CN109627361A - Polydactyl acid bio-matrix cyst material and its method for preparing bimolecular structure slow-releasing algae removal microcapsules - Google Patents
Polydactyl acid bio-matrix cyst material and its method for preparing bimolecular structure slow-releasing algae removal microcapsules Download PDFInfo
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
- A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/30—Nitrogen atoms not forming part of a nitro radical
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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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
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Abstract
The present invention relates to algae killing material fields, to solve the low for chemical pesticide improvement Chinese torreya green alga disease utilization rate of current urgent need to resolve, validity period is short, the problems such as polluting environment, a kind of method that the present invention proposes polydactyl acid bio-matrix cyst material and its prepares bimolecular structure slow-releasing algae removal microcapsules, using the new bio base molecular material of synthesis as wall material, the cortex cinnamomi aldehyde radical algae removal compound of synthesis is capsule-core, new sustained release algae removal microcapsules are made using emulsion process, with efficient, low-residual characteristic, the lasting period is acted on for extending algae removal, reduce high poison algicide amount of application, and pesticide efficiently has a very important significance using with environmental protection.
Description
Technical field
The present invention relates to algae killing material fields, and in particular to a kind of polydactyl acid bio-matrix cyst material and its preparation
The method of bimolecular structure slow-releasing algae removal microcapsules.
Background technique
Chinese torreya is Zhejiang Province's characteristic Foresty industry, develops within nearly 10 years the most close industry of self-employed tree cultivator's increase wealth, in economy
There is important strategic status in woods, there is unique effect to Economy of Zhejiang social development.In recent years, Chinese torreya disease outburst frequency by
Year improves, range constantly expands, economic loss is continuously increased, and disease, which has become, restricts the main bottle that Chinese torreya industry develops in a healthy way
Neck, and harm of the Chinese torreya green alga in primiparity woods is the most serious, there is an urgent need to actively develop the great disease prevention and control key skill of Chinese torreya
Art research, the great disease management technical level in General Promotion Chinese torreya producing region provide scientific and technological guarantor for the sustainable development of Chinese torreya industry
Barrier.
Now, Chinese torreya green alga mainly applies lime sulfur to be prevented and treated, lime sulfur bring sulphur is remaining, short-acting burst release,
The problems such as ecological environmental pollution, makes it endure disease dirt to the fullest extent in use.And kill two high-efficient class chemistry algicides of algae: oxidized form kills
Algae agent and flocculation-type algicide are applied limited at present.Oxidized form kills algae product can be close with metabolism in oxidizing microorganisms body
Relevant enzyme leads to microbial metabolism disorder so that death.However halides halogenation water body of this kind of algicide containing band is organic
Object generates carcinogenic substance, threatens human health.Flocculation-type algicide is mostly heavy metallic salt solution, is on the one hand pressed down by metal ion
The growth of the eubolism interference algae of algae processed, on the other hand then settles algae by the flocculation of metal ion and reaches
Except Cutleriales, but bring serious heavy metal pollution.Therefore, there is an urgent need to innovate Chinese torreya green alga disease prevention techniques, mesh is improved
Preceding efficient Chinese torreya green alga algicide forms green novel form, or screening efficiently, low toxicity compounds and the friendly safety of development environment
Novel environmentally-friendly biological base algicide seems very necessary.
Summary of the invention
For solve current urgent need to resolve for chemical pesticide administer Chinese torreya green alga disease utilization rate it is low, validity period is short, dirty
The problems such as contaminating environment, the present invention propose a kind of polydactyl acid bio-matrix cyst material and its prepare bimolecular structure slow-releasing to go out
The method of algae microcapsules has efficient, low-residual characteristic, for extending the algae removal effect lasting period, reducing the application of high poison algicide
Amount and pesticide efficiently have a very important significance using with environmental protection.
The present invention is achieved by the following technical solutions: a kind of polydactyl acid bio-matrix cyst material is by following step
Suddenly it is made:
(a) polylactic acid is weighed, is added in three-necked flask, is put into thermostat water bath, is heated to after adding toluene dissolution
Maleic anhydride and initiator are added after 90~100 DEG C, is reacted in the case where 90~100 DEG C of constant temperature stir, stirring rate is 180~
220r/min is precipitated after reacting 2~3h with methanol, and wash repeatedly with methanol dry after the remaining maleic anhydride of removal after obtain
To modified by maleic acid anhydride graft polylactic acid；
Preferably, the mass ratio of polylactic acid, maleic anhydride is 1: 0.33~10.2.
For toluene as solvent, usage amount is the amount for dissolving solute sufficiently, preferably, the mass ratio of polylactic acid, toluene
It is 1: 5.2~17.2.
Preferably, the mass ratio of polylactic acid and initiator is 80~100: 1, the initiator is 2,5- dimethyl-
2,5- di-t-butyls-peroxy-hexane.
(b) tetrahydrofuran solution containing ethylenediamine is added in the three-neck flask equipped with blender and thermometer, separately will
Modified by maleic acid anhydride graft polylactic acid is dissolved in tetrahydrofuran, is stirred in the lower tetrahydrofuran solution for instilling ethylenediamine, is controlled
Temperature of reaction system≤20 DEG C are added dropwise, and after heat preservation 10~15 minutes, then temperature are risen to 20~30 DEG C of 0.5~1h of reaction,
It after reaction product stirring is dissolved in tetrahydrofuran, then instills in distilled water, collects the film on surface, be washed with distilled water, repetition is washed
It washs until washing lotion PH=7~9；The film of collection is dried into 90~100h at 20~30 DEG C, obtains polydactyl acid biology
Matrix cyst material.
Preferably, the mass ratio of modified by maleic acid anhydride graft polylactic acid and ethylenediamine is 1: 2~2.5.
For tetrahydrofuran as solvent, usage amount is the amount for dissolving solute sufficiently, preferably, ethylenediamine with tetrahydro furan
The volume ratio muttered is 1: 10~1: 12.
Reaction structure formula is as follows:
Using polydactyl acid bio-matrix cyst material prepare bimolecular structure slow-releasing algae removal microcapsules method be with
Lower step:
(1) cortex cinnamomi aldehyde radical algae removal compound is prepared
(1.1) to the preparation of methoxycinnamic aldehyde: using tetrahydrofuran as solvent, P-methoxybenzal-dehyde and acetic acid is added
Vinyl acetate adds barium hydroxide, filters mixture after 30~45 DEG C of 1.5~2.5h of stirring, gone out with organic solvent extraction and separation
Organic layer in filtrate removes organic solvent using Rotary Evaporators and obtains solid, obtains Huang after 30~50 DEG C of dry 10~12h
Color to methoxycinnamic aldehyde；
Preferably, the volume mass ratio of P-methoxybenzal-dehyde, vinyl acetate resin, barium hydroxide be 1mL: 0.5~
1.3mL: 0.15~0.45g.
Preferably, organic solvent is selected from chloroform.
Reaction equation is as follows:
(1.2) preparation of 2- aminobenzimidazole: o-phenylenediamine and hydrochloric acid is (anti-in 85~95 DEG C of addition reaction vessels
Container is answered to be heated with oil bath pan), cyanamide solution is then added dropwise into reaction system with 5~7 drops/min, reacts 0.6~1.2h
After add sodium hydroxide solution, product that reaction obtains is filtered, uses deionized water by the reaction was continued 0.6~1.2h
Obtained solid is washed, obtains hazel 2- aminobenzimidazole after 50~65 DEG C of dry 10.5~13h；
Preferably, the molar ratio of hydrochloric acid and o-phenylenediamine is 1.1~1.3: 1, the molar ratio of cyanamide and o-phenylenediamine
It is 1.1~1.2: 1, the molar ratio of sodium hydroxide and o-phenylenediamine is 1.1~1.3: 1.
The mass fraction of above-mentioned hydrochloric acid is 20%~35%, and the mass fraction of cyanamide solution is 45%~50%, hydrogen-oxygen
Change the mass fraction 30%~50% of sodium solution.
Reaction equation is as follows:
(1.3) prepared by cortex cinnamomi aldehyde radical algae removal compound: (1.1) are obtained obtained to methoxycinnamic aldehyde and (1.2)
2- aminobenzimidazole is dissolved in methanol, and after 55~75 DEG C are stirred to react 0.6~1.2h, mixed solution is carried out ice bath, cold
But to 0~6 DEG C, the solid of yellow is precipitated, the solid being precipitated in solution is filtered, obtains N- after 35~40 DEG C of dry 10~12h
2- (4- methoxy cyclohexyl -2,4- dienylidene) ethylidene) -1-H- benzylimidazole -2- amine, i.e. cortex cinnamomi aldehyde radical algae removal chemical combination
Object；
Preferably, being 1: 1.1~1.2 to the molar ratio of methoxycinnamic aldehyde and 2- aminobenzimidazole；
Preferably, above-mentioned drying means is vacuum drying.
Reaction equation is as follows:
The cortex cinnamomi aldehyde radical algae removal compound of prepared synthesis is decomposed under the conditions of alkaline soil plant cell liquid with algae removal
Two monomeric substance of effect of sterilization, to achieve the effect that expected prevention and treatment Chinese torreya green alga.
(2) preparation of bimolecular structure slow-releasing algae removal microcapsules
Cortex cinnamomi aldehyde radical algicide is added in polydactyl acid bio-matrix cyst material/dichloromethane solution, 20~25
Homogenizer stirs 10~20s at DEG C, forms milky W/O microballoon；200~300rmin-118~20h of magnetic agitation, with evaporation
Fall the organic solvent (methylene chloride) in microballoon, then 10000rmin-1It is centrifuged 10min, precipitates microballoon；If being washed with distillation
Dry time, product is finally collected by centrifugation, is freeze-dried, seals bottle, is saved at 0~8 DEG C, obtain the micro- glue of bimolecular structure slow-releasing algae removal
Capsule, reaction schematic diagram are as shown in Figure 5.
Preferably, the mass ratio of polydactyl acid bio-matrix cyst material, cortex cinnamomi aldehyde radical algicide is 0.7~1.0
∶1。
Methylene chloride plays the role of solvent as organic solvent, and usage amount is the amount for dissolving solute.
The present invention is using polylactic acid as raw material, and gradually graft modification is amphiphilic (EMPLA), prepares new bio base point
Sub- capsule wall material；It is the medicament basis with extensive sterilization algae removal function based on cinnamic acid, 2- aminobenzimidazole, two-step method is closed
At 2- aminobenzimidazole novel intelligent cortex cinnamomi aldehyde radical algae removal compound；Using the new bio base molecular material of synthesis as wall
The cortex cinnamomi aldehyde radical algae removal compound of material, synthesis is capsule-core, and new sustained release algae removal microcapsules are made using emulsion process.New sustained release goes out
The algae microcapsules phase can solve current Chinese torreya green alga algae removal problem, and Chinese torreya industry is promoted to develop in a healthy way, and be the great disease control of Chinese torreya
Further investigation lay the foundation.
Compared with prior art, the beneficial effects of the present invention are: environmental type sustained release algicide Nano capsule combines
Many advantages, such as physical method algae removal, chemical agent algae removal, intellectual material are sustained effect is environmentally friendly algicide and efficient, low residual
The antibacterial pesticides new formulation stayed, it is efficiently sharp for extending algae removal effect lasting period, reduction high poison algicide amount of application and pesticide
It is had a very important significance with environmental protection.
Detailed description of the invention
Fig. 1 is polydactyl acid bio-matrix material hydrogen spectrogram in embodiment 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of cortex cinnamomi aldehyde radical algae removal compound in embodiment 1；
Fig. 3 is the infrared spectrum of polydactyl acid bio-matrix material hydrogen spectrogram in embodiment 1；
Fig. 4 is the infrared spectrum of cortex cinnamomi aldehyde radical algae removal compound in embodiment 1；
Fig. 5 is that bimolecular structure slow-releasing algae removal microcapsules react schematic diagram.
Specific embodiment
Below by attached drawing, the invention will be further described with specific embodiment, and following embodiment is intended to illustrate hair
It is prepared by bright rather than raw materials used commercially available in limitation of the invention further, embodiment or use conventional method.
Embodiment 1: the preparation of biomass-based molecular capsule cyst material
Firstly, weighing 15g polylactic acid, it is added in the three-necked flask with blender, is put after adding the dissolution of 100mL toluene
Enter in thermostat water bath, 5g maleic anhydride and 0.15g initiator (the tertiary fourth of 2,5- dimethyl -2,5- bis- are added after being heated to 95 DEG C
Base-peroxy-hexane), after reacting 2.5h under 95 DEG C of constant temperature stir, precipitated with methanol, and washed and gone repeatedly with methanol
Except drying obtains modified by maleic acid anhydride graft polylactic acid (MPLA) after remaining maleic anhydride.Then blender and thermometer are being housed
Three-neck flask in 5mL be added contain the THF solution of 9g ethylenediamine；4.5g MPLA is dissolved completely in 50mL THF solution,
Stirring is lower to be instilled in three-neck flask, controls 19 DEG C of temperature of reaction system.It is added dropwise, heat preservation ten minutes later, then by temperature rises to
25 DEG C are reacted 30 minutes, after reaction product stirring is dissolved in tetrahydrofuran, then are instilled in excessive distilled water, are collected surface
Film is washed with distilled water, and repeats aforesaid operations until washing lotion pH=8；Sediment is dried in vacuo 96h at 25 DEG C, is changed
Property polylactic acid bio-matrix material, as capsule wall material.
Preparation example 1: the preparation of Microencapsulated Slow algicide
(1) preparation of cortex cinnamomi aldehyde radical algae removal compound
(1.1) to the preparation of methoxycinnamic aldehyde: using 50mL tetrahydrofuran as solvent, 1mL is added to methoxybenzene first
Aldehyde and 0.5mL vinyl acetate, add 0.2g barium hydroxide, mixture are filtered after 40 DEG C of stirring 2.0h, with organic solvent chlorine
Imitative extraction and separation go out the organic layer in filtrate, remove organic solvent using Rotary Evaporators and obtain solid, after 40 DEG C of dry 10h
To yellow to methoxycinnamic aldehyde.
(1.2) preparation of 2- aminobenzimidazole: by 1moL o-phenylenediamine and 1.2moL, 20% hydrochloric acid of mass concentration is 90
In DEG C addition reaction vessel (reaction vessel is heated with oil bath pan), 1.1 moL, mass concentration 45% are then added dropwise with 7 drops/min
Cyanamide solution adds 1.1moL after reacting 0.7h, 30% sodium hydroxide solution of mass concentration continues anti-into reaction system
0.7h is answered, the product that reaction obtains is filtered, makes that obtained solid is washed with deionized, after 60 DEG C of vacuum drying 12h
To hazel 2- aminobenzimidazole.
(1.3) prepared by cortex cinnamomi aldehyde radical algae removal compound: by 1moL obtained above to methoxycinnamic aldehyde and 1.1 moL2-
Aminobenzimidazole is dissolved in methanol, and after 65 DEG C are stirred to react 0.8h, mixed solution is carried out ice bath, is cooled to 0 DEG C, is precipitated
The solid of yellow filters the solid being precipitated in solution, obtains cortex cinnamomi aldehyde radical algae removal compound (N-2- after 38 DEG C of dry 10h
(4- methoxy cyclohexyl -2,4- dienylidene) ethylidene) -1-H- benzylimidazole -2- amine).
(2) preparation of Microencapsulated Slow algicide
Polydactyl acid bio-matrix cyst material (0.8g)/methylene chloride (8mL) is added in 1g cortex cinnamomi aldehyde radical algicide
In solution, homogenizer stirs 20s at 25 DEG C, forms milky W/O microballoon；300r·min-1Magnetic agitation 20h, it is micro- to evaporate
Methylene chloride in ball, then 10000rmin-1It is centrifuged 10min, precipitates microballoon；With distillation washing 3 times, finally it is collected by centrifugation
Product, freeze-drying seal bottle, save at 8 DEG C, obtain bimolecular structure slow-releasing algae removal microcapsules.
Embodiment 2: the preparation of biomass-based molecular capsule cyst material
Firstly, weighing 20g polylactic acid, it is added in the three-necked flask with blender, is put after adding the dissolution of 120mL toluene
Enter in thermostat water bath, 8g maleic anhydride and 0.2g initiator (the tertiary fourth of 2,5- dimethyl -2,5- bis- are added after being heated to 100 DEG C
Base-peroxy-hexane), it is precipitated after 2h is reacted under 100 DEG C of stirrings with methanol, and wash removal residue repeatedly with methanol
It is dried after maleic anhydride, obtains modified by maleic acid anhydride graft polylactic acid (MPLA).Then in three equipped with blender and thermometer
The 5mL THF solution containing 10g ethylenediamine is added in neck flask；4g MPLA is dissolved completely in 70mL THF solution, is stirred
In lower instillation three-neck flask, 18 DEG C of temperature of reaction system are controlled.It is added dropwise, after heat preservation 15 minutes, then temperature is warmed to room temperature
(20 DEG C) are reacted 60 minutes, after reaction product stirring is dissolved in tetrahydrofuran, then are instilled in excessive distilled water, collect surface
Film is washed with distilled water, and repeats aforesaid operations until washing lotion is in neutrality pH=7；By sediment, (20 DEG C) vacuum is dry at room temperature
Dry 96h obtains polydactyl acid bio-matrix material, as capsule wall material.
Preparation example 2: the preparation of Microencapsulated Slow algicide
(1) preparation of cortex cinnamomi aldehyde radical algae removal compound
(1.1) to the preparation of methoxycinnamic aldehyde: using 50mL tetrahydrofuran as solvent, 1mL is added to methoxybenzene first
Aldehyde and 1mL vinyl acetate, add 0.3g barium hydroxide, filter mixture after 45 DEG C of stirring 1.5h, use organic solvents, chloroform
Extraction and separation go out the organic layer in filtrate, remove organic solvent using Rotary Evaporators and obtain solid, obtain after 50 DEG C of dry 12h
Yellow to methoxycinnamic aldehyde.
(1.2) preparation of 2- aminobenzimidazole: by 1moL o-phenylenediamine and 1.1moL, mass concentration is that 25% hydrochloric acid exists
In 90 DEG C of addition reaction vessels (reaction vessel is heated with oil bath pan), 1.2moL is then added dropwise with 6 drops/min, mass concentration is
50% cyanamide solution adds 1.2moL after reacting 0.7h into reaction system, and mass concentration is 40% sodium hydroxide solution,
The reaction was continued 0.7h filters product that reaction obtains, makes to be washed with deionized obtained solid, after 65 DEG C of dry 11h
Obtain hazel 2- aminobenzimidazole.
(1.3) prepared by cortex cinnamomi aldehyde radical algae removal compound: by 1moL obtained above to methoxycinnamic aldehyde and 1.2 moL
2- aminobenzimidazole is dissolved in methanol, and after 70 DEG C are stirred to react 1h, mixed solution is carried out ice bath, is cooled to 3 DEG C, is precipitated
The solid of yellow filters the solid being precipitated in solution, obtains cortex cinnamomi aldehyde radical algae removal compound (N-2- (4- after 35 DEG C of dry 12h
Methoxy cyclohexyl -2,4- dienylidene) ethylidene) -1-H- benzylimidazole -2- amine).
(2) preparation of Microencapsulated Slow algicide
Polydactyl acid bio-matrix cyst material (1g)/methylene chloride (10mL) is added in 1g cortex cinnamomi aldehyde radical algicide
In solution, homogenizer stirs 20s at 20 DEG C, forms milky W/O microballoon；300r·min-1Magnetic agitation 18h, it is micro- to evaporate
Methylene chloride in ball, then 10000rmin-1It is centrifuged 10min, precipitates microballoon；With distillation washing 4 times, finally it is collected by centrifugation
Product, freeze-drying seal bottle, save at 0 DEG C, obtain bimolecular structure slow-releasing algae removal microcapsules.
Embodiment 3: the preparation of biomass-based molecular material
Firstly, weighing 15g polylactic acid, it is added in the three-necked flask with blender, is put after adding the dissolution of 90mL toluene
Enter in thermostat water bath, 5g maleic anhydride and 0.17g initiator (the tertiary fourth of 2,5- dimethyl -2,5- bis- are added after being heated to 90 DEG C
Base-peroxy-hexane), 3h is reacted under 90 DEG C of constant temperature stirrings.Solution after the reaction was completed is precipitated with methanol, and uses first
Alcohol is dried after washing the remaining maleic anhydride of removal repeatedly, obtains modified by maleic acid anhydride graft polylactic acid (MPLA).Then it is being equipped with
The 5mLTHF solution of the ethylenediamine containing 9g is added in the three-neck flask of blender and thermometer；3.75g MPLA is dissolved completely in
In 60mLTHF solution, stirs in lower instillation three-neck flask, control 17 DEG C of temperature of reaction system.It is added dropwise, keeps the temperature 15 minutes
Afterwards, then temperature (23 DEG C) are warmed to room temperature to react 30 minutes.After reaction product stirring is dissolved in tetrahydrofuran, then instill excessive
In distilled water, the film on surface is collected, is washed with distilled water.Aforesaid operations are repeated until washing lotion is in alkalescent pH=9；By sediment
It is dried in vacuo 100h under room temperature (23 DEG C), polydactyl acid bio-matrix material is obtained, as capsule wall material.
Preparation example 3: the preparation of Microencapsulated Slow algicide
(1) preparation of cortex cinnamomi aldehyde radical algae removal compound
(1.1) to the preparation of methoxycinnamic aldehyde: using 50mL tetrahydrofuran as solvent, 1mL is added to methoxybenzene first
Aldehyde and 0.8mL vinyl acetate, add 0.35g barium hydroxide, mixture are filtered after 30 DEG C of stirring 2.0h, with organic solvent chlorine
Imitative extraction and separation go out the organic layer in filtrate, remove organic solvent using Rotary Evaporators and obtain solid, after 30 DEG C of dry 11h
To yellow to methoxycinnamic aldehyde.
(1.2) preparation of 2- aminobenzimidazole: by 1moL o-phenylenediamine and 1.3moL, mass concentration is that 30% hydrochloric acid exists
In 95 DEG C of addition reaction vessels (reaction vessel is heated with oil bath pan), 1.2moL is then added dropwise with 5 drops/min, mass concentration is
45% cyanamide solution adds 1.3moL after reacting 1.2h into reaction system, and mass concentration is 35% sodium hydroxide solution,
The reaction was continued 1.2h filters product that reaction obtains, makes to be washed with deionized obtained solid, after 50 DEG C of dry 13h
Obtain hazel 2- aminobenzimidazole.
(1.3) prepared by cortex cinnamomi aldehyde radical algae removal compound: by 1moL obtained above to methoxycinnamic aldehyde and 1.2 moL
2- aminobenzimidazole is dissolved in methanol, and after 75 DEG C are stirred to react 1.2h, mixed solution is carried out ice bath, is cooled to 6 DEG C, analysis
The solid of yellow out filters the solid being precipitated in solution, obtains cortex cinnamomi aldehyde radical algae removal compound (N-2- after 40 DEG C of dry 11h
(4- methoxy cyclohexyl -2,4- dienylidene) ethylidene) -1-H- benzylimidazole -2- amine).
(2) preparation of Microencapsulated Slow algicide
Polydactyl acid bio-matrix cyst material (0.9g)/methylene chloride (9mL) is added in 1g cortex cinnamomi aldehyde radical algicide
In solution, homogenizer stirs 15s at 25 DEG C, forms milky W/O microballoon；250r·min-1Magnetic agitation 20h, it is micro- to evaporate
Methylene chloride in ball, then 10000rmin-1It is centrifuged 10min, precipitates microballoon；Several times with distillation washing, finally centrifugation is received
Collect product, freeze-drying seals bottle, saves at 5 DEG C, obtain bimolecular structure slow-releasing algae removal microcapsules.
Test case 1
Compound obtained is tested using nuclear magnetic resonance chemical analyser.It takes minority specioz to be added in nuclear magnetic tube, adds
Enter deuterated chloroform dissolved samples, nuclear magnetic resonance spectroscopy test is carried out to sample.Polydactyl acid bio-matrix cyst wall in embodiment 1
The nucleus magnetic hydrogen spectrum figure of material is as shown in Figure 1, the nucleus magnetic hydrogen spectrum figure of cortex cinnamomi aldehyde radical algae removal compound is as shown in Figure 2 in embodiment 1.
Compound obtained is tested using infrared spectrometer.It takes minority specioz powder and potassium bromide to mix, grinds
Its infrared spectroscopy is surveyed in mill, tabletting within the scope of 0~4000cm-1.Polydactyl acid bio-matrix cyst material in embodiment 1
Infrared spectrum is as shown in figure 3, the infrared spectrum of cortex cinnamomi aldehyde radical algae removal compound is as shown in Figure 4 in embodiment 1.
Test case 2
Using growth rate method measurement Chinese torreya green alga to the sensibility of medicament.Selection is frequently grown in the green alga on Chinese torreya,
The culture medium for being suitble to chlorella growth is added in culture dish, and the sustained release algae removal microcapsules of preparation example preparation are added, identical and fit
It is cultivated under conditions of preferably, observes growing state of the green alga in culture dish, Microencapsulated Slow algicide concentration is contained according to gained
Rate (EE) calculates, and inhibiting rate calculation method is as follows:
Preparation example 1, the preparation example 2 calculated according to above formula be sustained the inhibiting rate of algae removal microcapsules be respectively 85.7%,
84.2%, illustrate that Nano capsule has preferable virulence to Chinese torreya green alga disease.
Test case 3
Practical prevention and treatment Preliminary Results: field trial is carried out in Zhejiang Province Chinese torreya main producing region.Take Chinese torreya tree vigo(u)r, soil types,
It is testing site that growth system, which has the plot of typicalness, if sustained release algae removal microcapsules prepared by 3 processing, respectively preparation example 3
(K1 group), 98% cortex cinnamomi aldehyde radical algae removal compound (B1 group), clear water blank control (CK group).Each processing cell random alignment, often
Processing cell is 3 plants of Chinese torreya trees, and 3 repetitions around set protection row.Chinese torreya green alga handles initial stage application, is sprayed using sufferer leaf
Mist is administered method, and (quality of liquid medicine concentration is 12.05mgL-1).Investigation method: the initial state of an illness of application same day investigation, the 4th, 7 day later
The state of an illness, record leaf green alga covering number and rank are investigated, disease index and control efficiency are calculated using following formula.Test effect is shown in
Table 1.
Field efficacy of the different algicides of table 1 to hickory nut dry rot
In field efficiency test, sustained release algae removal microcapsules show certain preventive effect to the improvement of Chinese torreya green alga, have
Long control effect mainly has the effect of algae removal due to the cortex cinnamomi aldehyde radical algae removal compound of algae removal capsule slow release to green alga
Fruit, simultaneously because the drug slow release in microcapsules, can increase the lasting effect of drug.
Claims (10)
1. a kind of polydactyl acid bio-matrix cyst material, which is characterized in that the polydactyl acid bio-matrix cyst wall material
Material is made of following steps:
(a) it is put into thermostat water bath after toluene dissolution being added in polylactic acid, maleic acid is added after being heated to 90~100 DEG C
Acid anhydride and initiator are reacted in the case where 90~100 DEG C of constant temperature stir；It is precipitated after 2~3h of reaction with methanol, and if being washed with methanol
Modified by maleic acid anhydride graft polylactic acid is obtained after drying after dry time；
(b) tetrahydrofuran solution containing ethylenediamine is added in a reservoir, modified by maleic acid anhydride graft polylactic acid is separately taken to be dissolved in
In tetrahydrofuran, to stir in the lower tetrahydrofuran solution for instilling ethylenediamine, control temperature of reaction system≤20 DEG C are added dropwise,
After heat preservation 10~15 minutes, then temperature risen into 20~30 DEG C of 0.5~1h of reaction, reaction product is dissolved in tetrahydrofuran solution
In, then instill in distilled water, the film on surface is collected, is washed with distilled water, is washed repeatedly until washing lotion PH=7~9；It will receive
The film of collection dry 90~100h at 20~30 DEG C, obtains polydactyl acid bio-matrix cyst material.
2. a kind of polydactyl acid bio-matrix cyst material according to claim 1, which is characterized in that in step (a)
Polylactic acid, maleic anhydride mass ratio be 1:0.33~10.2.
3. a kind of polydactyl acid bio-matrix cyst material according to claim 1, which is characterized in that in step (a)
The mass ratio of polylactic acid and initiator is 80~100:1, and the initiator is 2,5- dimethyl -2,5- di-t-butyl-peroxide
Base-hexane.
4. a kind of raw polydactyl acid bio-matrix cyst material according to claim 1, which is characterized in that step (b)
The mass ratio of middle modified by maleic acid anhydride graft polylactic acid and ethylenediamine is 1:2~2.5.
5. a kind of prepare bimolecular structure slow-releasing algae removal using polydactyl acid bio-matrix cyst material described in claim 1
The method of microcapsules, which is characterized in that the preparation method is following steps:
(1) cortex cinnamomi aldehyde radical algicide is prepared
(1.1) to the preparation of methoxycinnamic aldehyde: using tetrahydrofuran as solvent, P-methoxybenzal-dehyde and vinyl acetate is added
Ester adds barium hydroxide, filters mixture after 30 ~ 45 DEG C of 1.5 ~ 2.5 h of stirring, gone out in filtrate with organic solvent extraction and separation
Organic layer, remove organic solvent obtain solid, obtain after 30 ~ 50 DEG C of 10 ~ 12 h of drying to methoxycinnamic aldehyde；
(1.2) preparation of 2- aminobenzimidazole: by o-phenylenediamine and hydrochloric acid in 85 ~ 95 DEG C of addition reaction vessels, then with 5
Cyanamide solution is added dropwise into reaction system in ~ 7 drops/min, adds sodium hydroxide solution after reacting 0.6 ~ 1.2 h, the reaction was continued
0.6 ~ 1.2 h filters the obtained product of reaction, makes to be washed with deionized obtained solid, and 50 ~ 65 DEG C of dryings 10.5 ~
2- aminobenzimidazole is obtained after 13h；
(1.3) prepared by cortex cinnamomi aldehyde radical algicide: (1.1) are obtained to 2- aminobenzene made from methoxycinnamic aldehyde and (1.2)
And imidazoles is dissolved in methanol, after 55 ~ 75 DEG C are stirred to react 0.6 ~ 1.2h, mixed solution is carried out ice bath, is cooled to 0 ~ 6 DEG C,
Solid is precipitated, the solid being precipitated in solution is filtered, obtain after 35 ~ 40 DEG C of dry 10 ~ 12h N-2- (4- methoxy cyclohexyl -2,
4- dienylidene) ethylidene) -1-H- benzylimidazole -2- amine, i.e. cortex cinnamomi aldehyde radical algicide；
(2) preparation of bimolecular structure slow-releasing algae removal microcapsules
Cortex cinnamomi aldehyde radical algicide is added in the dichloromethane solution of polydactyl acid bio-matrix cyst material, at 20 ~ 25 DEG C
Stir 10 ~ 20 s, 200~300 rmin- 118 ~ 20 h are stirred, then 10000 rmin- 110 min are centrifuged, are precipitated micro-
Ball；Several times with distillation washing, product is finally collected by centrifugation, is freeze-dried, seal bottle, saved at 0 ~ 8 DEG C, obtain bimolecular structure
It is sustained algae removal microcapsules.
6. a kind of utilization polydactyl acid bio-matrix cyst material according to claim 5 prepares bimolecular structure slow-releasing
Algae removal microcapsule method, which is characterized in that the volume of P-methoxybenzal-dehyde, vinyl acetate, barium hydroxide in step (1.1)
Mass ratio is 1mL:0.5 ~ 1.3mL:0.15 ~ 0.45g.
7. a kind of utilization polydactyl acid bio-matrix cyst material according to claim 5 prepares bimolecular structure slow-releasing
Algae removal microcapsule method, which is characterized in that the molar ratio of hydrochloric acid and o-phenylenediamine is 1.1 ~ 1.3:1, cyanamide in step (1.2)
It is 1.1 ~ 1.2:1 with the molar ratio of o-phenylenediamine, the molar ratio of sodium hydroxide and o-phenylenediamine is 1.1 ~ 1.3:1.
8. a kind of according to claim 5 or 6 or 7 prepare bimolecular knot using polydactyl acid bio-matrix cyst material
Structure is sustained algae removal microcapsule method, which is characterized in that the mass concentration of hydrochloric acid is 20% ~ 35%, the mass concentration of cyanamide solution
It is 45% ~ 50%, the mass concentration 30% ~ 50% of sodium hydroxide solution.
9. a kind of utilization polydactyl acid bio-matrix cyst material according to claim 5 prepares bimolecular structure slow-releasing
Algae removal microcapsule method, which is characterized in that step (1.3) is 1 to the molar ratio of methoxycinnamic aldehyde and 2- aminobenzimidazole:
1.1~1.2。
10. it is slow that a kind of utilization polydactyl acid bio-matrix cyst material according to claim 5 prepares bimolecular structure
Release algae removal microcapsule method, which is characterized in that polydactyl acid bio-matrix material in step (2), cortex cinnamomi aldehyde radical algicide
Mass ratio is 0.7 ~ 1.0:1.
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| WO2002062856A2 (en) * | 2001-02-03 | 2002-08-15 | Clariant Gmbh | Microencapsulated biologically active substances that contain a water-soluble or water-dispersible comb polymer |
| CN1435438A (en) * | 2002-09-24 | 2003-08-13 | 重庆大学 | Diamine modified poly-latic acid, method for preparing same and use thereof |
| CN105557741A (en) * | 2016-03-04 | 2016-05-11 | 扬州大学 | Beta-cypermethrin microcapsule and preparation method thereof |
| CN108383797A (en) * | 2018-03-09 | 2018-08-10 | 浙江农林大学 | A kind of corrosion preventive compound and the preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002062856A2 (en) * | 2001-02-03 | 2002-08-15 | Clariant Gmbh | Microencapsulated biologically active substances that contain a water-soluble or water-dispersible comb polymer |
| CN1435438A (en) * | 2002-09-24 | 2003-08-13 | 重庆大学 | Diamine modified poly-latic acid, method for preparing same and use thereof |
| CN105557741A (en) * | 2016-03-04 | 2016-05-11 | 扬州大学 | Beta-cypermethrin microcapsule and preparation method thereof |
| CN108383797A (en) * | 2018-03-09 | 2018-08-10 | 浙江农林大学 | A kind of corrosion preventive compound and the preparation method and application thereof |
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| CN112120021A (en) * | 2020-09-30 | 2020-12-25 | 浙江农林大学 | Compound type slow-release algae removal microcapsule and preparation method thereof |
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