CN102617815B - Natural nutritional high-water-absorptivity resin and preparation method thereof - Google Patents
Natural nutritional high-water-absorptivity resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a natural nutritional high-water-absorptivity resin, belonging to the technical field of high molecular materials. Natural sheep manure powder (more than 120 meshes), acrylic acid and raw paligorskite are used as base materials, N,N'-methylene-bis-acrylamide is used as a crosslinking agent, and potassium persulfate is used as an initiator; and in a water solution, free-radical initiation is carried out, so that the acrylic acid, natural sheep manure powder and raw paligorskite are subjected to graft polymerization, thereby obtaining the natural nutritional high-water-absorptivity resin. The test on water absorptivity, water retention property, salt tolerance, elementary analysis and biodegradation proves that the composite material has the advantages of high water absorption rate, high water absorption amount, long water retention time, favorable salt tolerance, abundant nutrient elements, high biodegradability and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of High hydrophilous resin, relate in particular to a kind of natural sheep excrement powder, vinylformic acid, the former mineral of polygorskite natural nutrition type High hydrophilous resin as base material of take; The present invention also relates to the preparation method of this High hydrophilous resin simultaneously.
Background technology
High hydrophilous resin (Superabsorbent Polymers is called for short SAP) refers to that by hydration, can absorb rapidly the deadweight hundreds of is gel to several thousand times of distilled water or tens times of physiological saline, even, in the situation that pressurization also is difficult for a kind of lightly crosslinked high molecular polymer of dehydration, be a kind of Novel chemical preparation grown up in recent ten years.The superior performance of High hydrophilous resin, purposes is very extensive, at aspects such as various fields such as material of construction, daily-use chemical industry, petroleum industry, environment-protecting industrial, fiber industry, electronic industries, have broad application prospects, especially the aspects such as agricultural gardening and medical sanitary have become indispensable material; Simultaneously, High hydrophilous resin has extremely strong water-absorbent and water-retentivity, also has fertilizer efficiency concurrently after adding fertilizer component; Moreover, the development High hydrophilous resin will greatly enrich polymer science, particularly enrich the content of functional high molecule material science, the development of the processing Theory of Polymer Synthesizing theory and material will further be promoted, also enriched the content of elastogel science, particularly will make the macromolecule hydrogel theory bring new development; The exploitation of High hydrophilous resin also will bring the development of Relevant Subjects such as medical science, physiotechnology, physiological hygiene, waterborne, life science etc.So in short decades, High hydrophilous resin has caused the great attention of countries in the world, thereby obtains developing so rapidly.The in the past few years research work of the High hydrophilous resin of China development is rapider, presents one scene of flourishing life.
High hydrophilous resin generally adopts starch, Mierocrystalline cellulose and unsaturated organic monomers graft copolymerization to make, or directly synthetic with unsaturated organic monomers.Water-holding agent commonly used has solid-state and liquid two kinds, and solid-state have again powder, thin slice and fibrous three kinds, with Powdered most widely used.The U.S., at initial stage in the 60's development and application water-retaining agent at first, applies at west droughty area as " improving the important tool of water regime ", has obtained good effect.Research and the production development of Japan's water-retaining agent are very fast, and its water-retaining agent output is near total half of producing in the world.The area of China desert and arid area is large, using hydroscopic high-molecular resin to do water-loss reducer of soil is to solve the effective means of this problem of farm crop water saving, but this type of water-holding agent is due to expensive raw material price, price is high, there is certain difficulty in universal use, therefore around how reducing this type of water-holding agent cost, has carried out many research work.
The sheep excrement is a kind of quick-acting, slight alkalinity, and organic matter is many, and fertilizer efficiency is fast, is suitable for the hot manure of the natural green of various soil applications, its chemical composition: the sheep excrement contains organic matter 24～27%, nitrogen (N) 0.7～0.8%, phosphorus (P
2O
5) 0.45～0.6%, potassium (K
2O) 0.4～0.5%.The sheep excrement contains organic more than other animal manure, and excrement matter is thinner, and nutriment in a fertilizer is dense, and extensively model is for planting edible mushroom, trees, the growth of the farm crop such as orchard, flowers, vegetables; Simultaneously, the sheep excrement is a kind of good fertilizer by fermentation, uses it to make fertilizer, can improve soil property, is to prevent the hardening soil, and economic worth is fine.
Polygorskite soil is a kind of Shuifu County's alumina magnesia silicate that contains, and its molecular formula is Mg
5Si
8O
2(OH)
44H
2O, belong to the duplex structure (hornblende) of silicate and the transitional type between laminate structure (mica group), grows duplex structure along the c axle, grows laminate structure along a, b axle, forms and have the special layers chain crystalline structure that is different from layer mineral.In Jiangsu, the provinces such as Anhui, Gansu, polygorskite soil rich in mineral resources, it is bar-shaped or fibrous that its crystal is, length-to-diameter ratio is large, is a kind of natural monodimension nanometer material.As the filler of matrix material, can effectively improve the gel-strength of matrix material, thermotolerance etc.
At present, utilize absorbent resin prepared by natural matter to have a lot, for example, super absorbent resin prepared by the disclosed employing Wheat Straw of Chinese patent (CN101735396A), Chinese patent (CN102093513A) discloses a kind of yam starch and vinylformic acid of having utilized and has prepared High hydrophilous resin, Chinese patent (CN 101143957A) discloses a kind of acid heat treatment attapulgite clay composite water-loss reducer etc., but utilizes natural sheep excrement all not report in current document for raw material prepares composite material with high water absorption.
Summary of the invention
The purpose of this invention is to provide a kind of high water absorbing resin in nutrition type;
Another object of the present invention is to provide a kind of preparation method of high water absorbing resin in nutrition type.
(1) preparation of natural nutrition type High hydrophilous resin
Natural nutrition type High hydrophilous resin of the present invention, be take sheep excrement powder, the former mineral of polygorskite, vinylformic acid, be base material, with N, N '-methylene-bisacrylamide is linking agent, Potassium Persulphate is initiator, in water, cause by free radical, make the former mineral graft polymerization of vinylformic acid, sheep excrement powder and polygorskite and obtain.
The concrete preparation method of natural nutrition type High hydrophilous resin, be that the sheep excrement powder be crushed to more than 120 orders is evenly spread in water, and (concrete pressure is under 0.01Mpa ~ 0.04Mpa), is heated to 50 ~ 70 ℃, gelatinization 25 ~ 35min in nitrogen protection, reduced pressure; Cool to 55 ~ 65 ℃, add vinylformic acid, polygorskite soil and linking agent N, N '-methylene-bisacrylamide, stir 5 ~ 15min; Add again initiator potassium persulfate, in 65 ~ 75 ℃ of stirring 20 ~ 40min, obtain the crosslinking polymerization product, filter, wash, dry, pulverize, cross 20 mesh sieves, both.
Described sheep excrement powder, the former mineral of polygorskite, vinylformic acid be take the quality of 1: 0.5: 4 ~ 1: 2: 7 than proportioning (optimum formula is 1: 1: 5).
Described linking agent N, the consumption of N '-methylene-bisacrylamide are 0.1 ~ 0.3% of sheep excrement powder, vinylformic acid, the former mineral total mass of polygorskite.
The consumption of described initiator potassium persulfate is 0.4 ~ 0.6 % of sheep excrement powder, the former mineral of polygorskite, vinylformic acid total mass.
Described stirring velocity is 80 ~ 120 to turn/min.
The former mineral of described polygorskite are to be crushed to the above powder of 120 orders.
(2) performance test of natural nutrition type High hydrophilous resin
Suction amount of purified water below by the natural nutrition type High hydrophilous resin that best experimental formula is obtained is tested.
1, water regain test
Fig. 1 is that High hydrophilous resin is inhaled the distilled water curve.By Fig. 1, learnt, this water-absorbing resin becomes good linear growth substantially in front 210 min pick ups, and it is saturated at 240 min, to reach the imbibition swelling, and maximum liquid absorption is 586g/g.Illustrate that this water-absorbing resin has preferably rate of liquid aspiration and imbibition capacity.
2, water-retaining capacity test
Fig. 2 is High hydrophilous resin water conservation time curve.By Fig. 2, learnt, front 50 min of this water-absorbing resin have larger fluid loss, reason is that the runny water that is stored in the three-dimensional space of resin easily loses when adopting tea-bag suspension method test fluid loss property, front 50 min percentages of water loss are 1.12g/min, and the resin that this swelling is saturated reaches dehydration balance substantially after 120 min.Illustrate that this resin material has water retention capacity preferably.
3, repeat water absorption test
Fig. 3 is that High hydrophilous resin repeats the imbibition curve.By Fig. 3, learnt, this water-absorbing resin has repeated multiple times suction distilled water, the ability of tap water and 0.9% sodium chloride solution, and at every turn after repeating imbibition the washing lotion amount substantially remain constant, illustrate that this water-absorbing resin has outstanding imbibition ability repeatedly, has very large using value.
4, High hydrophilous resin infrared test
Fig. 4,5,6,7 is respectively the infrared spectrum of sheep excrement powder, polygorskite, sheep excrement/acrylic absorbent resin, sheep excrement/vinylformic acid/polygorskite water-absorbing resin.3419.78 cm of Fig. 4
-1For sheep excrement powder-OH stretching vibration absorption peak, 2920.22 cm
-1With 2851.65 cm
-1Be respectively C-H stretching vibration and flexural vibration absorption peak, 1036.73 cm
-1For C-O stretching vibration absorption peak.The 3553.08cm of Fig. 5
-1And 3402.58cm
-1Be respectively (the Al)-OH of polygorskite soil, (Si)-OH stretching vibration absorption peak, 1656.12cm
-1For-the crooked stretching vibration absorption peak of OH, 1024.95 cm
-1With 984.07 cm
-1For Si-O stretching vibration absorption peak, 478.83 cm
-1For Si-O flexural vibration absorption peak.1697.96 cm of Fig. 6
-1For acrylic acid C=O stretching vibration absorption peak, the charateristic avsorption band of sheep excrement has appearred in addition, illustrate that reaction has occurred for sheep excrement and acrylate.1036.73 cm of Fig. 7
-1For the Si-O stretching vibration absorption peak of polygorskite soil, 470.63 cm
-1For the Si-O flexural vibration absorption peak of polygorskite soil, 1732.07 cm
-1For acrylic acid C=O stretching vibration absorption peak, 2934.18 cm
-1For C-H stretching vibration absorption peak, this show in the process of reaction polygorskite soil, sheep excrement and acrylate occurred in conjunction with or bonding closely form this matrix material.
5, thermogravimetric test
Fig. 8 is the High hydrophilous resin thermogravimetric curve, and wherein a figure adds the super absorbent resin resin composite material that polygorskite soil prepares, and b figure does not add the super absorbent resin resin composite material that polygorskite soil prepares.Result by Fig. 8 is as can be known, a figure has reflected that this super absorbent resin resin composite material has larger changes in weight three times in the temperature range of 0 ℃ to 800 ℃, at 350 ℃, changes in weight for the first time appearred in the past wherein, analyzing reason is that at high temperature matrix material has lost inner free water and crystal water, and the burning of part sheep excrement is arranged, and rate of weight loss is approximately 35.6%, changes in weight is 350 ℃ to 500 ℃ larger changes in weight once for the second time, its reason is preparation this matrix material raw material propylene acid used burning of being heated, and rate of weight loss is approximately 30.0%, changes in weight is at 680 ℃ to 800 ℃ for the third time, analyzing its reason may be the organic compound combustion in polygorskite soil.And rate of weight loss is approximately 10%.Same b figure also reflects that similar thermogravimetric changes, but contrast a schemes and the experimental result of b figure can be found out, this super absorbent resin resin composite material adds the resistance toheat that polygorskite soil can improve this matrix material in preparation process.
6, sem test
Fig. 9,10,11,12 is respectively the scanning electron microscope (SEM) photograph of sheep excrement/acrylic absorbent resin, sheep excrement/acrylic absorbent resin, sheep excrement/vinylformic acid/polygorskite water-absorbing resin, sheep excrement/vinylformic acid/polygorskite water-absorbing resin.From the scanning electron microscope (SEM) photograph of four width different amplification, can learn, in the process of this matrix material of preparation, add polygorskite soil and can obviously change its surface tissue and make it structure in porous three-dimensional net that surface becomes coarse convex-concave, further increased water suction effective surface area and the rate of water absorption of matrix material.
7, ultimate analysis: adopt EDS to measure the content of N, P, K element in High hydrophilous resin, wherein the N constituent content at 0.65 ~ 0.92%, P constituent content at 0.40 ~ 0.75, K constituent content 0.40 ~ 0.55%.
8, gel-strength: the matrix material that swelling is saturated never takes out in absorption liquid, by knife cut, becomes the little square of 1cm * 1 cm * 1 cm.The gel-strength of the saturated matrix material of method test swelling of compression is adopted in this experiment, the result demonstration, and matrix material gel-strength prepared by the present invention is at 170 g/cm
2Above.
9, biological degradation test: accurately take the dry water-absorbing resin of 0.5g and be dissolved in 1000ml distilled water to reach swelling saturated, adopt the free water hung in the gel that tea-bag method elimination swelling is saturated to weigh, be designated as m
i.The gel of elimination free water is embedded in soil, measured gel weight, and be designated as m in each 15 days
j.Gel biological degradation amount m=m
i-m
j.By test, find that High hydrophilous resin prepared by the present invention is all degradable about 350 days.
10, salt tolerance: accurately take the sodium chloride solution that the dry water-absorbing resin of 0.5g is dissolved in different concns, measure desiccant gel in specified time in different sodium chloride solutions liquid absorption, assess its salt tolerance, by test, find, High hydrophilous resin prepared by the present invention is adsorbing sodium chloride solution all more than 90 g/g.
In sum, the present invention has the following advantages compared to existing technology:
1, high water absorbing resin in nutrition type of the present invention has that rate of water absorption is fast, water regain is large, water conservation time length, good salt tolerance, the advantage such as nutritive element is abundant and biological degradability is good;
2, high water absorbing resin in nutrition type of the present invention has retained effective nutritive ingredient of sheep excrement, when having the high-hydroscopicity energy, also has improvement, rich soil, promotes the healthy and strong growth of farm crop, regulates soil acidity or alkalinity, the effects such as raising crop anti-adversity ability.
3, the present invention be take natural sheep excrement and is base-material, has developed the new purposes of natural sheep excrement, has enlarged effective utilization of resource, simultaneously the large-area applications that enlarges the water conservation matrix material is had to potential important meaning.
The accompanying drawing explanation
Fig. 1 is that High hydrophilous resin is inhaled the distilled water curve
Fig. 2 is High hydrophilous resin water conservation time curve
Fig. 3 is that High hydrophilous resin repeats the imbibition curve
Fig. 4 is the infrared general figure of sheep excrement
Fig. 5 is the polygorskite infrared spectrum
Fig. 6 is sheep excrement/acrylic absorbent resin infrared spectrum
Fig. 7 is sheep excrement/vinylformic acid/polygorskite water-absorbing resin infrared spectrum
Fig. 8 is the High hydrophilous resin thermogravimetric curve
Fig. 9 is sheep excrement/acrylic absorbent resin scanning electron microscope (SEM) photograph
Figure 10 is sheep excrement/acrylic absorbent resin scanning electron microscope (SEM) photograph
Figure 11 is sheep excrement/vinylformic acid/polygorskite water-absorbing resin scanning electron microscope (SEM) photograph
Figure 12 is sheep excrement/vinylformic acid/polygorskite water-absorbing resin scanning electron microscope (SEM) photograph.
Embodiment
Below by preparation and the performance of specific embodiment to high water absorbing resin in nutrition type of the present invention, be described further.
Embodiment 1
(1) preparation of high water absorbing resin in nutrition type: the accurate not natural sheep excrement of weighing 3g powder, add in the four-hole boiling flask that fills 30ml distilled water, whipping appts, condensing works, nitrogen protection device are installed.Under reduced pressure (concrete pressure 0.01Mpa), be heated to 50 ℃ of gelatinization 25 min, cool to 55 ℃, add 12 g vinylformic acid, 1.5 g polygorskite raw ore and 0.0165 g linking agent high-speed stirring 5min, add again 0.066 g initiator potassium persulfate, stir 20min at 65 ℃, obtain the crosslinking polymerization product.Take out cross-linking products, with anhydrous methanol dehydration 2 times, then be placed in baking oven with absolute ethanol washing, in 70 ℃ of oven dry, pulverize, cross 20 mesh sieves.
(2) performance test
Water regain: distilled water 583g/g, sodium chloride solution 146 g/g.
Gel-strength: 182 g/cm
2.
Embodiment 2
(1) preparation of high water absorbing resin in nutrition type: the accurate not natural sheep excrement of weighing 3g powder, add in the four-hole boiling flask that fills 30ml distilled water, whipping appts, condensing works, nitrogen protection device are installed.Under reduced pressure (concrete pressure 0.02Mpa), be heated to 50 ℃ of gelatinization 25 min, cool to 55 ℃, add 15 g vinylformic acid, 2.5 g polygorskite raw ore and 0.041 g linking agent high-speed stirring 10 min, add again 0.103 g initiator potassium persulfate, stir 30min at 70 ℃, obtain the crosslinking polymerization product.Take out cross-linking products, with anhydrous methanol dehydration 2 times, then be placed in baking oven with absolute ethanol washing, in 70 ℃ of oven dry, pulverize, cross 20 mesh sieves.
(2) performance test
Water regain: distilled water 547 g/g, sodium chloride solution 110 g/g.
Gel-strength: 190 g/cm
2.
Embodiment 3
(1) preparation of high water absorbing resin in nutrition type: the accurate not natural sheep excrement of weighing 3g powder, add in the four-hole boiling flask that fills 30ml distilled water, whipping appts, condensing works, nitrogen protection device are installed.Under reduced pressure (concrete pressure 0.03Mpa), be heated to 60 ℃ of gelatinization 30 min, cool to 60 ℃, add 18 g vinylformic acid, 3.5 g polygorskite raw ore and 0.049 g linking agent high-speed stirring 15min, add again 0.098 g initiator potassium persulfate, stir 40 min at 75 ℃, obtain the crosslinking polymerization product.Take out cross-linking products, with anhydrous methanol dehydration 2 times, then be placed in baking oven with absolute ethanol washing, in 70 ℃ of oven dry, pulverize, cross 20 mesh sieves.
(2) performance test
Water regain: distilled water 580 g/g, sodium chloride solution 137 g/g.
Gel-strength: 179 g/cm
2.
Embodiment 4
(1) preparation of high water absorbing resin in nutrition type: the accurate not natural sheep excrement of weighing 3g powder, add in the four-hole boiling flask that fills 30ml distilled water, whipping appts, condensing works, nitrogen protection device are installed.Under reduced pressure (concrete pressure 0.03Mpa), be heated to 60 ℃ of gelatinization 30 min, cool to 60 ℃, add 19 g vinylformic acid, 4.5 g polygorskite raw ore and 0.053 g linking agent high-speed stirring 5min, add again 0.159 g initiator potassium persulfate, stir 20 min at 65 ℃, obtain the crosslinking polymerization product.Take out cross-linking products, with anhydrous methanol dehydration 2 times, then be placed in baking oven with absolute ethanol washing, in 70 ℃ of oven dry, pulverize, cross 20 mesh sieves.
(2) performance test
Water regain: distilled water 534 g/g, sodium chloride solution 97 g/g.
Gel-strength: 171 g/cm
2.
(1) preparation of high water absorbing resin in nutrition type: the accurate not natural sheep excrement of weighing 3g powder, add in the four-hole boiling flask that fills 30ml distilled water, whipping appts, condensing works, nitrogen protection device are installed.Under reduced pressure (concrete pressure 0.02 Mpa), be heated to 70 ℃ of gelatinization 35 min, cool to 65 ℃, add 20 g vinylformic acid, 5.5 g polygorskite raw ore and 0.057 g linking agent high-speed stirring 10 min, add again 0.157 g initiator potassium persulfate, stir 30 min at 70 ℃, obtain the crosslinking polymerization product.Take out cross-linking products, with anhydrous methanol dehydration 2 times, then be placed in baking oven with absolute ethanol washing, in 70 ℃ of oven dry, pulverize, cross 20 mesh sieves.
(2) performance test
Water regain: distilled water 566 g/g, sodium chloride solution 121 g/g.
Gel-strength: 185 g/cm
2.
Embodiment 6
(1) preparation of high water absorbing resin in nutrition type: the accurate not natural sheep excrement of weighing 3g powder, add in the four-hole boiling flask that fills 30ml distilled water, whipping appts, condensing works, nitrogen protection device are installed.Under reduced pressure (concrete pressure 0.04 Mpa), be heated to 70 ℃ of gelatinization 35 min, cool to 65 ℃, add 21 g vinylformic acid, 6.0 g polygorskite raw ore and 0.09 g linking agent high-speed stirring 15 min, add again 0.18 g initiator potassium persulfate, stir 40 min at 75 ℃, obtain the crosslinking polymerization product.Take out cross-linking products, with anhydrous methanol dehydration 2 times, then be placed in baking oven with absolute ethanol washing, in 70 ℃ of oven dry, pulverize, cross 20 mesh sieves.
(2) performance test
Water regain: distilled water 520 g/g, sodium chloride solution 92 g/g.
Gel-strength: 197 g/cm
2
In above-described embodiment, the source of laboratory sample is as follows:
Sheep excrement: Huining County, Gansu Province; Vinylformic acid: Tianjin Kermel Chemical Reagent Co., Ltd., analytical pure; Potassium Persulfate: Chinese Laiyang City is chemical industry company limited in pairs, analytical pure; N, N '-methylene-bisacrylamide: Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure; Polygorskite: Baiyin City, gansu Province Huining County broken thread stone raw ore; Anhydrous methanol: Jinhuada Chemical Agent Co., Ltd., Guangzhou City; Dehydrated alcohol: Jinhuada Chemical Agent Co., Ltd., Guangzhou City; Sodium hydroxide; Tianjin chemical industry all generations company limited, analytical pure.
Claims (7)
1. the preparation method of a natural nutrition type High hydrophilous resin, to take sheep excrement powder, the former mineral of polygorskite, vinylformic acid to be base material, with N, N '-methylene-bisacrylamide is linking agent, Potassium Persulphate is initiator, in water, cause by free radical, make the former mineral graft polymerization of vinylformic acid, sheep excrement powder and polygorskite and obtain.
2. the preparation method of natural nutrition type High hydrophilous resin as claimed in claim 1, be that the sheep excrement powder be crushed to more than 120 orders is evenly spread in water, under nitrogen protection, reduced pressure, is heated to 50 ~ 70 ℃, gelatinization 25 ~ 35min; Cool to 55 ~ 65 ℃, add vinylformic acid, the former mineral of polygorskite and linking agent N, N '-methylene-bisacrylamide, stir 5 ~ 15min; Add again initiator potassium persulfate, in 65 ~ 75 ℃ of stirring 20 ~ 40min, obtain the crosslinking polymerization product, filter, wash, dry, pulverize and get final product.
3. the preparation method of natural nutrition type High hydrophilous resin as claimed in claim 1 or 2, it is characterized in that: described sheep excrement powder, the former mineral powder of polygorskite, vinylformic acid compare proportioning with the quality of 1: 0.5: 4 ~ 1: 2: 7.
4. the preparation method of natural nutrition type High hydrophilous resin as claimed in claim 1 or 2 is characterized in that: described linking agent N, the consumption of N '-methylene-bisacrylamide are 0.1 ~ 0.3% of sheep excrement powder, vinylformic acid, the former mineral total mass of polygorskite.
5. the preparation method of natural nutrition type High hydrophilous resin as claimed in claim 1 or 2 is characterized in that: the consumption of described initiator potassium persulfate is 0.4 ~ 0.6% of sheep excrement powder, the former mineral powder of polygorskite, vinylformic acid total mass.
6. the preparation method of natural nutrition type High hydrophilous resin as claimed in claim 1 or 2 is characterized in that: described stirring velocity is 80 ~ 120 to turn/min.
7. the preparation method of natural nutrition type High hydrophilous resin as claimed in claim 1 or 2, it is characterized in that: the former mineral of described polygorskite are the above powder of 120 orders.
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| CN102633942B (en) * | 2012-03-26 | 2014-08-20 | 黑龙江八一农垦大学 | Preparation method of agricultural nutritional super absorbent resin |
| CN102838995B (en) * | 2012-09-21 | 2015-01-07 | 西北师范大学 | Environment-friendly composite water retention agent, preparation and using method thereof |
| CN103755897B (en) * | 2014-01-03 | 2016-08-17 | 西北师范大学 | The preparation method of palygorskite base salt tolerance composite material with high water absorption |
| CN105254454A (en) * | 2015-11-23 | 2016-01-20 | 江苏省农业科学院 | Rapid water-storage and fertilization compound material for hill soil and preparation method of rapid water-storage and fertilization compound material |
| CN106674430A (en) * | 2016-11-22 | 2017-05-17 | 唐林元 | Preparation method of degradable agricultural water-retaining agent |
| CN106748091A (en) * | 2016-12-12 | 2017-05-31 | 蚌埠市亿丰生物有机肥有限公司 | A kind of water storage type organic substrate high for being complexed stone flour mineral and preparation method thereof |
| CN110591722B (en) * | 2019-09-19 | 2020-12-22 | 西北师范大学 | Preparation method of high-water-absorptivity composite resin with functions of preventing soil epidermis from shrinking and reducing water evaporation |
| CN112690160A (en) * | 2020-10-19 | 2021-04-23 | 西北师范大学 | Wild gymnosperm introduction domestication and breeding method |
| CN112876307B (en) * | 2021-01-21 | 2022-09-20 | 西北师范大学 | Degradable super absorbent resin with nitrogen fertilizer slow-release effect and preparation method thereof |
| CN114736687B (en) * | 2022-05-05 | 2023-04-11 | 中国农业大学 | Soil water-retaining agent and preparation method and application thereof |
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