CN108659847A - A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof - Google Patents
A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof Download PDFInfo
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- CN108659847A CN108659847A CN201710220388.XA CN201710220388A CN108659847A CN 108659847 A CN108659847 A CN 108659847A CN 201710220388 A CN201710220388 A CN 201710220388A CN 108659847 A CN108659847 A CN 108659847A
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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
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/20—Vinyl polymers
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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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
A kind of environmental type soil-repairing agent (AZTR) be monomer with polypropylene glycol ester monomer and the unsaturated double-bond containing vinyl and can with the fluorescent monomer of fluorescent tracing and the magnetic ferroferric oxide containing unsaturated double-bond carry out it is free-radical polymerized after must, general structure is as follows：
Description
Technical field
It is that one kind being suitable for Chinese herbal medicine plantation and agriculture the present invention relates to Chinese herbal medicine planting soil renovation agent and preparation method thereof
The soil-repairing agent of industry plantation, is particularly suitable for the reparation of high content of beary metal soil.
Background technology
With the fast development of city industrialization, the burning of " three wastes " and fossil fuel of various industrial and mining enterprises' discharges
With the excessive use of fertilizer and pesticide, heavy metal, chemical pollutant enter soil by all means, and quantity is far super with speed
The carrying capacity and purification speed of soil.The current heavy metal pollution of soil problem very severe in China, China Geological Survey Bureau
China's multiple target regional geochemistry investigation result of implementation show 13% national territorial area region soil exist pollution, south with
Based on heavy metal problem, heavy metal pollution destroys the self-repairing capability of soil, and soil quality is caused to deteriorate, and directly affects
The normal growth and development of Chinese herbal medicine causes herbal product yield and quality to decline, has seriously affected the drug effect of Chinese herbal medicine, reduces
The effect of Chinese herbal medicine cures the sickness to save the patient, the problem of due to heavy-metal residual, the worlds general export E Jinzhan of the current Chinese medicine in China
The sales volume of autonomic drug 1% or so.
For a long time, people are more deep to water pollution and atmosphere pollution understanding, but are generally deposited to the understanding of soil pollution
In deficiency, soil contamination problem in China unlike water pollution and atmosphere pollution are noticeable, in recent years, the developed countries such as U.S.
The numerous and confused soil contamination problem that begins one's study, China also begins to formulate《Soil temperature and soil moisture content》First draft payes attention to soil contamination problem.
Common heavy metal pollution includes copper, zinc, lead, chromium, nickel etc. in soil pollution, and food medicine secure context major limitation is copper, chromium
Deng in existing all standard, heavy metal element height of content in Chinese medicine, which is increasingly becoming, weighs Chinese medicine quality, product
Bad one crucial evaluation metrics of fine quality, therefore, during prevention and control and the improvement of Chinese herbal medicine planting base heavy metal in soil content are
The major issue of medicinal material urgent need to resolve.
At present China in terms of soil remediation using it is more be microorganism remediation, chemical remediation and phytoremediation.Mesh
The metal-chelator that preceding chemical remediation is commonly used has hydroxycarboxylic acid and polycarboxylic acid etc., although these chelating agents can be fine
Ground chelated mineral, but chelate after heavy metal still can remaining in the soil, after a period of time again can dissociate in the soil, " control
Mark does not effect a permanent cure ", microorganism remediation is harsher to the selection of microorganism, and it is difficult to ensure that microorganism survival rate, plant repaiies
Multiple excessive cycle and relatively difficult to the selection of enriching heavy metal plant.Chemical remediation belongs to in-situ immobilization, and operation is easy to
Implement and cost is easy to control, for the soil of mild or moderate heavy metal pollution, repairing effect is preferable, and is suitable in large area
The reparation of herbal medicine planting soil pollution.
A kind of chemical regulator improvement soil pollution is disclosed in CN20031010891.0, main component is low molecular weight
Chitosan, main function are used as eluent, and CN20121023142.2 discloses a kind of heavy metal adsorption flocculation
Agent, the flocculant being mainly used in adsorbed water body, although these chelating agents can chelated mineral well, a huge sum of money after chelating
Belong to still remaining can dissociate in the soil after a period of time again in the soil, " palliative ".
Therefore, exploitation one kind can restoration of soil polluted by heavy metal, and can recoverable soil-repairing agent, for controlling
The reparation for managing China's Chinese herbal medicine planting soil heavy metal pollution has great application value and environment protection significance.The purpose of the present invention
Being to provide a kind of Chinese herbal medicine planting soil renovation agent and its application, the soil-repairing agent has excellent absorption heavy metal
Can, it is environmentally friendly can be with recycling.
Invention content
Technical problem：The present invention is using the monomer and acrylic acid, maleic anhydride, allyl sulphur for carrying the structure containing polypropylene glycol
The small molecule monomer of the carboxy-containing acid groups such as sour sodium and can with the fluorescent monomer of fluorescent tracing and magnetism four containing hydroxyl oxidation
Three iron particles synthesize recyclable without phosphorus copolymer metal-chelator, have excellent chelating heavy metal effect, while in magnetic
There is recyclable recycling property energy under field action, be a kind of environmental-friendly environment protection type soil renovation agent.
Technical solution：A kind of environmental type soil-repairing agent (AZTR) be with polypropylene glycol ester monomer with containing vinyl not
Be saturated double bond monomer and can with the fluorescent monomer of fluorescent tracing and the magnetic ferroferric oxide containing unsaturated double-bond carry out
After free-radical polymerized, general structure is as follows：
Wherein：A is the constitutional repeating unit after the monomer copolymerization of the unsaturated double-bond containing vinyl, and B is to contain unsaturated double-bond
Fluorescent monomer polymerization after constitutional repeating unit, C is the magnetic ferroferric oxide containing unsaturated double-bond, and degree of polymerization x, y, z is 1
~5000, number of repeat unit m, n is 1~100.
A kind of preparation method of above-mentioned soil-repairing agent is：
In N2Under atmosphere, on the basis of allyl polypropylene glycol ether quality, by allyl polypropylene glycol ether and 0.05~5 times of alkene
The maleic anhydride of propyl polypropylene glycol ether quality is added in reaction kettle, and 1~10h is reacted at 60~160 DEG C, obtains polyether carboxylic acid
Ester reaction monomers.After reaction temperature is adjusted to 50~95 DEG C, add 0.2~5 times of allyl polypropylene glycol ether quality contains second
The fluorescence list containing unsaturated double-bond of the monomer of alkenyl unsaturated double-bond, 0.001~0.5 times of allyl polyglycol monoether quality
The ferroso-ferric oxide containing unsaturated double-bond, 0.1~5 times of allyl of body, 0.001~0.5 times of allyl polyglycol monoether quality
The inorganic initiator aqueous solution that mass percentage concentration is 5%~50% is added dropwise after mixing for the water of base polypropylene glycol ether quality, inorganic
The addition of initiator is 0.01~0.5 times of allyl polypropylene glycol ether quality, and 1~5h is dripped off, and is continued 50~95 after dripping off
0.5~10h is reacted at DEG C, is cooled to room temperature, and the environmental type soil-repairing agent that solid content is 5~70wt% is made.
The monomer of unsaturated double-bond containing vinyl described in the preparation method of above-mentioned environmental type soil-repairing agent is
Acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, maleic anhydride, acrylic acid
One or more combinations of hydroxypropyl acrylate, maleic acid, itaconic acid.The fluorescent monomer containing unsaturated double-bond is N- phenyl-
One or two kinds of group in vinyl benzyl-naphthalidine 8- sodium sulfonates and N- phenyl-acryloyls-naphthalidine 8- sodium sulfonates
It closes；
Inorganic initiator described in the preparation method is sodium peroxydisulfate, potassium peroxydisulfate, lays particular stress on sulfinic acid sodium, lays particular stress on sub- sulphur
The combination of one or more of sour potassium, persulfonic acid sodium, persulfonic acid potassium, hydrogen peroxide.
Advantageous effect：The soil-repairing agent of the present invention has following excellent properties：
(1) soil-repairing agent not Nitrogen-and Phosphorus-containing etc. has good heavy metal chelating performance, is a kind of novel environment-friendly type
Soil-repairing agent.Its preparation process green environment is friendly, and building-up process is using environmental protection, inexpensive water as reaction dissolvent, reaction
Process uses " treating different things alike " mode, simple to operate, production cost is relatively low without separation.
(2) containing the strong sulfonic acid group of hydrophily in the soil-repairing agent structure, and can be chelated with heavy metal ion
Carboxylic acid ion has efficient inhibiting effect to the heavy metal ion in Chinese herbal medicine planting soil, and in addition the soil-repairing agent contains
Some magnetic ferroferric oxides have good recuperability energy.
(3) compatibility of the soil-repairing agent is good, can be used in compounding with soil-repairing agents such as sepiolite, lime, also can be single
Solely use.
Specific implementation mode
Example 1：
In N2100g allyl polypropylene glycol ethers are added in the reaction kettle of protection, 80g maleic anhydrides are added at 70 DEG C
(being dissolved in 100g water) and 100g water add 80g maleic anhydrides, 0.5g N- phenyl-ethenyls benzyl-naphthalidine 8- sodium sulfonates,
10g sodium peroxydisulfates (being dissolved in 50g water) are added dropwise after mixing for 100g water, and after being added dropwise, continuation reacts 2h at 80 DEG C, is down to room
A kind of soil-repairing agent (AZTR1) is made in Wen Hou
Example 2：In N2100g allyl polypropylene glycol ethers are added in the reaction kettle of protection, 65g maleics are added at 50 DEG C
Dicarboxylic anhydride (being dissolved in 100g water) and 100g water add 70g maleic anhydrides, 0.4g N- phenyl-acryloyls-naphthalidine 8- sulphurs
12g sodium peroxydisulfates (being dissolved in 50g water) are added dropwise after mixing for sour sodium, 100g water, and after being added dropwise, 2h is reacted in continuation at 75 DEG C, drops
To room temperature, a kind of soil-repairing agent (AZTR2) is made
Example 3：In N2100g allyl polypropylene glycol ethers are added in the reaction kettle of protection, 45g maleics are added at 37 DEG C
Dicarboxylic anhydride (being dissolved in 100g water) and 100g water add 60g maleic anhydrides, 0.3g N- phenyl-acryloyls-naphthalidine 8- sulphurs
16g sodium peroxydisulfates (being dissolved in 50g water) are added dropwise after mixing for sour sodium, 100g water, and after being added dropwise, 2h is reacted in continuation at 75 DEG C, drops
To room temperature, a kind of soil-repairing agent (AZTR3) is made
Containing heavy metal Cu2+Soil in content of copper ion be 20mg/L, by the soil-repairing agent of embodiment 1 to 3 spend from
Sub- water dilution is configured to fixed concentration (soil remediation agent content is 20mg concentration) aqueous solution, soil dissolving is added in aqueous solution
Copper ion in soil lysate is measured in liquid (soil of copper ions takes out supernatant liquid with deionized water dissolving), after 3h to contain
Amount is as a result as follows：
From in the rehabilitating soil of embodiment in terms of the result of copper ion, the chelating of soil-repairing agent of the invention for copper ion
Ability significant effect.
Claims (4)
1. a kind of environmental type soil-repairing agent (AZTR) is with polypropylene glycol ester monomer and unsaturated double-bond containing vinyl
Monomer and can with the fluorescent monomer of fluorescent tracing and the magnetic ferroferric oxide containing unsaturated double-bond carry out it is free-radical polymerized
Afterwards, general structure is as follows：
Wherein：A is the constitutional repeating unit after the monomer copolymerization of the unsaturated double-bond containing vinyl, and B is containing the glimmering of unsaturated double-bond
Constitutional repeating unit after light monomer polymerization, C are the magnetic ferroferric oxides containing unsaturated double-bond, degree of polymerization x, y, z is 1~
5000, number of repeat unit m, n is 1~100.
2. a kind of environmental type soil-repairing agent (AZTR) a kind of as described in claim 1 and preparation method thereof, feature
It is that the preparation method is：
In N2Under atmosphere, on the basis of allyl polypropylene glycol ether quality, by allyl polypropylene glycol ether and 0.05~5 times of allyl
The maleic anhydride of polypropylene glycol ether quality is added in reaction kettle, and 1~10h is reacted at 60~160 DEG C, it is anti-to obtain polyether carboxylate
Answer monomer.After reaction temperature is adjusted to 50~95 DEG C, add 0.2~5 times of allyl polypropylene glycol ether quality contains vinyl
The monomer of unsaturated double-bond, 0.001~0.5 times of allyl polyglycol monoether quality the fluorescent monomer containing unsaturated double-bond,
The ferroso-ferric oxide containing unsaturated double-bond of 0.001~0.5 times of allyl polyglycol monoether quality, 0.1~5 times of allyl are poly-
The inorganic initiator aqueous solution that mass percentage concentration is 5%~50%, inorganic initiation are added dropwise after mixing for the water of propylene glycol quality
The addition of agent is 0.01~0.5 times of allyl polypropylene glycol ether quality, and 1~5h is dripped off, and is continued at 50~95 DEG C after dripping off
0.5~10h is reacted, room temperature is cooled to, the environmental type soil-repairing agent that solid content is 5~70wt% is made.
3. a kind of environmental type soil-repairing agent (AZTR) according to claim 2 and preparation method thereof above-mentioned green
The monomer of unsaturated double-bond containing vinyl described in the preparation method of environment-friendly type polyether carboxylate corrosion inhibiting and descaling agent is acrylic acid, first
Base acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, maleic anhydride, hydroxypropyl acrylate, horse
Carry out sour, itaconic acid one or more combination.The fluorescent monomer containing unsaturated double-bond is N- phenyl-ethenyls benzyl-
One or two kinds of combination in naphthalidine 8- sodium sulfonates and N- phenyl-acryloyls-naphthalidine 8- sodium sulfonates.
4. a kind of environmental type soil-repairing agent (AZTR) according to claim 2 and preparation method thereof, feature exists
Inorganic initiator described in the preparation method is sodium peroxydisulfate, potassium peroxydisulfate, lay particular stress on sulfinic acid sodium, lay particular stress on sulfinic acid potassium,
The combination of one or more of persulfonic acid sodium, persulfonic acid potassium or hydrogen peroxide.
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| CN201710220388.XA CN108659847A (en) | 2017-03-28 | 2017-03-28 | A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof |
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| CN201710220388.XA CN108659847A (en) | 2017-03-28 | 2017-03-28 | A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718722A (en) * | 2019-03-18 | 2020-09-29 | 安徽中医药大学 | Modified polypropylene glycol soil remediation agent and preparation method thereof |
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