CN102516476A - Synthesis of amphiphilic ionic high polymer soil conditioner - Google Patents
Synthesis of amphiphilic ionic high polymer soil conditioner Download PDFInfo
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- CN102516476A CN102516476A CN2011103976638A CN201110397663A CN102516476A CN 102516476 A CN102516476 A CN 102516476A CN 2011103976638 A CN2011103976638 A CN 2011103976638A CN 201110397663 A CN201110397663 A CN 201110397663A CN 102516476 A CN102516476 A CN 102516476A
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Abstract
The invention relates to an amphiphilic ionic high polymer soil conditioner and a synthesis method thereof. The soil conditioner can be widely applied in the fields of drought resistance and seedling protection, soil improvement, wind sheltering and sand fixation, water and soil conservation and the like, and is particularly suitable for improving poor soil suffering from soil firmness, hardening, erosion, salinization, acidification, element imbalance, chemical pollution, organic matter loss, degeneration of fauna and flora, and the like. A high polymer grafting and copolymerizing process is adopted, so that intra-intermolecular grafting of humic acid and starch is performed while copolymerization of polymer negative and positive ionic monomers is realized, agglomerates formed by reacting a synthetic product with soil are more natural, and plant growth is facilitated.
Description
Technical field
The present invention relates to a kind of soil improvement agent, be specifically related to a kind of pair of property ion superpolymer soil improvement agent, be particularly useful for material and form the unbalance and not normal poor soil of structure, and the working method of said pair of property ion superpolymer soil improvement agent.
Background technology
Continuous development along with economy and society; The Soil degradation problem becomes increasingly conspicuous; Mainly show as soil compaction and sclerosis, erosion, salinization, acidifying, element is unbalance, chemical pollution, the organic loss and the degeneration of plant-animal fauna etc., has seriously limited the development of fertility.Poor soil be because material form unbalance with structure not normal due to.
Crumb structure is that soil has the substruction that agronomy is worth, and natural granule is the structural agent that is formed by soil organic substance, and the main humic acid of organic structuring agent is seen from chemical structure, and it is made up of many aromatic nucleus monomers.Belong to aromatic series or phenyl polycarboxylic acid class macromolecular substance; Its polar group (like carboxyl, hydroxyl, carboxamido-group etc.) is with electrostatic force and Van der Waals force and adsorption of metal ions; Exchange and adsorption take place through positively charged ion bridge and soil particle; Form natural granule, its hydrophilic polar group is that it has the activity functional groups that connects mineral particle.
The soil organism such as selection and humic acid have the superpolymer of identity function group; Apply deterioration wait improve the soil; The simulated soil organic matter is the effect of humic acid particularly, makes soil form crumb structure and has agronomy value, is different from the novel method of traditional soil improvement method; This superpolymer with the effect of improving the soil is called soil improvement agent, is called for short the superpolymer modifying agent.
Using soil improvement agent is one of important measures of repairing degenerated soil.Soil improvement agent can improve soil physical and chemical property and soil nutrient status effectively, and soil microorganisms is produced positive influence, thereby improves the yield-power of degenerated soil.Therefore, its research has important theory and realistic meaning with application to the control Soil degradation.
Summary of the invention
The purpose of this invention is to provide a kind of working method that is applied to two property ion superpolymer soil improvement agents in eagroforestry field; This modifying agent has the resistance that stimulating plant grew, increased crop, the effect of improving plant nutrition; Can improve the fertile water retention capacity of guarantor of soil again; And product cost is low, can be widely used in keeping crop seedling from drought, increasing both production and income, improves the soil, checks winds and fixes drifting sand, soil conservation etc., also can dress seed.
For synthetic above-mentioned pair of property ion superpolymer soil improvement agent; The technical scheme of being taked is following: soil improvement agent of the present invention has adopted macromolecular grafted copolymerization process, when having realized polymkeric substance zwitterion monomer, cross-linker molecules copolymerization, humic acid and starch is carried out the intramolecularly grafting.
The proportioning of each ingredients constitute feed liquid gross weight is in the copolymerized grafting process:
(a) acrylic amide of 10 to 20 weight % (AM);
(b) vinylformic acid of 5 to 20 weight % (AA);
(c) starch of 5 to 10 weight % (ST);
(d) USAF RH-1 of 1 to 5 weight % (MAM);
(e) cationic monomer of 1 to 5 weight % (DMC, DAC, DMDAC);
(f) humate of 5 to 10 weight % (HA);
(g) 0.002 to 0.008 weight % linking agent (MBA, PEGDA);
(h) its surplus is a water.
The synthesis step of above-mentioned pair of property ion soil modifying agent is following:
(1) reaction raw materials such as selected acrylic amide, vinylformic acid, starch, USAF RH-1, a kind of cationic monomer, humate and linking agent carry out proportioning according to a certain percentage;
(2), regulate that to add alkali speed control system temperature be 70～90 ℃ with in the Pottasium Hydroxide and vinylformic acid;
(3) when temperature is lower than 80 ℃, begins to add starch slurry and carry out gelatinization, gelatinization 1～2h;
(4), system temperature adds acrylic amide, USAF RH-1, cationic monomer and linking agent, stirring and dissolving when being cooled to below 40 ℃;
(5) add humate, stir and form the homogeneous system;
(6) the adjustment feed temperature is 15 ± 1 ℃;
(7) produce radical with aqueous solution catalyst method and make above-mentioned monomer generation polymerization.
In with the process of aqueous solution polymerization, need solution nitrogen blowing 20 minutes to remove the dissolved oxygen in anhydrating, is added catalyzer then under protection of nitrogen gas; Stop nitrogen blowing and polymeric kettle is airtight; Brought out 10-15 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; Be regarded as causing successfully, otherwise need add the catalyzer re-initiation again.Under the insulation air tight condition, finish, be incubated 3 hours until heating up.
For the not special restriction of said catalyzer.The oxygenant of polymerizing catalyst is persulphate or superoxide, for example ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, Lucidol or tert-butyl peroxide.Can use oxygenant to form redox system with reductive agent among the present invention, said reductive agent can be sulphite, hydrosulphite, protosalt, organic amine etc.
Azo cpd also is one of preferred catalyzer of the present invention, and the typical azo cpd that is suitable for is Diisopropyl azodicarboxylate (AZDN), ABVN (V65), azo diisobutyl amidine hydrochloride (V50) etc.
Can use two or more above-mentioned catalyzer simultaneously, the amount of catalyzer is generally the 0.001-3% weight of reaction feed liquid.
Humic acids is a kind of natural organic macromolecule compound; It is generally acknowledged that it is a mixture complicated, the inhomogenous hydroxybenzene carboxylic acid of molecular weight; The unit that forms humic acids have carbon, hydrogen, oxygen, nitrogen, sulphur and a spot of phosphorus; Contain multiple functional group in the humic acids, the character and the application of these functional groups and humic acids have much relations, and there are carboxyl, phenolic hydroxyl group, alcoholic extract hydroxyl group, quinonyl, methoxyl group, carbonyl etc. in wherein main functional group.Starch is to be the natural polymer of structural unit with the Glucopyranose, and intramolecularly contains a large amount of activity hydroxies, can with vinyl monomer generation graft copolymerization; In the reaction soln of humic acids hydrochlorate and starch, vinyl monomer; At first be the autohemagglutination and the copolymerization of vinyl monomer; Humic acids, starch and SEPIGEL 305 generation graft copolymerization afterwards carry out crosslinkedly between last polyacrylamide amine side chain, form the network structure of water-fast complicacy.The method of this aqueous solution graft copolymerization is fixed in the macromolecular structure humic acids and starch, can bring into play the multiple biological activity of its inherent.
Of the present invention pair of property ion superpolymer soil improvement agent compared with prior art has many advantages and positively effect: (1) is improved the water conservation of soil physical property, enhancing soil and is protected native ability; Strengthen the validity of nutritive element in the soil, increase soil fertility; (2) improve useful microbe and enzymic activity in the soil, suppress pathogenic micro-organism, the resistance of enhancement of plant; (3) transfer ability of heavy metal Cd, Pb, Zn, Co, Cu, Ni etc. in the reduction heavy-metal contaminated soil suppresses crop heavy metal is absorbed;
Embodiment
To do detailed explanation to of the present invention pair of property ion superpolymer soil improvement agent compound method according to concrete embodiment below.
Embodiment 1
The weight percent of each monomer and water is following:
Acrylic amide (AM): 15%
Vinylformic acid (AA): 10%
W-Gum (ST): 8%
USAF RH-1 (MAM): 3%
Methylacryoyloxyethyl trimethyl ammonium chloride (DMC): 3%
Humate (HA): 8%
N,N methylene bis acrylamide MBA:0.005%
Zero(ppm) water: 53%
The preparation of solution: in the 2000ml beaker, add zero(ppm) water 388g and vinylformic acid (AA) 100g, the adding speed of control Pottasium Hydroxide makes system temperature maintain 70～90 ℃, and the Pottasium Hydroxide consumption is 62g, and this moment, the vinylformic acid degree of neutralization was about 80%; W-Gum 80g is dissolved in stirring formation starch in the 80g zero(ppm) water; Starch slurry is joined gelatinization 1～2h in the neutral vinylformic acid system; When reaction solution is cooled to 40 degree when following, begin to add 150g acrylic amide, 30g USAF RH-1,30g methylacryoyloxyethyl trimethyl ammonium chloride and 0.05g linking agent N,N methylene bis acrylamide, stirring and dissolving; Add the 80g ammonium humate again, stir and form the homogeneous system.
The adjustment of solution: 15 ± 1 ℃ of attemperation.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes adds catalyst V 650.5g/L, V50 0.05g/L successively under nitrogen protection; Ammonium persulphate 0.03g/L, sodium formaldehyde sulphoxylate 0.03g/L stops nitrogen blowing and polymeric kettle is airtight; Brought out 15-20 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; Be regarded as causing successfully, otherwise need add the catalyzer re-initiation again.Under the insulation air tight condition, finish, be incubated 3 hours until heating up.
The aftertreatment of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders.
Claims (11)
1. the compound method of two property ion superpolymer soil improvement agents is characterized in that: with in the Pottasium Hydroxide and vinylformic acid, degree of neutralization is 75～85mol%; Add starch pasting, behind the gelatinization certain hour, add acrylic amide, USAF RH-1, cationic monomer and linking agent; Stirring and dissolving; Add humate, stir and form the homogeneous system, produce radical with aqueous solution catalyst method at last and make above-mentioned monomer generation polymerization.
2. soil improvement agent according to claim 1 is characterized in that: the proportioning of each ingredients constitute feed liquid gross weight is in the copolymerized grafting process:
(a) acrylic amide of 10 to 20 weight % (AM);
(b) vinylformic acid of 5 to 20 weight % (AA);
(c) starch of 5 to 10 weight % (ST);
(d) USAF RH-1 of 1 to 5 weight % (MAM);
(e) cationic monomer of 1 to 5 weight %;
(f) humate of 5 to 10 weight % (HA);
(g) linking agent of 0.002 to 0.008 weight %;
(h) its surplus is a water.
3. the compound method of according to claim 1 pair of property ion superpolymer soil improvement agent is characterized in that:
With in the Pottasium Hydroxide and behind the vinylformic acid, add starch slurry again, utilize acid-base neutralisation heat that starch is carried out gelatinization, temperature is controlled at 58～80 ℃, gelatinization time 1～2 hour; ,, when temperature is lower than 80 ℃, begins to add starch slurry and carry out gelatinization at 70～90 ℃ through the speed control system temperature in the adjusting alkali adding acid; Add acrylic amide, USAF RH-1, cationic monomer and linking agent when gelatinization is cooled to below 40 ℃, stirring and dissolving adds humate again, stirs to form the homogeneous slurry.
4. the compound method of according to claim 1 pair of property ion superpolymer soil improvement agent; It is characterized in that: said aqueous solution initiator method is meant at first will protect 20 minutes to the monomer solution nitrogen blowing for preparing; In solution, add the aqueous solution initiator that configures then; Bring out 10-15 minute with the generation radical, thereby make monomer generation polymerization.
5. according to the compound method of said pair of property of claim 1 ion superpolymer soil improvement agent, it is characterized in that: said starch can be W-Gum, tapioca(flour), yam starch.
6. according to the compound method of said pair of property of claim 1 ion superpolymer soil improvement agent, it is characterized in that: said cationic monomer can be acrylyl oxy-ethyl-trimethyl salmiac (DAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC), dimethyl diallyl ammonium chloride (DMDAC).
7. according to the compound method of said pair of property of claim 1 ion superpolymer soil improvement agent, it is characterized in that: said linking agent is N,N methylene bis acrylamide (MBA), polyoxyethylene glycol double methacrylate (PEGDA).
8. according to the compound method of said pair of property of claim 1 ion superpolymer soil improvement agent, it is characterized in that: said humate is Sodium salts humic acids, ammonium humate, potassium humate, humic acids magnesium, calcium humate.
9. according to the compound method of said pair of property of claim 1 ion superpolymer soil improvement agent, it is characterized in that: said initiator is persulphate or superoxide; Perhaps form redox system with reductive agent for persulphate or superoxide; It perhaps is azo cpd; Said catalyzer also can be made up of two kinds in the above-mentioned catalyst type or more kinds of catalyzer.
10. method as claimed in claim 9 is characterized in that: said persulphate is one or more in ammonium persulphate, Potassium Persulphate, the Sodium Persulfate; Said superoxide is one or more in hydrogen peroxide, peroxo-benzene, formyl and the tert-butyl peroxide; Said reductive agent is one or more in sulphite, hydrosulphite, protosalt, the organic amine; Said azo cpd is one or more in Diisopropyl azodicarboxylate, ABVN, the azo diisobutyl amidine hydrochloride.
11. method as claimed in claim 2 is characterized in that: the amount of catalyzer is the 0.001-3% of reaction feed liquid weight.
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Cited By (7)
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| CN104311328A (en) * | 2014-10-20 | 2015-01-28 | 柳州市天姿园艺有限公司 | Using method of humic acid fertilizer |
| CN104311322A (en) * | 2014-10-20 | 2015-01-28 | 柳州市天姿园艺有限公司 | Method for preparing humic acid fertilizer |
| CN105199057A (en) * | 2015-09-16 | 2015-12-30 | 西安石油大学 | Method for preparing multifunctional high-temperature-resistant drilling fluid treating agent |
| CN108641727A (en) * | 2018-04-25 | 2018-10-12 | 常州市蓝勖化工有限公司 | A kind of preparation method of soil conditioner |
| CN110317295A (en) * | 2018-03-29 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of bioactive molecule thinner and preparation method thereof |
| CN110724535A (en) * | 2019-11-01 | 2020-01-24 | 河南城建学院 | Novel ecological garden greening soil remediation treatment agent and preparation method thereof |
| CN113999680A (en) * | 2021-11-08 | 2022-02-01 | 中国科学院兰州化学物理研究所 | Organic polymer saline soil modifier and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311328A (en) * | 2014-10-20 | 2015-01-28 | 柳州市天姿园艺有限公司 | Using method of humic acid fertilizer |
| CN104311322A (en) * | 2014-10-20 | 2015-01-28 | 柳州市天姿园艺有限公司 | Method for preparing humic acid fertilizer |
| CN105199057A (en) * | 2015-09-16 | 2015-12-30 | 西安石油大学 | Method for preparing multifunctional high-temperature-resistant drilling fluid treating agent |
| CN105199057B (en) * | 2015-09-16 | 2017-11-17 | 西安石油大学 | A kind of preparation method of multi-functional high temperature resistant drilling fluids inorganic agent |
| CN110317295A (en) * | 2018-03-29 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of bioactive molecule thinner and preparation method thereof |
| CN110317295B (en) * | 2018-03-29 | 2021-06-11 | 中国石油化工股份有限公司 | Active molecule viscosity reducer and preparation method thereof |
| CN108641727A (en) * | 2018-04-25 | 2018-10-12 | 常州市蓝勖化工有限公司 | A kind of preparation method of soil conditioner |
| CN110724535A (en) * | 2019-11-01 | 2020-01-24 | 河南城建学院 | Novel ecological garden greening soil remediation treatment agent and preparation method thereof |
| CN113999680A (en) * | 2021-11-08 | 2022-02-01 | 中国科学院兰州化学物理研究所 | Organic polymer saline soil modifier and preparation method thereof |
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Effective date of registration: 20190509 Address after: 226400 North Road of Yangkou Port Lingang Industrial Park Center, Changsha Town, Rudong County, Nantong City, Jiangsu Province Patentee after: Nantong Keyi Chemical Co., Ltd. Address before: 101309 Beijing Xitao Technology Development Co., Ltd. No. 9 Yangmu Road, Qianwanggezhuang, Mulin Town, Shunyi District, Beijing Patentee before: Beijing Xitao Development Tech Co., Ltd. |
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