CN109054846A - A kind of preparation method of the soil conditioner based on LBL self-assembly microballoon - Google Patents
A kind of preparation method of the soil conditioner based on LBL self-assembly microballoon Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- 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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Abstract
The present invention relates to a kind of preparation methods of soil conditioner based on LBL self-assembly microballoon, the preparation, the preparation of potassium alginate/chitosan/N-isopropylacrylamide microballoon including spherical calcium carbonate particle, the preparation of the microballoon containing soil conditioner.Compared with prior art, the present invention discharges intracapsular substance, plays the role of sustained release, adapt to the growth cycle of crop using the material of substance and wall material in template to the pH value sensitivity of soil.Soil porosity, chesson are improved simultaneously, and crosslinking agent is added without additional.
Description
Technical field
The present invention relates to a kind of preparation method of soil conditioner, more particularly, to a kind of based on LBL self-assembly microballoon
The preparation method of soil conditioner.
Background technique
Soil conditioner be by agricultural water-loss reducer and rich in organic matter, humic acid natural peat or other organic matters based on
Raw material is wanted, being aided with bioactive ingredients and nutrient composition, the product being process through scientific technology has highly significant
" water conservation, is breathed freely at getting fat " three big soil conditioning performances.
Microballoon be intracapsular space and its exterior space are kept apart by film forming matter to be formed there is particular geometric shape
The substance of shape, shape is based on spherical shape and various irregular shapes.The inside of microballoon can be filling, be also possible to
Hollow.The cyst wall of microballoon is usually made of natural or synthetic high molecular material or inorganic material, and the thickness of cyst wall generally exists
Between several nanometers to several microns.The cyst wall of microballoon is isolated by the intracapsular external space, if substance to be wrapped in intracapsular, the object of substance itself
Physicochemical, biology performance are then unaffected, while being played a protective role again to the substance wrapped up, by its with the external world every
From.The barrier and osmotic adjustment performance that cyst wall has, can reduce or regulate and control the rate of release of embedding substance, to play sustained release
With the effect of control release.It is widely used in the multiple fields such as chemical industry, biological medicine, food, cosmetics, for soil conditioner
The research in direction is seldom, nearest micro-sphere material multiselect alginate and chitosan these natural polymers, without secondary after decomposition
Pollution generates, and its monosaccharide after natural degradation can be used as carbon source and directly be absorbed, and show good non-toxic degradable, life
Object compatibility is environmentally friendly material.Improvement as soil physico-chemical property has unique advantage.
Chinese patent CN106588445A discloses the dedicated seaweed microbial soil conditioner in salt-soda soil.But the patent
Only laying particular emphasis on using various there is nutritional ingredient to mix composition soil conditioner, and adjustment mechanism is single.Chinese patent CN
107652977A is prepared using oil-phase separating method, and invention reaches load conditioning ingredients and slow release using core-shell structure, and has
There are temperature sensitive, wet sensitive and pH sensitivity etc. intelligent, is conducive to the conditioning effect for further promoting conditioner and conditioning efficiency.But the mistake
Journey is at high cost, need to consume a large amount of flocculating agents, easily contain a large amount of chemical substance in product, and laminated assembling technology is mutually tied with template
Conjunction prepare microballoon can form, size, cyst wall composition, wall thickness, structure, transparent performance and function of surface to capsule adjust
Control.This method has many advantages, such as that from a wealth of sources, operating method is simple, low in cost, and the preparation and application to microballoon are a huge
Big breakthrough.But crosslinking agent such as glutaraldehyde or Geniposide are used in LBL self-assembly, using for they is limited as soil more
The nontoxic or cheap requirement of earth conditioner.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind based on layer by layer from group
Fill the preparation method of the soil conditioner of microballoon.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the soil conditioner based on LBL self-assembly microballoon, using following steps:
(1) carboxymethyl cellulose of 0.05~0.1wt% is added in calcium chloride water, after 20~80 DEG C of stirrings that heat up
Aqueous sodium carbonate is added to continue to stir 1h, is then freeze-dried, carbonic acid calcisphere is prepared；
(2) alginate, chitosan are dissolved in respectively in the aqueous solution containing acetic acid, specifically, really weigh 25~
50mg chitosan is dissolved into a certain amount of 0.3~0.6M sodium chloride solution, and is added after calculating according to volume ratio (0.1%)
25ul glacial acetic acid and shelve overnight.Taking change sodium solution to adjust pH value with 1.0M hydrogen is 4.1~5.10, for use；Potassium alginate solution:
25~50mg sodium alginate is weighed to be dissolved in 0.1M sodium chloride solution and shelve overnight.Adjusting pH value with 0.1M citric acid solution is
4.1~5.10.It is that cyst material assembles to obtain 8 layers by core material, chitosan and potassium alginate of the calcium carbonate microparticle of above-mentioned preparation
Microballoon；
(3) calcium carbonate microspheres are added into chitosan solution at room temperature, are warming up to 20~70 DEG C, stir 1~2h, keep
Alginate solution is added after centrifugation in 2~4h, is dried to obtain alginate/chitosan compound microsphere, specifically, first layer
Assembling: CaCO3It is suspended in the NaCl aqueous solution of 10~50ml 0.3M, it is ultrasonic under 80~100W power, 10~50ml shell is added
Glycan solution, machine stir 10~15min, and 10~50ml 0.05MNaCl aqueous solution is added after centrifugation, shake 5~10 minutes, from
It the heart 5~10 minutes, washs 3 times.Second layer assembling: the NaCl aqueous solution of 10~50ml 0.05M is added in particle obtained as above
Suspension is made, under 80~100W power after ultrasound, 10~50ml potassium alginate solution is added, 10~15min is stirred, after centrifugation
Addition 10~50ml centrifugal treating, 3 0.05~0.1M NaCl aqueous solutions of repeated washing, 10~15min of stirring, centrifugal treating,
Repeated washing repeats aforesaid operations until being assembled into 8 layers, and outermost layer is potassium alginate.2~4%CaCl is added2Solution solidification, 1
~2h.Then it is air-dried at room temperature, obtains potassium alginate/chitosan microball.
(4) n-isopropyl acrylamide is added in alginate/chitosan compound microsphere, at 20~30 DEG C, with 800
The revolving speed of~1200rpm stirs 10~30min, obtains alginate/chitosan/polyisopropyl acrylamide complex microsphere；
(5) soil conditioning material is dissolved in solvent, the coupling of 1~10wt% calcium chloride is added, then by soil conditioning material
Material solution and sodium ethylene diamine tetracetate aqueous solution are added in alginate/chitosan/polyisopropyl acrylamide complex microsphere；
(6) 100~400rpm of revolving speed is controlled, 1~3h is persistently stirred in 0~50 DEG C, obtains milky white solution；By the solution
1~30min is centrifugated at 3000~8000rpm, distilled water washs precipitating, constant pressure and dry to constant weight repeatedly.
Alginate described in step (2) is potassium alginate or calcium alginate.
The weight ratio of alginate described in step (2) and acetic acid aqueous solution is 1:100-200, the pH value of acetic acid aqueous solution
It is 4~5.
The weight ratio of chitosan and alginate is 10-20:80-100 in step (2).
N-isopropyl acrylamide described in step (4) and alginate/chitosan compound microsphere weight ratio are 1-50:
15-200。
Soil conditioning material described in step (4) is humic acid, gallic acid gypsum or carboxymethyl cellulose, and described is molten
Agent is the aqueous solution of acetic acid or citric acid.
Alginate/chitosan/polyisopropyl acrylamide complex microsphere weight concentration is 1~3% in step (5).
The N- deacetylation of the chitosan is 85%-95%；Viscosity is 1000mPa/s, polyisopropyl acrylamide
Number-average molecular weight is 40000-50000.
Compared with prior art, present invention employs one kind is added crosslinking agent without additional, preparation stabilization, bio-compatible,
The soil conditioner of biodegradable microballoon, using the material of substance in template and wall material to the sensitive journey of pH value of soil
Degree, discharges intracapsular substance, plays the role of sustained release, adapt to the growth cycle of crop.Soil porosity, loose soil are improved simultaneously
Earth.There is the intelligence release of temperature sensitive, wet sensitive and pH sensitivity simultaneously.This also increases the conditioning effect of conditioner and utilization rates.And
It for preparing conditioner using LBL self-assembly, and obtains playing the role of sustained release and controls release, can effectively solve to change
Kind soil quality, adjusts soil texture, preparation process is simple, production cost is low, easy to implement, provides possibility for mass production
Property.
Detailed description of the invention
Fig. 1 is the calcium carbonate microspheres SEM picture containing carboxymethyl cellulose；
Fig. 2 is the sodium alginate/chitosan microballoon SEM picture containing soil conditioner.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
Take 1g anhydrous calcium chloride and 1g natrium carbonicum calcinatum, after adding 100ml deionized water to make it dissolve in volumetric flask constant volume
The reactant solution obtained, and (reaction system CMC0.1wt%) in carboxymethyl cellulose addition calcium chloride solution is stand-by.It takes
State calcium chloride solution with water mix after, be vigorously stirred it is lower by sodium carbonate liquor be quickly poured into the above system.About stop stirring afterwards
It mixes and rapid centrifugation is handled, washing is filtered all over rear, naturally dry in air, for use.
Chitosan solution: it really weighs 25mg chitosan and is dissolved into a certain amount of 0.3M sodium chloride solution, and according to volume
25ul glacial acetic acid is added after calculating than (0.1%) and shelves overnight.Taking change sodium solution to adjust pH value with 1.0M hydrogen is 4.1, for use；
Potassium alginate solution: it weighs 25mg sodium alginate and is dissolved in 0.1M sodium chloride solution and shelves overnight.With 0.1M citric acid solution
Adjusting pH value is 4.1.It is that cyst material assembles to obtain by core material, chitosan and potassium alginate of the calcium carbonate microparticle of above-mentioned preparation
2 layers of microballoon, are summarized as follows: first layer assembling: CaCO3It is suspended in the NaCl aqueous solution of 10ml 0.3M, it is ultrasonic under 80W power,
10ml chitosan solution is added, machine stirs 10min, and the NaCl aqueous solution of 10ml 0.05M is added after centrifugation, it shakes 5 minutes, from
It the heart 5 minutes, washs 3 times.Second layer assembling: the NaCl aqueous solution that 10ml 0.05M is added in particle obtained as above, which is made, to suspend
Liquid under 80W power after ultrasound, is added 10ml potassium alginate solution, stirs 10min, 10ml centrifugal treating is added after centrifugation, repeats
3 0.05M NaCl aqueous solutions are washed, 10min, centrifugal treating are stirred, repeated washing repeats aforesaid operations until being assembled into 4
Layer, outermost layer is potassium alginate.2wt%CaCl is added2Solution solidification, 1h.Then be air-dried at room temperature, by obtained potassium alginate/
Chitosan microball.Then obtained potassium alginate/chitosan microball is dissolved into 0.05M NaCl aqueous solution, at 30 DEG C, 2000
Turn/min under the N of temperature sensing material-N-isopropylacrylamide is added, machine stirs 10min, centrifugal treating, repeated washing.Shape
At potassium alginate/chitosan/N-isopropylacrylamide microballoon.Then the EDTA of 5ml 0.1M (is completed) in about 30 minutes in dropwise addition
Solution stirs at low speed lower lasting 10min；Bottom liquid is washed after carefully pipetting section top clear liquid after centrifugation, centrifugation.Then through cold
Freeze-drying drying prescription obtains solid, powdery material.As thus obtained microsphere.By obtained microballoon, stirring adds under low speed in solution at pH4.1
Enter humic acid, gypsum or carboxymethyl cellulose and persistently stir 1h in 30 DEG C, is centrifugated at 7,000 turns/min, deionized water
It washs repeatedly, air drying, obtains white powdery solid, obtained soil conditioner as of the invention.It is containing carboxylic that Fig. 1, which is shown,
The calcium carbonate microspheres SEM picture of methylcellulose.Fig. 2 shows be the sodium alginate/chitosan microballoon SEM figure containing soil conditioner
Piece.
Embodiment 2
(1) preparation of spherical calcium carbonate particle:
Take 3g anhydrous calcium chloride and 3g natrium carbonicum calcinatum, after adding 500ml deionized water to make it dissolve in volumetric flask constant volume
The reactant solution obtained, and (reaction system CMC0.2wt%) in carboxymethyl cellulose addition calcium chloride solution is stand-by.It takes
State calcium chloride solution with water mix after, be vigorously stirred it is lower by sodium carbonate liquor be quickly poured into the above system.About stop stirring afterwards
It mixes and rapid centrifugation is handled, washing is filtered all over rear, naturally dry in air, for use.
Chitosan solution: it really weighs 35mg chitosan and is dissolved into a certain amount of 0.4M sodium chloride solution, and according to volume
25ul glacial acetic acid is added after calculating than (0.1%) and shelves overnight.Taking change sodium solution to adjust pH value with 1.0M hydrogen is 4.5, for use；
Potassium alginate solution: it weighs 35mg sodium alginate and is dissolved in 0.1M sodium chloride solution and shelves overnight.With 0.1M citric acid solution
Adjusting pH value is 4.5.It is that cyst material assembles to obtain by core material, chitosan and potassium alginate of the calcium carbonate microparticle of above-mentioned preparation
8 layers of microballoon, are summarized as follows: first layer assembling: CaCO3It is suspended in the NaCl aqueous solution of 10ml 0.3M, it is ultrasonic under 90W power,
3ml chitosan solution is added, machine stirs 12min, and after centrifugation plus 35ml 0.05MNaCl aqueous solution, concussion 8 minutes are centrifuged 5
It~10 minutes, washs 3 times.Second layer assembling: the NaCl aqueous solution system of 10~50ml 0.05M is added in particle obtained as above
Suspension is obtained, under 90W power after ultrasound, 35ml potassium alginate solution is added, stirs 12min, is added at 35ml centrifugation after centrifugation
Reason washes repeatedly 3 0.08M NaCl aqueous solutions, stirs 12min, centrifugal treating, and repeated washing repeats aforesaid operations until group
Dress is 6 layers, and outermost layer is potassium alginate.3wt%CaCl is added2Solution solidification, 1.5h.Then it is air-dried at room temperature, the sea that will be obtained
Potassium alginate/chitosan microball.Then obtained potassium alginate/chitosan microball is dissolved into 0.08M NaCl aqueous solution, 35
DEG C, the N of temperature sensing material-N-isopropylacrylamide is added under 2500 turns/min, machine stirs 12min, and centrifugal treating repeats
Washing.Form potassium alginate/chitosan/N-isopropylacrylamide microballoon.Then 8ml (is completed) in about 30 minutes in dropwise addition
The EDTA solution of 0.25M stirs at low speed lower lasting 35min；Bottom liquid is washed after carefully pipetting section top clear liquid after centrifugation, from
The heart.Then solid, powdery material is obtained for freeze-dried dose.As thus obtained microsphere.By microballoon among the above in pH4.8 solution
Stirring is added humic acid, gypsum or carboxymethyl cellulose and persistently stirs 2h in 40 DEG C under low speed, the centrifugation point at 8,000 turns/min
From deionized water is washed repeatedly, air drying, obtains white powdery solid, obtained soil conditioner as of the invention.
Embodiment 3
Take 4g anhydrous calcium chloride and 4g natrium carbonicum calcinatum, after adding 800ml deionized water to make it dissolve in volumetric flask constant volume
The reactant solution obtained, and (reaction system CMC0.4wt%) in carboxymethyl cellulose addition calcium chloride solution is stand-by.It takes
State calcium chloride solution with water mix after, be vigorously stirred it is lower by sodium carbonate liquor be quickly poured into the above system.About stop stirring afterwards
It mixes and rapid centrifugation is handled, washing is filtered all over rear, naturally dry in air, for use.Chitosan solution: it is poly- really to weigh 45mg shell
Sugar is dissolved into a certain amount of 0.4M sodium chloride solution, and 25ul glacial acetic acid is added after calculating according to volume ratio (0.1%) and puts
It sets overnight.Taking change sodium solution to adjust pH value with 1.0M hydrogen is 4.80, for use；Potassium alginate solution: it is molten to weigh 45mg sodium alginate
Solution is in 0.1M sodium chloride solution and shelves overnight.Adjusting pH value with 0.1M citric acid solution is 5.10.With the carbonic acid of above-mentioned preparation
Calcium particle is that core material, chitosan and potassium alginate are that cyst material assembles to obtain 8 layers of microballoon, is summarized as follows: first layer assembling:
CaCO3It is suspended in the NaCl aqueous solution of 50ml 0.3M, it is ultrasonic under 100W power, 40ml chitosan solution, machine stirring is added
15min, after centrifugation plus 50ml 0.05MNaCl aqueous solution, concussion 10 minutes are centrifuged 10 minutes, are washed 3 times.Second layer assembling:
Suspension is made in the NaCl aqueous solution that 50ml 0.05M is added in particle obtained as above, under 100W power after ultrasound, is added
40ml potassium alginate solution stirs 15min, and 50ml centrifugal treating is added after centrifugation, and the NaCl for washing repeatedly 3 0.1M is water-soluble
Liquid stirs 15min, centrifugal treating, and repeated washing repeats aforesaid operations until being assembled into 6 layers, and outermost layer is potassium alginate.Add
Enter 4wt%CaCl2Solution solidification, 2h.Then it is air-dried at room temperature, the potassium alginate/chitosan microball that will be obtained.Then it will obtain
Potassium alginate/chitosan microball is dissolved into 0.1M NaCl aqueous solution, under 37 DEG C, 3000 turns/min that the N-of temperature sensing material is different
Propylacrylamide is added, and machine stirs 15min, centrifugal treating, repeated washing.Form potassium alginate/chitosan/isopropyl third
Acrylamide microballoon.Then the EDTA solution for (completing) 10ml 0.5M in about 30 minutes in dropwise addition stirs at low speed lower lasting 30min；
Bottom liquid is washed after carefully pipetting section top clear liquid after centrifugation, centrifugation.Then solid, powdery material is obtained for freeze-dried dose.
As thus obtained microsphere.By microballoon among the above, humic acid, gypsum or carboxymethyl cellulose is added in stirring under low speed in pH5.1 solution
Element persistently stirs 3h in 50 DEG C, is centrifugated at 9,000 turns/min, and deionized water is washed repeatedly, and air drying obtains white
The soil conditioner that powdery solid, the as present invention obtain.
Embodiment 4
Take 5g anhydrous calcium chloride and 5g natrium carbonicum calcinatum, after adding 1000ml deionized water to make it dissolve in volumetric flask constant volume
The reactant solution obtained, and (reaction system CMC0.5wt%) in carboxymethyl cellulose addition calcium chloride solution is stand-by.It takes
State calcium chloride solution with water mix after, be vigorously stirred it is lower by sodium carbonate liquor be quickly poured into the above system.About stop stirring afterwards
It mixes and rapid centrifugation is handled, washing is filtered all over rear, naturally dry in air, for use.Chitosan solution: it is poly- really to weigh 50mg shell
Sugar is dissolved into a certain amount of 0.6M sodium chloride solution, and 25ul glacial acetic acid is added after calculating according to volume ratio (0.1%) and puts
It sets overnight.Taking change sodium solution to adjust pH value with 1.0M hydrogen is 5.10, for use；Potassium alginate solution: it is molten to weigh 50mg sodium alginate
Solution is in 0.1M sodium chloride solution and shelves overnight.Adjusting pH value with 0.1M citric acid solution is 5.10.With the carbonic acid of above-mentioned preparation
Calcium particle is that core material, chitosan and potassium alginate are that cyst material assembles to obtain 8 layers of microballoon, is summarized as follows: first layer assembling:
CaCO3It is suspended in the NaCl aqueous solution of 50ml 0.3M, it is ultrasonic under 100W power, 50ml chitosan solution, machine stirring is added
15min, after centrifugation plus the NaCl aqueous solution of 50ml 0.05M, concussion 10 minutes are centrifuged 10 minutes, are washed 3 times.Second layer group
Dress: suspension is made in the NaCl aqueous solution that 50ml 0.05M is added in particle obtained as above, under 100W power after ultrasound, is added
50ml potassium alginate solution,.15min is stirred, 50ml centrifugal treating is added after centrifugation, it is water-soluble to wash repeatedly 3 0.08M NaCl
Liquid stirs 15min, centrifugal treating, and repeated washing repeats aforesaid operations until being assembled into 8 layers, and outermost layer is potassium alginate.Add
Enter 6wt%CaCl2Solution solidification, 2h.Then it is air-dried at room temperature, the potassium alginate/chitosan microball that will be obtained.Then it will obtain
Potassium alginate/chitosan microball is dissolved into 0.1M NaCl aqueous solution, by temperature sensing material under 30~40 DEG C, 3000 turns/min
N-N-isopropylacrylamide is added, and machine stirs 15min, centrifugal treating, repeated washing.Formation potassium alginate/chitosan/different
Propylacrylamide microballoon.Then the EDTA solution for (completing) 10ml0.5M in about 30 minutes in dropwise addition, stirs at low speed lower lasting
30min；Bottom liquid is washed after carefully pipetting section top clear liquid after centrifugation, centrifugation.Then solid powder is obtained for freeze-dried dose
Shape material.As thus obtained microsphere.By microballoon among the above, humic acid, gypsum or carboxylic is added in stirring under low speed in pH5.1 solution
Methylcellulose persistently stirs 3h in 60 DEG C, is centrifugated at 10,000 turns/min, and deionized water is washed repeatedly, and room temperature is dry
It is dry, white powdery solid is obtained, obtained soil conditioner as of the invention.
Infrared spectroscopy, thermal weight loss central temperature and the particle size range of 1 alginate composite intelligent microballoon of table
The Intelligent controlled release performance of 2 alginate composite intelligent microballoon of table
| Embodiment | 0℃ | 25℃ | 35℃ | 40℃ | 45℃ |
| Embodiment 1 | 0 | 4% | 25% | 50% | 75% |
| Embodiment 2 | 0 | 8% | 35% | 55% | 85% |
| Embodiment 3 | 0 | 16% | 45% | 60% | 88% |
Embodiment 5
A kind of preparation method of the soil conditioner based on LBL self-assembly microballoon, using following steps:
(1) carboxymethyl cellulose of 0.05wt% is added in calcium chloride water, heats up 20 DEG C and carbonic acid is added after stirring
Sodium water solution continues to stir 1h, is then freeze-dried, carbonic acid calcisphere is prepared；
(2) potassium alginate, chitosan are dissolved in respectively containing acetic acid, in the aqueous solution that pH value is 4, potassium alginate and acetic acid
The weight ratio of aqueous solution is 1:100, and the N- deacetylation of chitosan is 85%；Viscosity is 1000mPa/s, chitosan and alginic acid
The weight ratio of potassium is 10:80；
(3) calcium carbonate microspheres are added into chitosan solution at room temperature, are warming up to 20 DEG C, stir 1h, keep 2h, centrifugation
Potassium alginate solution is added afterwards, is dried to obtain alginate/chitosan compound microsphere；
(4) n-isopropyl acrylamide is added in alginate/chitosan compound microsphere, n-isopropyl acrylamide
It is 1:15 with alginate/chitosan compound microsphere weight ratio, at 20 DEG C, 10min is stirred with the revolving speed of 800rpm, obtains sea
Alginates/chitosan/polyisopropyl acrylamide complex microsphere；
(5) soil conditioning material humic acid is dissolved in acetic acid aqueous solution, the coupling of 1wt% calcium chloride is added, it then will be native
It is multiple that earth conditioning materials solution and sodium ethylene diamine tetracetate aqueous solution are added to alginate/chitosan/polyisopropyl acrylamide
It closes in microballoon, alginate/chitosan/polyisopropyl acrylamide complex microsphere weight concentration is 1%, wherein poly- isopropyl
The number-average molecular weight of acrylamide is 40000；
(6) revolving speed 100rpm is controlled, 1h is persistently stirred in 0 DEG C, obtains milky white solution；At 3,000 rpm by the solution
It is centrifugated 1min, distilled water washs precipitating, constant pressure and dry to constant weight repeatedly.
Embodiment 6
A kind of preparation method of the soil conditioner based on LBL self-assembly microballoon, using following steps:
(1) carboxymethyl cellulose of 0.1wt% is added in calcium chloride water, heats up 80 DEG C and sodium carbonate is added after stirring
Aqueous solution continues to stir 1h, is then freeze-dried, carbonic acid calcisphere is prepared；
(2) calcium alginate, chitosan are dissolved in respectively containing acetic acid, in the aqueous solution that pH value is 5, potassium alginate and acetic acid
The weight ratio of aqueous solution is 1:200, and the N- deacetylation of chitosan is 95%；Viscosity is 1000mPa/s, chitosan and alginic acid
The weight ratio of potassium is 20:100；
(3) calcium carbonate microspheres are added into chitosan solution at room temperature, are warming up to 70 DEG C, stir 2h, keep 4h, centrifugation
After alginate solution is added, be dried to obtain alginate/chitosan compound microsphere；
(4) n-isopropyl acrylamide is added in alginate/chitosan compound microsphere, n-isopropyl acrylamide
It is 50:200 with alginate/chitosan compound microsphere weight ratio, at 30 DEG C, 30min is stirred with the revolving speed of 1200rpm, is obtained
Obtain alginate/chitosan/polyisopropyl acrylamide complex microsphere；
(5) soil conditioning material carboxymethyl cellulose is dissolved in the aqueous solution of citric acid, 10wt% calcium chloride coupling is added
It closes, soil conditioning material solution and sodium ethylene diamine tetracetate aqueous solution is then added to alginate/chitosan/poly- isopropyl
In acrylamide complex microsphere, alginate/chitosan/polyisopropyl acrylamide complex microsphere weight concentration is 3%,
The number-average molecular weight of middle polyisopropyl acrylamide is 50000；
(6) revolving speed 400rpm is controlled, 3h is persistently stirred in 50 DEG C, obtains milky white solution；By the solution at 8000rpm
It is centrifugated 30min, distilled water washs precipitating, constant pressure and dry to constant weight repeatedly.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. a kind of preparation method of the soil conditioner based on LBL self-assembly microballoon, which is characterized in that this method is using following
Step:
(1) carboxymethyl cellulose of 0.05~0.1wt% is added in calcium chloride water, is added after 20~80 DEG C of stirrings that heat up
Aqueous sodium carbonate continues to stir 1h, is then freeze-dried, carbonic acid calcisphere is prepared；
(2) alginate, chitosan are dissolved in respectively in the aqueous solution containing acetic acid；
(3) calcium carbonate microspheres are added into chitosan solution at room temperature, are warming up to 20~70 DEG C, stir 1~2h, keep 2~
Alginate solution is added after centrifugation in 4h, is dried to obtain alginate/chitosan compound microsphere；
(4) n-isopropyl acrylamide is added in alginate/chitosan compound microsphere, at 20~30 DEG C, with 800~
The revolving speed of 1200rpm stirs 10~30min, obtains alginate/chitosan/polyisopropyl acrylamide complex microsphere；
(5) soil conditioning material is dissolved in solvent, the coupling of 1~10wt% calcium chloride is added, it is then that soil conditioning material is molten
Liquid and sodium ethylene diamine tetracetate aqueous solution are added in alginate/chitosan/polyisopropyl acrylamide complex microsphere；
(6) 100~400rpm of revolving speed is controlled, 1~3h is persistently stirred in 0~50 DEG C, obtains milky white solution；The solution is existed
1~30min is centrifugated under 3000~8000rpm, distilled water washs precipitating, constant pressure and dry to constant weight repeatedly.
2. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, alginate described in step (2) is potassium alginate or calcium alginate.
3. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, the weight ratio of alginate described in step (2) and acetic acid aqueous solution is 1:100-200, and the pH value of acetic acid aqueous solution is
4-5。
4. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, the weight ratio of chitosan and alginate is 10-20:80-100 in step (2).
5. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, n-isopropyl acrylamide described in step (4) and alginate/chitosan compound microsphere weight ratio are 1-50:15-
200。
6. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, soil conditioning material described in step (4) is humic acid, gallic acid gypsum or carboxymethyl cellulose, the solvent
For acetic acid or the aqueous solution of citric acid.
7. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, alginate/chitosan/polyisopropyl acrylamide complex microsphere weight concentration is 1~3% in step (5).
8. a kind of preparation method of soil conditioner based on LBL self-assembly microballoon according to claim 1, feature
It is, the N- deacetylation of the chitosan is 85%-95%；Viscosity is 1000mPa/s, and the number of polyisopropyl acrylamide is equal
Molecular weight is 40000-50000.
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