer that n is 0~100, the integer that m is 0~100, the sum of n and m for 1~100 integer.
For further optimisation technique scheme, the sum of n and m for 10~50 integer.
For further optimisation technique scheme, the sum of n and m for 20~40 integer.
For further optimisation technique scheme, polyurethane soft segment includes the series of Jiangsu Zhongshang Chemical Co., Ltd.'s production
Block polyether 210 (epoxypropane polymer molecular weight M1000), block polyether 330 (M3000), block polyether 2802 (glycerol with
Epoxypropane polymer M3000) or block polyether 1618A (glycerol and propylene oxide, ethylene oxide block polymers M5000, ring
Oxidative ethane segment accounting 6%), polyurethane soft segment capsule material further includes polyglycol ether Series P EG200, PEG400 of BASF production
Or PEG1000；Polyurethane soft segment capsule material further include propylene oxide epoxyethane block copolymer Pluronic series agriculture breast 400 or
Nongru-700.
For further optimisation technique scheme, the structural formula of polyester polyol are as follows:
R1For C2~C6Carbon chain compound, R2For C2H5, n be 1~100 integer.
For further optimisation technique scheme, polyurethane soft segment capsule material includes adipic acid system polyester-diol.
For further optimisation technique scheme, polyurethane soft segment capsule material includes PEA-1000, PEA-2000, PEA-
3000, PBA-580, PBA-1000, PBA-2000, PDA-1000, PDA-2000, PHA-1000, PHA-2000 or PHA-3000
One or more of.
Wherein, PEA-1000, PEA-2000 and PEA-3000 are the polyethylene glycol adipate glycol of Yantai Hua Da chemistry
(PEA) class；PBA-580, PBA-1000, PBA-2000 are polybutylene glyool adipate (PBA) class；PDA-1000,PDA-
2000 be polyadipate diethylene glycol (DEG) esterdiol (PDA) class；PHA-1000, PHA-2000, PHA-3000 are polyadipate hexylene glycol
Esterdiol (PHA) class.
For further optimisation technique scheme, chain extender includes diamine, the structural formula of diamine in step (5) are as follows:
H2N-R-NH2
R includes C1~C12Carbon chain compound；R further includes the copolymer of propylene oxide and ethylene oxide, propylene oxide with
The structural formula of the copolymer of ethylene oxide is
For further optimisation technique scheme, chain extender includes ethylenediamine, hexamethylene diamine, 3, and 3 '-two chloro- 4,4 '-hexichol
Methylmethane diamines (MOCA), 3,5- dimethythiotoluene diamine (DMTDA), 3,5- diethyl toluene diamine (DETDA), 4,4 '-
Di-2-ethylhexylphosphine oxide (the chloro- 2,6- diethylaniline of 3-) (M-CDEA), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- diethyl) aniline (M-DEA) or
One of 4,4 '-di-2-ethylhexylphosphine oxides (2,6- diisopropyl) aniline (M-DIPA) is a variety of.
For further optimisation technique scheme, chain extender include Yangzhou morning new material CAM-2070, CAM-2005,
CAED-900 or CAED-600.
For further optimisation technique scheme, the mass percent that capsule material accounts for pesticide micro-capsule is 2%~25%.
For further optimisation technique scheme, the mass percent that organic solvent accounts for pesticide micro-capsule is 0-30%.
For further optimisation technique scheme, oil-soluble pesticide includes chlopyrifos, phoxim, pirimiphos-methyl, thiazole
Phosphorus, cypermethrin, fenvalerate, Fenpropathrin, gamma cyhalothrin, decis, Biphenthrin, pyraclostrobin, fourth
Carbosulfan, Prochloraz, trefanocide, clomazone or emamectin benzoate are one such or a variety of.
For further optimisation technique scheme, organic solvent include dimethylbenzene, solvent naphtha, methyl oleate, vegetable oil or
One of mineral oil is a variety of, and the mass percent that organic solvent accounts for pesticide micro-capsule is 0~45%.
The present invention also provides a kind of pesticide microcapsule preparation methods that can easily be accommodated rate of release, specifically include following step
It is rapid:
(1) according to a kind of pesticide micro-capsule that can easily be accommodated rate of release as described above, and it is 2~5 according to mass ratio:
8~5 weigh isocyanates and polyurethane soft segment, while weighing chain extender and organic solvent, spare；
(2) isocyanates, polyurethane soft segment and oiliness pestsides synthesis are formed uniformly oily mutually or by isocyanates, polyurethane
Soft segment capsule material and pesticide, which are added in organic solvent, is configured to oily phase, and by oily heat phase to 40-70 DEG C, spare；
(3) dispersing agent, defoaming agent are uniformly mixed with water and are configured to water phase, and by heated aqueous to 40-70 DEG C；Dispersing agent
1%-10%, defoaming agent 0%-2%, dispersing agent include lignosulfonates, APES formaldehyde condensation product, high score
Any one or a few mixing in sub- carboxylate, the naphthalene sulfonate of modification, alkyl phenol polyoxyethylene ether or EO/PO block polyether
Object；Defoaming agent is organic silicon defoaming agent or polyether antifoam agent；
(4) oil is added into water phase, forms stable O/W type lotion by emulsion process；
(5) chain extender is added into O/W type lotion, pesticide micro-capsule then is prepared by cross-linking and curing reaction.
For further optimisation technique scheme, the step (in 4) mutually adds water phase and oil respectively according to 1:1-2 flow velocity
Enter into micro passage reaction, obtains uniform O/W lotion；It is added dropwise and expands into O/W lotion obtained above in the step (5)
Chain agent, then through pipeline reactor under the conditions of 40-70 DEG C, curing reaction 0.5-100min.
For further optimisation technique scheme, oil is mutually poured into water phase in the step (4), then in 1000r/min
3min is stirred under revolving speed forms O/W type lotion；It is dripped under 400r/min speed of agitator into O/W type lotion in the step (5)
Add chain extender, 5h cross-linking and curing reaction is then carried out at 50 DEG C, pesticide micro-capsule is prepared.
Embodiment 1
A kind of preparation method for the 20% trefanocide microcapsule suspending agent can easily be accommodated rate of release, specifically includes following step
It is rapid:
(1) 40g trefanocide, 5g toluene di-isocyanate(TDI), 5g PEA1000 (polyethylene glycol adipate two are weighed respectively
Alcohol, molecular weight 1000), 3g lignin sulfonic acid dipersant, 0.2g organic silicon defoamer, 2g ethylenediamine chain extender and 46.8g water,
It is spare；
(2) oil is mutually prepared: by 40g trefanocide, 5g toluene di-isocyanate(TDI), 5g PEA1000 (polyethylene glycol adipate
Glycol, molecular weight 1000) be uniformly mixed, be heated to 70 DEG C it is spare；
(3) prepared by water phase: 3g lignin sulfonic acid dipersant, 0.2g organic silicon defoamer and 46.8g water are uniformly mixed,
Be heated to 70 DEG C it is spare；
(4) it emulsifies: first water phase being added into cutter, setting cutter revolving speed is 1000r/min, then will be oily mutually slow
It is slow to be added dropwise as in water phase, continued after shearing 3min, obtain uniform O/W lotion.
(5) solidify: uniform O/W lotion obtained above being stirred with 400r/min mixing speed, is then added dropwise
2g ethylenediamine chain extender solidifies 5h, obtains 20% stable trefanocide pesticide micro-capsule under then continuing under the conditions of 70 DEG C.
(6) the Kathon CG preservative of 0.2g xanthan gum thickener, 0.2g are added into mixed system obtained above, obtains steady
20% fixed trefanocide microcapsule suspending agent.
Embodiment 2
5g PEA1000 used in above-described embodiment 1 (polyethylene glycol adipate glycol, molecular weight 1000) is replaced
For 5g PEA2000 (polyethylene glycol adipate glycol, molecular weight 2000), other operating procedures, technical parameter and embodiment 1
It is identical.
Embodiment 3
5g PEA1000 used in above-described embodiment 1 (polyethylene glycol adipate glycol, molecular weight 1000) is replaced
For 5g PEA2000 (polyethylene glycol adipate glycol, molecular weight 2000), other operating procedures, technical parameter and embodiment 1
It is identical.
Embodiment 4
The usage amount of PEA1000 in above-described embodiment 1 (polyethylene glycol adipate glycol, molecular weight 1000) is replaced by 5g
It is changed to 10g, other operating procedures, technical parameter are same as Example 1.
Embodiment 5
The usage amount of PEA1000 in above-described embodiment 1 (polyethylene glycol adipate glycol, molecular weight 1000) is replaced by 5g
It is changed to 20g, other operating procedures, technical parameter are same as Example 1.
Embodiment 6
The usage amount of PEA1000 in above-described embodiment 1 (polyethylene glycol adipate glycol, molecular weight 1000) is replaced by 5g
It is changed to 45g, other operating procedures, technical parameter are same as Example 1.
Embodiment 7
2g ethylenediamine chain extender used in above-described embodiment 1 is replaced with into 2g hexamethylene diamine, other operating procedures, technology ginseng
Number is same as Example 1.
Embodiment 8
2g ethylenediamine chain extender used in above-described embodiment 1 is replaced with into 2g3,5 diethyl toluene diamines (DETDA),
Other operating procedures, technical parameter are same as Example 1.
Embodiment 9
A kind of preparation method for the 30% pyraclostrobin microcapsule suspending agent can easily be accommodated rate of release, specifically includes as follows
Step:
(1) 60g pyraclostrobin, 20g vegetable oil, 2g methyl diphenylene diisocyanate, 2g hexa-methylene are weighed respectively
Diisocyanate, 2g polyoxyethylene polyoxypropylene ether block polymer PDA1000,4g polymeric carboxylic dipersant, 0.5g have
Machine silicon defoaming agent, 95.5g water, 4gMOCA chain extender, it is spare；
(2) oil is mutually prepared: by 60g pyraclostrobin, 20g vegetable oil, 2g methyl diphenylene diisocyanate, six methylene of 2g
Group diisocyanate, 2g polyoxyethylene polyoxypropylene ether block polymer be uniformly mixed, be heated to 40 DEG C it is spare.
(3) prepared by water phase: 4g polymeric carboxylic dipersant, 0.5g organic silicon defoamer and 95.5g water are uniformly mixed,
Be then heated to 50 DEG C it is spare.
(4) it emulsifies: water phase is mutually added separately to pipe reaction according to 15ml/min flow velocity according to 10ml/min flow velocity, oil
In device, uniform O/W lotion is obtained.
(5) solidify: uniform O/W lotion obtained above being stirred with 400r/min mixing speed, is then added dropwise
4gMOCA chain extender then continues to solidify 5h under the conditions of 50 DEG C, obtains 30% stable pyraclostrobin micro-capsule.
(6) the 2g aluminium-magnesium silicate into mixed system obtained above, 0.5g benzoic acid obtain stable microcapsule suspending agent.
Embodiment 10~21
60g pyraclostrobin in embodiment 9 is replaced with into the oil-soluble pesticide in following table 1, other operating procedures, technology
Parameter is identical as embodiment.
Table 1
Embodiment 22
A kind of preparation method for the 70% chlopyrifos microcapsulated granule can easily be accommodated rate of release, specifically comprises the following steps:
(1) weigh respectively 10g poly methylene poly phenyl poly isocyanate, 30g block polyether 210,100g chlopyrifos,
10gEO/PO block polyether, 0.5g polyether antifoam agent, 89.5g water and 4gMOCA, it is spare；
(2) oil is mutually prepared: first 10g poly methylene poly phenyl poly isocyanate is uniformly mixed with 30g block polyether 210,
Then under 50 DEG C, dry nitrogen protective condition, pre-polymerization 5h obtains base polyurethane prepolymer for use as；Then it is added into 100g chlopyrifos,
It is stirred evenly under the conditions of 50 DEG C；
(3) prepared by water phase: 10g dispersing agent, 0.5g defoaming agent and 89.5g water are uniformly mixed, are heated to 50 DEG C, it is spare；
(4) water phase is mutually added with the flow velocity of 10ml/min into microreactor respectively with 5ml/min flow velocity, oil, is obtained
Uniform O/W lotion；
(5) solidify: 4gMOCA chain extender being added dropwise into O/W lotion obtained above, by pipeline reactor in 50 DEG C of items
Solidify 20min under part and obtains 70% stable chlopyrifos micro-capsule.
(6) 7.5g lignosulfonates, 10g starch are added into 70% chlopyrifos micro-capsule obtained above, by spraying
It is dried to obtain 70% stable chlopyrifos microcapsulated granule.
Embodiment 23
A kind of preparation method for the 5% gamma cyhalothrin microcapsule powder can easily be accommodated rate of release, specifically include as
Lower step:
(1) 50g gamma cyhalothrin, 30g solvent naphtha, 2g isophorone diisocyanate, 4g are weighed respectively to benzene two
Isocyanates, 240 polyethers of 2g, 4g dispersing agent, 0.5g defoaming agent, 95.5g water and 4gMOCA chain extender, it is spare；
(2) oil is mutually prepared: by 50g gamma cyhalothrin, 30g solvent naphtha, 2g isophorone diisocyanate, 4g to benzene
Diisocyanate, 240 polyethers of 2g are uniformly mixed, and are heated to 40 DEG C, spare.
(3) prepared by water phase: 4g dispersing agent, 0.5g defoaming agent and 95.5g water are uniformly mixed, are heated to 50 DEG C, it is spare.
(4) it emulsifies: water phase and oil being mutually added according to the flow velocity of 30ml/min into microreactor respectively, obtain uniform
O/W lotion；
(5) solidify: uniform O/W lotion obtained above being stirred with 400r/min mixing speed, is then added dropwise
4gMOCA chain extender then continues to solidify 5h under the conditions of 50 DEG C, obtains 5% stable gamma cyhalothrin micro-capsule；
(6) 1g polyvinyl alcohol thickeners, 0.5g sorbic acid are added into 5% gamma cyhalothrin micro-capsule obtained above
Potassium preservative obtains 5% stable gamma cyhalothrin microcapsule powder.
One, performance comparison is carried out to the 20% trefanocide microcapsule suspending agent that above-described embodiment 1~3 is prepared
1, performance detection is carried out to the 20% trefanocide microcapsule suspending agent that above-described embodiment 1~3 is prepared, it is as a result as follows
Shown in table 1.
2, the rate of release for the 20% trefanocide microcapsule suspending agent that simultaneously, above-described embodiment 1~3 is prepared is examined
It surveys, as a result as shown in Figure 1.
Detection method are as follows: weigh effective component raw medicine and each 1g of sample, mixed respectively with a certain amount of diatomite, mixing is equal
It is added separately to after even in two glass columns (H=50cm, D=4.5cm) equipped with diatomite (H=35cm), adds respectively daily
Add 100ml deionized water into pillar.After 30d, the diatomite of surface layer 5cm height is excavated, remaining part, as unit of 2cm
Soil sample is successively taken out, acetonitrile extraction is used after drying, is filtered, filtrate is taken, surveys effective component mass fraction, draws diatomite depth
Relational graph between leaching.
3, the drug effect for the 20% trefanocide microcapsule suspending agent that above-described embodiment 1~3 is prepared detects, as a result such as
Shown in the following table 2.
Table 1
Table 2
It can obviously be learnt by the above results: introduce the polyethylene glycol adipate glycol of three kinds of different molecular weights as capsule
The polyurethane soft segment material of material, can obtain stable CS product.But as the molecular weight of soft segment increases, capsule material molecular structure rule
Whole property is higher, and capsule material intensity is bigger, and rupture velocity is slower, and rate of release is also slower.Trefanocide is as closing herbicide, release speed
Degree is too slow, can not play in weeds rudiment and effectively prevent effect, cause efficacy testing result poor.
Two, performance comparison is carried out to the 20% trefanocide microcapsule suspending agent that above-described embodiment 1,4~6 is prepared
1, the rate of release for the 20% trefanocide microcapsule suspending agent that above-described embodiment 1,4~6 is prepared detects,
As a result as shown in Figure 2.
Detection method are as follows: weigh effective component raw medicine and each 1g of sample, mixed respectively with a certain amount of diatomite, mixing is equal
It is added separately to after even in two glass columns (H=50cm, D=4.5cm) equipped with diatomite (H=35cm), adds respectively daily
Add 100ml deionized water into pillar.After 30d, the diatomite of surface layer 5cm height is excavated, remaining part, as unit of 2cm
Soil sample is successively taken out, acetonitrile extraction is used after drying, is filtered, filtrate is taken, surveys effective component mass fraction, draws diatomite depth
Relational graph between leaching.
It can obviously be learnt by above-mentioned testing result: Analysis of conclusion: as polyurethane soft segment accounts for the ratio of polyurethane prepolymer
Example increases, and isocyanates reactivity reduces, it is easier to form the big capsule material of the degree of cross linking, rate of release is slack-off.Capsule material is total simultaneously
The increase of amount also makes capsule thickness become larger, and rate of release is slack-off.
Three, performance comparison is carried out to the 20% trefanocide microcapsule suspending agent that above-described embodiment 1,7~8 is prepared
1, the rate of release for the 20% trefanocide microcapsule suspending agent that above-described embodiment 1,7~8 is prepared detects,
As a result as shown in Figure 3.
Detection method are as follows: weigh effective component raw medicine and each 1g of sample, mixed respectively with a certain amount of diatomite, mixing is equal
It is added separately to after even in two glass columns (H=50cm, D=4.5cm) equipped with diatomite (H=35cm), adds respectively daily
Add 100ml deionized water into pillar.After 30d, the diatomite of surface layer 5cm height is excavated, remaining part, as unit of 2cm
Soil sample is successively taken out, acetonitrile extraction is used after drying, is filtered, filtrate is taken, surveys effective component mass fraction, draws diatomite depth
Relational graph between leaching.
Can be learnt by above-mentioned testing result: hexamethylene diamine reactivity is higher than DETDA, and capsule material cross-linking reaction speed is fast, more
The capsule material of densification easy to form, therefore rate of release is slack-off.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of pesticide micro-capsule that can easily be accommodated rate of release, which is characterized in that including capsule-core and capsule material；The capsule material is by different
Cyanate, polyurethane soft segment and chain extender pass through the polyurethane that crosslinking curing obtains, and the capsule material accounts for the matter of the pesticide micro-capsule
Measuring percentage is 2%~40%；The capsule-core includes oil-soluble pesticide and organic solvent；It is micro- that the organic solvent accounts for the pesticide
The mass percent of capsule is 0~45%.
2. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 1, which is characterized in that the isocyanic acid
Ester includes methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate, paraphenylene diisocyanate, dimethyl
Biphenyl diisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate, two isocyanide of dicyclohexyl methyl hydride
One of acid esters, hexamethylene diisocyanate or cyclohexanedimethyleterephthalate diisocyanate are a variety of.
3. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 1, which is characterized in that the polyurethane
Soft segment includes polyether polyol or polyester polyol.
4. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 3, which is characterized in that the polyethers is more
First alcohol is that ethylene oxide and propylene oxide have rule or statistic copolymer, the structural formula of the polyether polyol are as follows:
The integer that the n is 0~100, the integer that the m is 0~100, the sum of the n and m for 1~100 integer.
5. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 3, which is characterized in that the polyester is more
The structural formula of first alcohol are as follows:
The R1For C2~C6Carbon chain compound, the R2For C2H5, the n be 1~100 integer.
6. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 1, which is characterized in that the chain extender
Including diamine, the structural formula of the diamine are as follows:
H2N-R-NH2
The R includes C1~C12Carbon chain compound；The R further includes the copolymer of propylene oxide and ethylene oxide, the ring
The structural formula of the copolymer of Ethylene Oxide and ethylene oxide is
7. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 1, which is characterized in that the oil-soluble
Pesticide includes chlopyrifos, phoxim, pirimiphos-methyl, lythidathion, cypermethrin, fenvalerate, Fenpropathrin, efficient chlorine fluorine cyanogen
Pyrethroids, decis, Biphenthrin, pyraclostrobin, carbosulfan, Prochloraz, trefanocide, clomazone or emamectin benzoate its
One of or it is a variety of.
8. a kind of pesticide micro-capsule that can easily be accommodated rate of release according to claim 1, which is characterized in that described organic molten
Agent includes one of dimethylbenzene, solvent naphtha, methyl oleate, vegetable oil or mineral oil or a variety of.
9. a kind of pesticide microcapsule preparation method that can easily be accommodated rate of release, which is characterized in that specifically comprise the following steps:
(1) a kind of pesticide micro-capsule that can easily be accommodated rate of release described in any one according to claim 1~8, weighs each original
Expect spare；
(2) isocyanates, polyurethane soft segment and oiliness pestsides synthesis are formed uniformly oily mutually or by isocyanates, polyurethane soft segment
Capsule material and pesticide, which are added in organic solvent, is configured to oily phase；
(3) dispersing agent, defoaming agent are uniformly mixed with water and are configured to water phase；
(4) oil is added into water phase, forms stable O/W type lotion by emulsion process；
(5) chain extender is added into O/W type lotion, pesticide micro-capsule then is prepared by cross-linking and curing reaction.
10. a kind of application of pesticide micro-capsule that can easily be accommodated rate of release according to claim 1, which is characterized in that institute
Pesticide micro-capsule is stated for being processed as microcapsule suspending agent, microcapsule powder or microcapsulated granule.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112155011A (en) * | 2020-09-17 | 2021-01-01 | 惠州市银农科技股份有限公司 | Emamectin benzoate microcapsule suspending agent and preparation method thereof |
| CN112189675A (en) * | 2020-08-04 | 2021-01-08 | 北京宇悦生物科技有限公司 | Pesticide nano drug-loading system and preparation method thereof |
| CN112335675A (en) * | 2020-11-20 | 2021-02-09 | 江苏精禾界面科技有限公司 | Pesticide preparation containing fosthiazate and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1059811A (en) * | 1996-08-22 | 1998-03-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Termite controlling agent-containing dispersion |
| CN1355267A (en) * | 2001-12-24 | 2002-06-26 | 王申 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
| CN102993401A (en) * | 2012-12-05 | 2013-03-27 | 中国科学院山西煤炭化学研究所 | Method for synthesizing room-temperature cured polyurethane composite material for coating solid medicine |
| CN105076129A (en) * | 2014-04-22 | 2015-11-25 | 广东华润涂料有限公司 | Insecticide microcapsules and preparation method thereof |
| CN108029686A (en) * | 2017-11-28 | 2018-05-15 | 天津工业大学 | A kind of pirimiphos-methyl microcapsule pesticide and preparation method thereof |
| CN108353897A (en) * | 2018-03-27 | 2018-08-03 | 江苏精禾界面科技有限公司 | A kind of pesticide microcapsule suspending agent and preparation method thereof |
-
2018
- 2018-12-21 CN CN201811573288.6A patent/CN109699642A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1059811A (en) * | 1996-08-22 | 1998-03-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Termite controlling agent-containing dispersion |
| CN1355267A (en) * | 2001-12-24 | 2002-06-26 | 王申 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
| CN102993401A (en) * | 2012-12-05 | 2013-03-27 | 中国科学院山西煤炭化学研究所 | Method for synthesizing room-temperature cured polyurethane composite material for coating solid medicine |
| CN105076129A (en) * | 2014-04-22 | 2015-11-25 | 广东华润涂料有限公司 | Insecticide microcapsules and preparation method thereof |
| CN108029686A (en) * | 2017-11-28 | 2018-05-15 | 天津工业大学 | A kind of pirimiphos-methyl microcapsule pesticide and preparation method thereof |
| CN108353897A (en) * | 2018-03-27 | 2018-08-03 | 江苏精禾界面科技有限公司 | A kind of pesticide microcapsule suspending agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汪多仁: "《绿色医药化学品》", 31 July 2008, 科学技术文献出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112189675A (en) * | 2020-08-04 | 2021-01-08 | 北京宇悦生物科技有限公司 | Pesticide nano drug-loading system and preparation method thereof |
| CN112155011A (en) * | 2020-09-17 | 2021-01-01 | 惠州市银农科技股份有限公司 | Emamectin benzoate microcapsule suspending agent and preparation method thereof |
| CN112335675A (en) * | 2020-11-20 | 2021-02-09 | 江苏精禾界面科技有限公司 | Pesticide preparation containing fosthiazate and preparation method thereof |
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