CN113667071B - Potassium fulvate-based slow-release substrate acrylic water-absorbent resin - Google Patents
Potassium fulvate-based slow-release substrate acrylic water-absorbent resin Download PDFInfo
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- CN113667071B CN113667071B CN202110990225.6A CN202110990225A CN113667071B CN 113667071 B CN113667071 B CN 113667071B CN 202110990225 A CN202110990225 A CN 202110990225A CN 113667071 B CN113667071 B CN 113667071B
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- potassium fulvate
- sodium acrylate
- potassium
- resin
- heating
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000011591 potassium Substances 0.000 title claims abstract description 127
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 127
- 239000011347 resin Substances 0.000 title claims abstract description 121
- 229920005989 resin Polymers 0.000 title claims abstract description 121
- 239000002250 absorbent Substances 0.000 title claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 123
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229940047670 sodium acrylate Drugs 0.000 claims abstract description 90
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 31
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 229920001519 homopolymer Polymers 0.000 claims abstract description 21
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000003337 fertilizer Substances 0.000 abstract description 56
- 239000000126 substance Substances 0.000 abstract description 8
- 238000007306 functionalization reaction Methods 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 57
- 238000006731 degradation reaction Methods 0.000 description 57
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 42
- 239000012153 distilled water Substances 0.000 description 42
- 238000010521 absorption reaction Methods 0.000 description 34
- 238000013270 controlled release Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 13
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 239000005416 organic matter Substances 0.000 description 12
- 229910001414 potassium ion Inorganic materials 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000013268 sustained release Methods 0.000 description 7
- 239000012730 sustained-release form Substances 0.000 description 7
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 6
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002509 fulvic acid Substances 0.000 description 6
- 229940095100 fulvic acid Drugs 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 235000015097 nutrients Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010413 gardening Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000015816 nutrient absorption Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to a slow-release substrate acrylic water-absorbent resin based on potassium fulvate, which comprises: preparing a certain amount of potassium fulvate and sodium acrylate into an aqueous solution, and standing overnight; adding epichlorohydrin into the prepared aqueous solution, stirring uniformly, putting into a water bath, heating at constant temperature for dissolution, heating to 60-80 ℃ after the potassium fulvate is completely dissolved, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture; and cooling the obtained mixture of the potassium fulvate/sodium acrylate graft copolymer and the homopolymer, adding a curing agent ammonium persulfate and epichlorohydrin, uniformly stirring, heating to 60-80 ℃, and carrying out curing reaction for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin. The application can realize the preparation of resin and the one-time completion of product functionalization and solidification, and can be used in the fields of chemical fertilizers, pesticides, petroleum exploitation and the like.
Description
Technical Field
The application relates to a slow-release material, in particular to a slow-release base material acrylic water-absorbent resin based on potassium fulvate.
Background
One of the more widely used slow release materials is resins, with the most widely used water-absorbing resins. The high water absorbing agent is a functional polymer material with strong water absorption and excellent water retention, and has stable performance, excellent quality and wide raw material sources. Because the water purifier has a three-dimensional space network structure, the water purifier can quickly absorb liquid water which is hundreds times heavier than the water purifier and thousands times heavier than the water purifier through hydration, and therefore the water purifier is widely applied to the fields of agriculture and forestry, gardening, petroleum exploitation, daily chemical industry, environmental protection, food processing and the like.
The common problems of water-soluble resins in all sustained-release materials at present are: the graft resin has higher homopolymer content, and the system has higher years after being dissolved in water, mainly caused by the homopolymer, and causes certain difficulty for many applications. The aqueous solution polymerization yield is low, the polymerization speed is low, the product performance is poor, and the product post-treatment is difficult. In order to overcome the disadvantages of aqueous solution polymerization, non-aqueous solution polymerization is often employed, but the cost and process of non-aqueous solution polymerization are both more complex than aqueous solution polymerization and are costly.
The slow-release material is used in the fields of chemical fertilizers, pesticides and medicines at home and abroad, compared with the quick-acting fertilizer, the controlled-release fertilizer has the advantages of saving the fertilizer consumption, having obvious effect, protecting the ecological environment and having great economic benefit and environmental protection benefit. The coating method is most common in slow-release fertilizers.
The action mechanism of the coating method is physical controlled release, and the influencing factor is mainly temperature, so that the control of nutrient release time and quantity is easy and accurate, and the controlled release performance of the coating method is measured by a set of more perfect method. However, since the controlled release material and equipment are expensive, the cost of the product is high and it is difficult to enter the field. Therefore, new materials for coating equipment need to be developed in a new way.
The improvement of the fertilizer utilization rate by using different technical methods is a core in researching how to prevent or reduce the nutrient leaching problem, and the controlled release fertilizer (Controlled Release Fertilizers, abbreviated as CRFs) is an important means for solving the core problem. In a strict sense, controlled release fertilizers and slow release fertilizers (Slow Release Fertilizers, abbreviated as SRFs) are distinguished, the slow release fertilizers can only delay the release speed of the fertilizers, the aim of complete controlled release cannot be achieved, and the so-called controlled release fertilizers comprise the controlled release fertilizers and the slow release fertilizers.
Controlled release fertilizers (Controlled Release Fertilizers, abbreviated as CRFs) are prepared by various methods
The technical measures preset the release mode of the fertilizer in the growing season of crops, so that the nutrient release rule and nutrient absorption of the crops are synchronized as much as possible, and the fertilizer for improving the fertilizer efficiency is achieved. The names of the long-acting fertilizer, the slow-release fertilizer, the coated fertilizer, the fertilizer efficiency adjusting fertilizer, the controlled-release fertilizer and the like are different names of the fertilizer with the nutrient controlled-release characteristic according to the effect of the fertilizer or the main technical measures for developing the fertilizer in different stages of research and development of the fertilizer.
The ideal controlled release fertilizer should be one-time fertilization and can gradually release nutrients for the crops to absorb according to the needs of the crops in each growth period after application, thereby greatly reducing the loss caused by decomposition and volatilization and washing loss of the fertilizer, ensuring the crops to thrive, achieving the purposes of increasing the yield, improving the quality and saving the fertilizer, and having the advantages of saving the fertilizer, saving the labor, increasing the yield, increasing the income, improving the ecological environment, preventing excessive fertilizers from causing the burning seedlings of the crops and the like. Meanwhile, in order to avoid secondary pollution, the method is truly safe and environment-friendly, and the slow-release base material is required to have biodegradability and be harmless to soil and environment. The gradual degradation of the base material is utilized to achieve the aim of controlling the release of the pesticide.
At present, the consumption of common fertilizers in developed countries has a trend of zero growth and even negative growth, but the consumption of coated fertilizers still has high development at an annual growth rate of 9% -10%, the total annual consumption of coated fertilizers in the countries such as the United states, france and Japan is about 65 Wt%, and the consumption of the United states is about 70% at the maximum, and the coated fertilizers are mainly used in modern cultivation systems of golf courses, flowers, nursery gardens and gardening and large farms, are less in application in general agricultural production, and are only about 10% used in planting vegetables, fruits, rice and the like.
Although the slow release/controlled release fertilizer research in China starts later, the research can reach the unprecedented place. The slow release/controlled release fertilizer which is suitable for the conditions of China is developed in competition of various research institutes in China.
According to the related reports, the method is equivalent to the construction of a plurality of large-scale chemical fertilizer plants only by improving the utilization rate of the existing urea by 6 percent. The cost of the added fertilizer is deducted by calculating the yield increase by 10%, the yield value can be increased by about 200 hundred million yuan, and the economic and social benefits are obvious. Research and development of slow-release fertilizers are increasingly important, and the slow-release fertilizers have better utilization value than common fertilizers and are also increasingly accepted by consumers. Slow release/controlled release fertilizers have become an important development direction for 21 st century fertilizers. Although slow release/controlled release fertilizers have been commercialized and technology has been developed, the cost is not widely accepted due to the higher cost, and the cost is only below 0.5% of the total consumption of chemical fertilizers in the world. To widen the application of the slow-release fertilizer, the problems of improving the slow-release property of the fertilizer, reducing environmental pollution and the like by continuously perfecting the technology, and meanwhile, more work must be done in the aspect of seeking cheaper base materials and processes.
Disclosure of Invention
The application aims to provide a potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is used for realizing the preparation of the resin and the one-time completion of product functionalization and solidification.
The technical scheme adopted for solving the technical problems is as follows: the slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-40% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) Cooling the obtained mixture of the potassium fulvate/sodium acrylate graft copolymer and the homopolymer to 35-40 ℃, adding 1g of ammonium persulfate as a curing agent and 1.2g of epichlorohydrin, uniformly stirring, heating the system to 60-80 ℃, and curing for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is the potassium fulvate/sodium acrylate resin with a body structure.
The slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-40% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) Cooling the obtained potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture to 35-40 ℃, adding a certain amount of phosphate, stirring and dissolving, adding 1g of ammonium persulfate as a curing agent and 1.2g of epichlorohydrin, heating the system to 60-80 ℃ after uniform stirring, and curing for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is rich in phosphate type structural potassium fulvate/sodium acrylate resin.
The slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-30% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) Cooling the obtained potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture to 35-40 ℃, adding a certain amount of urea, stirring and dissolving, adding 1g of ammonium persulfate as a curing agent and 1-2g of epichlorohydrin, heating the system to 60-80 ℃ after uniform stirring, and curing for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is rich in urea type structural potassium fulvate/sodium acrylate resin.
The slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-30% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) And cooling the obtained mixture of the potassium fulvate/sodium acrylate graft copolymer and the homopolymer to 35-40 ℃, adding a certain amount of phosphate and urea, stirring for dissolution, adding 1g of ammonium persulfate as a curing agent and 1.2g of epichlorohydrin, heating the system to 60-80 ℃ after uniform stirring, and carrying out curing reaction for 0.5-1 hour to obtain the potassium fulvate/sodium acrylate resin rich in phosphate and urea type structures.
The addition amount of the phosphate and the urea in the application is added according to the use requirement.
The application has the following beneficial effects:
1. the application provides a potassium fulvate as a base material, which is prepared by graft copolymerization and then is prepared into various functional slow release products by a post-curing technology. The innovative technology of the application is that the preparation of the resin, the functionalization and the solidification of the product are completed at one time, and the application has wide performance adjustment range and wide application range.
2. The slow-release substrate of the potassium fulvate/sodium acrylate resin prepared by the application has the characteristics of simple curing process, easy functionalization, controllable slow-release time and the like. The prepared potassium fulvate/sodium acrylate resin slow-release base material can be used as a slow-release base material in a plurality of fields such as chemical fertilizers, pesticides, oil exploitation and the like, has the advantages of environmental protection, degradability and the like, has no pollution to the environment, and has wide application prospect and social and economic benefits.
3. The application provides a base material with a slow release effect and a reaction curing technology thereof, and determines the influence of the selection of a curing agent and a curing reaction technology on resin functionalization in the preparation process of potassium fulvate/acrylic resin.
4. The application mainly solves the problems of application limitation, complex manufacturing process and the like in the current slow-release material field, and simultaneously carries out effective control technology on the slow-release material, in particular to the effective period in the chemical fertilizer and pesticide field.
Drawings
FIG. 1 is a graph of degradation amount versus time.
Detailed Description
The application is further described below:
example 1:
(A) 30g of sodium acrylate is weighed, added into 70g of distilled water, stirred and dissolved, and stood for standby.
(B) Adding 10g of potassium fulvate and 5g of epichlorohydrin into the solution (30% sodium acrylate aqueous solution), putting the mixed solution into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 1g of initiator potassium persulfate, stirring fully, and initiating polymerization reaction for 4-6 hours.
(C) Cooling the reaction system to below 45 ℃, adding 1g of ammonium persulfate and 1.2g of epichlorohydrin serving as a curing initiator, after the curing initiator is uniformly dispersed, raising the temperature of the system to 65-70 ℃, and carrying out curing reaction for 0.5 hour to obtain the potassium fulvate/sodium acrylate grafted resin.
(D) And (3) measuring the water absorption multiple, cutting and drying the obtained fulvic acid potassium/sodium acrylate grafted resin, drying the resin to constant weight at 45 ℃ under vacuum, weighing a certain amount of resin, putting the resin into distilled water and 0.9% saline, and measuring the water absorption multiple in the distilled water and the 0.9% saline respectively.
(E) Sustained release degradation experiment: crushing the dried resin, weighing the resin with certain granularity and certain mass, putting the resin into distilled water and 0.9% saline water, measuring the total organic matter content and potassium ion concentration in the degradation liquid at intervals, and determining a resin degradation speed and time relation curve.
Taking the potassium fulvate/sodium acrylate grafted resin prepared according to the method of example 1, and respectively measuring the water absorption times and degradation curves of the potassium fulvate/sodium acrylate grafted resin in distilled water and 0.9% saline water in a beaker, wherein the water absorption times and the water absorption times of the water absorbent resin prepared in example 1 are 60-90 times of distilled water and 40-60 times of 0.9% saline water; the degradation rate curve shows that after the resin is added into water and saline water, the concentration of degradation liquid is saturated within 24-48 hours respectively, and the total organic matter content and the potassium ion concentration in the solution are not increased any more; filtering out the saturated degradation liquid, adding new distilled water or 0.9% saline, continuing the degradation experiment, repeating the above operation until the resin is completely degraded, and recording the relationship curve of the whole degradation amount and time, wherein the result is shown in figure 1 (dry resin mass is 1.57 g).
Example 2:
(A) Weighing 20g of sodium acrylate, adding into 80g of distilled water, stirring for dissolution, and standing overnight for later use.
(B) 7.5g of potassium fulvate and 4g of epichlorohydrin are added into the solution (20% sodium acrylate aqueous solution), the mixed solution is put into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolution, after the potassium fulvate is completely dissolved, the system temperature is raised to 60-80 ℃, 1g of initiator potassium persulfate is added, and the mixture is fully stirred to initiate polymerization reaction for 3-5 hours.
(C) Cooling the reaction system to below 45 ℃, adding 1g of ammonium persulfate and 1.2g of epichlorohydrin serving as a curing initiator, after the curing initiator is uniformly dispersed, raising the temperature of the system to 65-70 ℃, and carrying out curing reaction for 0.8 hour to obtain the potassium fulvate/sodium acrylate grafted resin.
(D) And (3) measuring the water absorption multiple, cutting and drying the obtained fulvic acid potassium/sodium acrylate grafted resin, drying the resin to constant weight at 45 ℃ under vacuum, weighing a certain amount of resin, putting the resin into distilled water and 0.9% saline, and measuring the water absorption multiple in the distilled water and the 0.9% saline respectively.
(E) Sustained release degradation experiment: crushing the dried resin, weighing the resin with certain granularity and certain mass, putting the resin into distilled water and 0.9% saline water, measuring the total organic matter content and potassium ion concentration in the degradation liquid at intervals, and determining a resin degradation speed and time relation curve.
Taking the potassium fulvate/sodium acrylate grafted resin prepared according to the method of example 2, and respectively measuring the water absorption times and degradation curves of the potassium fulvate/sodium acrylate grafted resin in distilled water and 0.9% saline in a beaker, wherein the water absorption times and the water absorption times of the water absorbent resin prepared in case 2 are 68 times and 46 times in the distilled water and the 0.9% saline; the degradation rate curve shows that after the resin is added into water and saline water, the concentration of degradation liquid is saturated within 24-48 hours respectively, and the total organic matter content and the potassium ion concentration in the solution are not increased any more; filtering out the saturated degradation liquid, adding new distilled water or 0.9% saline, continuing the degradation experiment, repeating the above operation until the resin is completely degraded, and recording the relation curve of the whole degradation amount and time.
Example 3:
(A) 30g of sodium acrylate is weighed, added into 70g of distilled water, stirred and dissolved, and stood for standby.
(B) 5g of potassium fulvate and 3g of epichlorohydrin are added into the solution (30% sodium acrylate aqueous solution), the mixed solution is put into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolution, after the potassium fulvate is completely dissolved, the system temperature is increased to 60-80 ℃, 1g of initiator potassium persulfate is added, and the mixture is stirred fully to initiate polymerization reaction for 2-4 hours.
(C) Cooling the reaction system to below 45 ℃, adding 1g of ammonium persulfate and 1.2g of epichlorohydrin as a curing initiator, after the curing initiator is uniformly dispersed, raising the temperature of the system to 65-70 ℃, and carrying out curing reaction for 1 hour to obtain the potassium fulvate/sodium acrylate grafted resin.
(D) And (3) measuring the water absorption multiple, cutting and drying the obtained fulvic acid potassium/sodium acrylate grafted resin, drying the resin to constant weight at 45 ℃ under vacuum, weighing a certain amount of resin, putting the resin into distilled water and 0.9% saline, and measuring the water absorption multiple in the distilled water and the 0.9% saline respectively.
(E) Sustained release degradation experiment: crushing the dried resin, weighing the resin with certain granularity and certain mass, putting the resin into distilled water and 0.9% saline water, measuring the total organic matter content and potassium ion concentration in the degradation liquid at intervals, and determining a resin degradation speed and time relation curve.
Taking the potassium fulvate/sodium acrylate grafted resin prepared according to the method of example 3, and respectively measuring the water absorption multiple and degradation curve of the potassium fulvate/sodium acrylate grafted resin in distilled water and 0.9% saline, wherein the water absorption multiple and 60 times of the distilled water and the 0.9% saline are obtained as a result of the water absorption multiple of the water absorbent resin prepared in case 3; the degradation rate curve shows that after the resin is added into water and saline water, the concentration of degradation liquid is saturated within 24-48 hours respectively, and the total organic matter content and the potassium ion concentration in the solution are not increased any more; filtering out the saturated degradation liquid, adding new distilled water or 0.9% saline, continuing the degradation experiment, repeating the above operation until the resin is completely degraded, and recording the relation curve of the whole degradation amount and time.
Example 4:
(A) 30g of sodium acrylate is weighed, added into 70g of distilled water, stirred and dissolved, and stood for standby.
(B) Adding 10g of potassium fulvate and 5g of epichlorohydrin into the solution (30% sodium acrylate aqueous solution), putting the mixed solution into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 1g of initiator potassium persulfate, stirring fully, and initiating polymerization reaction for 4-6 hours.
(C) Cooling the reaction system to below 45 ℃, adding 5g of sodium dihydrogen phosphate, stirring and dissolving, adding 1g of ammonium persulfate and 1.2g of epichlorohydrin as curing initiator, after the curing initiator is uniformly dispersed, raising the temperature of the system to 65-70 ℃, and carrying out curing reaction for 2-10 hours to obtain the phosphorus-containing potassium fulvate/sodium acrylate grafted resin.
(D) And (3) measuring the water absorption multiple, cutting and drying the obtained fulvic acid potassium/sodium acrylate grafted resin, drying the resin to constant weight at 45 ℃ under vacuum, weighing a certain amount of resin, putting the resin into distilled water and 0.9% saline, and measuring the water absorption multiple in the distilled water and the 0.9% saline respectively.
(E) Sustained release degradation experiment: crushing the dried resin, weighing the resin with certain granularity and certain mass, putting the resin into distilled water and 0.9% saline water, measuring the total organic matter content and potassium ion concentration in the degradation liquid at intervals, simultaneously measuring the phosphorus content, and determining a resin degradation speed and time relation curve.
Taking the potassium fulvate/sodium acrylate grafted resin prepared according to the method of example 4, and respectively measuring the water absorption times and degradation curves of the potassium fulvate/sodium acrylate grafted resin in distilled water and 0.9% saline in a beaker, wherein the water absorption times and 48 times of the distilled water and the 0.9% saline are respectively measured, so that the water absorption times and 48 times of the water absorption resin prepared in the case 4 are obtained; the degradation rate curve shows that after the resin is added into water and saline water, the concentration of degradation liquid is saturated within 24-48 hours respectively, and the total organic matter content and the potassium ion concentration in the solution are not increased any more; filtering out the saturated degradation liquid, adding new distilled water or 0.9% saline, continuing the degradation experiment, repeating the above operation until the resin is completely degraded, and recording the relation curve of the whole degradation amount and time.
Example 5:
(A) 30g of sodium acrylate is weighed, added into 70g of distilled water, stirred and dissolved, and stood for standby.
(B) Adding 10g of potassium fulvate and 5g of epichlorohydrin into the solution (30% sodium acrylate aqueous solution), putting the mixed solution into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 1g of initiator potassium persulfate, stirring fully, and initiating polymerization reaction for 4-6 hours.
(C) Cooling the reaction system to 45 ℃, adding 5g of urea, stirring and dissolving, adding 1g of ammonium persulfate and 1-2g of epichlorohydrin as curing initiator, after the curing initiator is uniformly dispersed, raising the temperature of the system to 65-70 ℃, and carrying out curing reaction for 2-10 hours to obtain the urea-containing potassium fulvate/sodium acrylate grafted resin.
(D) And (3) measuring the water absorption multiple, cutting and drying the obtained fulvic acid potassium/sodium acrylate grafted resin, drying the resin to constant weight at 45 ℃ under vacuum, weighing a certain amount of resin, putting the resin into distilled water and 0.9% saline, and measuring the water absorption multiple in the distilled water and the 0.9% saline respectively.
(E) Sustained release degradation experiment: crushing the dried resin, weighing the resin with certain granularity and certain mass, putting the resin into distilled water and 0.9% saline water, measuring the total organic matter content and potassium ion concentration in the degradation liquid at intervals, simultaneously measuring the nitrogen content, and determining a resin degradation speed and time relation curve.
Taking the potassium fulvate/sodium acrylate grafted resin prepared according to the method of example 5, and respectively measuring the water absorption times and degradation curves of the potassium fulvate/sodium acrylate grafted resin in distilled water and 0.9% saline in a beaker, wherein the water absorption times and 48 times of the distilled water and the 0.9% saline are respectively measured, so that the water absorption times and 48 times of the water absorption resin prepared in case 5 are obtained; the degradation rate curve shows that after the resin is added into water and saline water, the concentration of degradation liquid is saturated within 24-48 hours respectively, and the total organic matter content and the potassium ion concentration in the solution are not increased any more; filtering out the saturated degradation liquid, adding new distilled water or 0.9% saline, continuing the degradation experiment, repeating the above operation until the resin is completely degraded, and recording the relation curve of the whole degradation amount and time.
Example 6:
(A) 30g of sodium acrylate is weighed, added into 70g of distilled water, stirred and dissolved, and stood for standby.
(B) Adding 10g of potassium fulvate and 5g of epichlorohydrin into the solution (30% sodium acrylate aqueous solution), putting the mixed solution into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 1g of initiator potassium persulfate, stirring fully, and initiating polymerization reaction for 4-6 hours.
(C) Cooling the reaction system to below 45 ℃, adding 5g of sodium dihydrogen phosphate, 5g of urea, 1g of ammonium persulfate and 1.2g of epichlorohydrin as curing initiator, after the curing initiator is uniformly dispersed, raising the temperature of the system to 65-70 ℃, and carrying out curing reaction for 2-10 hours to obtain the urea-containing potassium fulvate/sodium acrylate grafted resin.
(D) And (3) measuring the water absorption multiple, cutting and drying the obtained fulvic acid potassium/sodium acrylate grafted resin, drying the resin to constant weight at 45 ℃ under vacuum, weighing a certain amount of resin, putting the resin into distilled water and 0.9% saline, and measuring the water absorption multiple in the distilled water and the 0.9% saline respectively.
(E) Sustained release degradation experiment: crushing the dried resin, weighing the resin with certain granularity and certain mass, putting the resin into distilled water and 0.9% saline water, measuring the total organic matter content and potassium ion concentration in the degradation liquid at intervals, simultaneously measuring the nitrogen and phosphorus content, and determining a resin degradation speed and time relation curve.
Taking the potassium fulvate/sodium acrylate grafted resin prepared according to the method of example 6, and respectively measuring the water absorption times and degradation curves of the potassium fulvate/sodium acrylate grafted resin in distilled water and 0.9% saline in a beaker, wherein the water absorption times and 48 times of the distilled water and the 0.9% saline are obtained as a result of the water absorption times and the 48 times of the water absorption resin prepared in case 6; the degradation rate curve shows that after the resin is added into water and saline water, the concentration of degradation liquid is saturated within 24-48 hours respectively, and the total organic matter content and the potassium ion concentration in the solution are not increased any more; filtering out the saturated degradation liquid, adding new distilled water or 0.9% saline, continuing the degradation experiment, repeating the above operation until the resin is completely degraded, and recording the relation curve of the whole degradation amount and time.
The application takes potassium fulvate as a base material, and performs graft polymerization with acrylic monomers under the action of an initiator to obtain a graft copolymer and a homopolymer, a crosslinking curing agent is added for further reaction to obtain resin, and various functional substances can be added before curing to obtain a corresponding slow-release material.
The water-soluble slow-release base material is always lack of a universal material, and the application adopts green and environment-friendly potassium fulvate and acrylic monomers to polymerize, and then endows the resin with corresponding functions in the process of crosslinking and curing. The potassium fulvate is a degradable basic skeleton structure in the resin, the sodium acrylate is a branched chain structure mainly absorbing water in the resin after polymerization, and the crosslinking curing agent is a function of crosslinking the graft copolymer and controlling the release speed and degradation speed.
Claims (4)
1. A potassium fulvate-based slow-release substrate acrylic water-absorbent resin, which is characterized in that: the slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-40% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) Cooling the obtained mixture of the potassium fulvate/sodium acrylate graft copolymer and the homopolymer to 35-40 ℃, adding 1g of ammonium persulfate as a curing agent and 1.2g of epichlorohydrin, uniformly stirring, heating the system to 60-80 ℃, and curing for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is the potassium fulvate/sodium acrylate resin with a body structure.
2. A potassium fulvate-based slow-release substrate acrylic water-absorbent resin, which is characterized in that: the slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-40% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) Cooling the obtained potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture to 35-40 ℃, adding a certain amount of phosphate, stirring and dissolving, adding 1g of ammonium persulfate as a curing agent and 1.2g of epichlorohydrin, heating the system to 60-80 ℃ after uniform stirring, and curing for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is rich in phosphate type structural potassium fulvate/sodium acrylate resin.
3. A potassium fulvate-based slow-release substrate acrylic water-absorbent resin, which is characterized in that: the slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-30% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) Cooling the obtained potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture to 35-40 ℃, adding a certain amount of urea, stirring and dissolving, adding 1g of ammonium persulfate as a curing agent and 1-2g of epichlorohydrin, heating the system to 60-80 ℃ after uniform stirring, and curing for 0.5-1 hour to obtain the potassium fulvate-based slow-release substrate acrylic water-absorbent resin which is rich in urea type structural potassium fulvate/sodium acrylate resin.
4. A potassium fulvate-based slow-release substrate acrylic water-absorbent resin, which is characterized in that: the slow-release base material acrylic water-absorbent resin based on the potassium fulvate is prepared by the following steps:
(A) A certain amount of potassium fulvate and sodium acrylate are prepared into a 15-30% aqueous solution, wherein the weight percentages of the potassium fulvate and the sodium acrylate are as follows: 14-30% of potassium fulvate, 70-86% of sodium acrylate and standing overnight;
(B) Taking 100-140g of the prepared aqueous solution, adding 3-8 g of epichlorohydrin, uniformly stirring, putting into a water bath with the temperature of 40-60 ℃ for constant-temperature heating and dissolving, after the potassium fulvate is completely dissolved, heating the system to the temperature of 60-80 ℃, adding 0.5-1 g of initiator potassium persulfate, and reacting for 2-6 hours to obtain a potassium fulvate/sodium acrylate graft copolymer and homopolymer mixture;
(C) And cooling the obtained mixture of the potassium fulvate/sodium acrylate graft copolymer and the homopolymer to 35-40 ℃, adding a certain amount of phosphate and urea, stirring for dissolution, adding 1g of ammonium persulfate as a curing agent and 1.2g of epichlorohydrin, heating the system to 60-80 ℃ after uniform stirring, and carrying out curing reaction for 0.5-1 hour to obtain the potassium fulvate/sodium acrylate resin rich in phosphate and urea type structures.
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| JP2003082041A (en) * | 2001-09-12 | 2003-03-19 | Tokyo Metropolis | Water-absorbing material, method for producing the same, water-absorptive material |
| CN101967260A (en) * | 2010-10-09 | 2011-02-09 | 内蒙古大学 | Method for preparing plant nutrient and sodium fulvate-containing super water absorbent resin |
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| CN109912755A (en) * | 2019-03-27 | 2019-06-21 | 陕西科技大学 | A kind of fulvic acid type three-dimensional network composite material and preparation method and application |
| CN112521226A (en) * | 2020-11-26 | 2021-03-19 | 河南省科学院高新技术研究中心 | Water-retention and fertilizer loss-control additive and continuous production process thereof |
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| JP2003082041A (en) * | 2001-09-12 | 2003-03-19 | Tokyo Metropolis | Water-absorbing material, method for producing the same, water-absorptive material |
| CN101967260A (en) * | 2010-10-09 | 2011-02-09 | 内蒙古大学 | Method for preparing plant nutrient and sodium fulvate-containing super water absorbent resin |
| CN108948293A (en) * | 2018-06-15 | 2018-12-07 | 陕西省土地工程建设集团有限责任公司 | A kind of humic acid base compound water retaining agent and preparation method thereof |
| CN109912755A (en) * | 2019-03-27 | 2019-06-21 | 陕西科技大学 | A kind of fulvic acid type three-dimensional network composite material and preparation method and application |
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