CN101974130B - Process formula of superabsorbent resin containing covalent type and ion type nitrogen elements - Google Patents
Process formula of superabsorbent resin containing covalent type and ion type nitrogen elements Download PDFInfo
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Abstract
The invention discloses a process formula for synthesizing superabsorbent resin containing covalent type and ion type nitrogen elements by using potato starch or carboxymethyl potato starch, crylic acid, acrylamide and ammonia water as main raw materials. The water absorption of the prepared superabsorbent resin containing different types of nitrogen elements is greatly improved, the superabsorbent resin also contains the nitrogen elements required by plant growth, and like products are not available on the market. The superabsorbent resin containing different types of nitrogen elements can have great application values in the aspects of water retention, desert prevention and control, plant growth, and the like in arid regions.
Description
Technical field
The present invention relates to be used for the prescription of the super absorbent resin fat prod of agricultural, forestry, livestock industry and gardening, be meant that especially with yam starch or carboxymethyl potato starch, vinylformic acid, acrylamide, ammoniacal liquor be the synthetic prescription that contains different kenel nitrogen element High hydrophilous resins of main raw material.
Background technology
Super absorbent resin also claims the super-strong moisture absorbing polymkeric substance, it is a kind of high molecular polymer that contains strongly hydrophilic groups such as carboxyl, hydroxyl and have the water swelling type of certain degree of crosslinking, the water insoluble organic solvent that also is insoluble to, can absorb the hundred times of own wt even thousands of times water, and the gel that generates after the water-swelling has good water-retentivity and weathering resistance, in case water-swelling becomes hydrogel, even pressurization also is difficult to water sepn is come out.Simultaneously, super absorbent resin can be recycled.Therefore, more and more be subjected to people's attention.At present, super absorbent resin is used widely in fields such as industry, agricultural, forestry, sanitary product, and demonstrates vast potential for future development.
The preparation method of High hydrophilous resin is a lot, and synthesis material is abundant, and production technique is different.Though China is obtaining certain achievement aspect the research of High hydrophilous resin, but with abroad compare, gap is also quite big, and is low as the suction multiple of resin, salt resistant character is poor, suction back gel-strength is low, complex manufacturing, product cost height, kind are single etc.We should give full play to the resourceful advantage of China's yam starch, produce the High hydrophilous resin of high-quality suitable China's national situation, for becoming important agrochemicals and be applied to association area, High hydrophilous resin lays the foundation, have advantages such as the multiplying power of absorption height, speed be fast with the High hydrophilous resin of yam starch and carboxymethyl potato starch preparation, therefore have more wide application prospect.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of yam starch or carboxymethyl potato starch prepares the technical recipe that contains covalent type and ionic nitrogen element High hydrophilous resin with acrylamide, vinylformic acid and sodium salt thereof, ammoniacal liquor respectively.
Technical problem of the present invention is solved by following scheme: the technical recipe that contains covalent type and ionic nitrogen element High hydrophilous resin; it is characterized in that (1) is the synthetic High hydrophilous resin that contains covalent type and ionic nitrogen element of raw material with the yam starch: under the ice-water bath cooling; with concentration is that 25% sodium hydroxide solution and the vinylformic acid of removing stopper carry out neutralization reaction; cofabrication acrylamide soln; wherein yam starch and vinylformic acid; acrylamide; the mass ratio of sodium hydroxide is: 1: 3-5.25: 0.75-3: 0.168-2.624; yam starch and deionized water are with 1: the mass ratio of 4-6 under agitation mixes; under condition of water bath heating, carry out gelatinization; with vinylformic acid and sodium salt solution thereof; acrylamide soln mixes with yam starch after the gelatinization; and the persulphate that adds the 1.5%-1.9% of yam starch quality is made initiator; under nitrogen protection, stir certain hour; reactant is mixed; heat up gradually with heating in water bath then and reach 60 ℃-80 ℃ until temperature; make yam starch and vinylformic acid and sodium salt thereof; acrylamide carries out graft copolymerization in this temperature range; reaction process is carried out under nitrogen protection; and make product under the boiling water bath condition, be incubated 1-2h; then product is dried in baking oven to constant weight; pulverize; obtain containing the High hydrophilous resin of covalent nitrogen; soaked 1-2 days with 1.20-12.65g ammoniacal liquor; elimination free ammoniacal liquor; emanate with dehydrated alcohol again; naturally dried under the room temperature 1-2 days; product is dried in baking oven to constant weight; pulverize, promptly being able to yam starch is the High hydrophilous resin that contains covalent type and ionic nitrogen element of raw material.
Technique scheme is described, and the prepared vinylformic acid degree of neutralization that contains covalent type and ionic nitrogen element High hydrophilous resin is 10%-90%, and its degree of neutralization can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.The preferred 10%-50% of degree of neutralization, most preferably 20%-40%.
The described persulphate of technique scheme, preferred Potassium Persulphate, ammonium persulphate, Sodium Persulfate, most preferably Potassium Persulphate.
Technique scheme is described, and the initiator persulphate is 1.5%-1.9% (weight) with respect to the consumption of yam starch, preferred 1.4%-2.0% (weight), most preferably 1.6%-1.8% (weight).
(2) with the carboxymethyl potato starch the synthetic High hydrophilous resin that contains covalent type and ionic nitrogen element of raw material: under the ice-water bath cooling; carry out neutralization reaction with sodium hydroxide solution and the vinylformic acid of removing stopper; acrylamide is dissolved in and is mixed with solution in the deionized water; with carboxymethyl potato starch and the vinylformic acid and the sodium salt solution thereof that make; acrylamide soln mixes; wherein carboxymethyl potato starch and vinylformic acid; acrylamide; the mass ratio of sodium hydroxide is 1: 6-14: 8-12: 0.39-3.34; the persulphate that adds carboxymethyl potato starch quality 1.00%-2.00% is made initiator; the N of 0.005%-0.05%; N '-methylene-bisacrylamide is made linking agent; at room temperature stir certain hour; mixture is stirred; heat up gradually with heating in water bath afterwards and reach 60 ℃-80 ℃ until temperature; make carboxymethyl potato starch and vinylformic acid and sodium salt thereof; acrylamide carries out graft copolymerization; reaction process is carried out under nitrogen protection; and make mixture insulation reaction 1-2h under the condition of boiling water bath heating; in baking oven, dry; obtain containing the High hydrophilous resin of covalent nitrogen; soaked 1-2 days with 1.1-8.75g ammoniacal liquor; elimination free ammoniacal liquor; emanate with dehydrated alcohol again; naturally dried under the room temperature 1-2 days; product is dried in baking oven to constant weight; pulverize, promptly get and contain covalent type and ionic nitrogen element High hydrophilous resin.
Technique scheme is described, and the vinylformic acid degree of neutralization of prepared High hydrophilous resin is 20%-60%, and its degree of neutralization can be 20%, 30%, 35%, 40%, 50%, 60%.The preferred 30%-60% of degree of neutralization, most preferably 35%-50%.
The described persulphate of technique scheme, preferred Potassium Persulphate, ammonium persulphate, Sodium Persulfate, most preferably Potassium Persulphate.
Technique scheme is described, and the initiator persulphate is 1.00%-2.00% (weight) with respect to the consumption of carboxymethyl potato starch, preferred 1.00%-1.72% (weight), most preferably 1.00%-1.52% (weight).
Technique scheme is described, linking agent N, and N '-methylene-bisacrylamide is 0.005%-0.05% (weight) with respect to the consumption of carboxymethyl potato starch, preferred 0.012%-0.044% (weight), most preferably 0.016%-0.032% (weight).
The present invention is in the outstanding feature of main application fields: this product contains covalent type and ionic nitrogen element.The nitrogen element is the essential nutrient of plant-growth, and it is the important component part of each viable cell.Plant-growth needs a large amount of nitrogen elements, general is the chemical fertilizer of main component with the nitrogen nutrition element, comprise bicarbonate of ammonia, urea, ammonium nitrate, ammoniacal liquor, ammonium chloride, ammonium sulfate etc., too much use and to cause soil compaction, Land capability to reduce, aggravate environmental pollution, waste a large amount of narrow resources, and general nitrogenous fertilizer runs off easily.And this product contains covalent type and ionic nitrogen element, and it is slow liberating nitrogen element both, can provide the nitrogen element quickly again, thereby increases soil fertility and for plant provides moisture, so this product has broad application prospects.
Advantage of the present invention is: 1, the excellent property of this product: (1) with the yam starch be feedstock production contain covalent type and the highest suction amount of deionized water of ionic nitrogen element High hydrophilous resin doubly at 2000-2200, inhale from the beginning the water yield doubly, the other products that its water regain will be higher than in the market to be sold at 300-310.(2) with the carboxymethyl potato starch be feedstock production contain covalent type and the highest suction amount of deionized water of ionic nitrogen element High hydrophilous resin be 2400-2500 doubly, inhaling from the beginning, the water yield is about 480-500 times, compare with like product on the market, inhaling the pure water amount is that it is more than twice.3, contain necessary for plant growth nitrogen element in this product, being used for the soil moisture maintenance is the product that kills two birds with one stone.4, the raw material of producing this product is yam starch or carboxymethyl potato starch (being made by yam starch), and yam starch is the very large agricultural-food of the northern area of China output, the promotion conference of this product expands out a new road for the deep processing of the northern area of China agricultural-food, and the peasant is increased income.5, proportioning raw materials among the present invention, dosage of crosslinking agent, initiator amounts etc. all have different significantly with the technology of other products, specific as follows: the proportioning of (1) reactant is meant yam starch or carboxymethyl potato starch and vinylformic acid, sodium hydroxide, acrylamide, the ratio of the quality of ammoniacal liquor, proportioning raw materials is one of important factor that influences water-intake rate, because the ratio of vinylformic acid and acrylamide and ammoniacal liquor has a direct impact water-intake rate and product nitrogen content, when the acrylamide consumption is too much, because amide group is poorer than carboxylic acid group's wetting ability, thereby the High hydrophilous resin water-intake rate that causes making descends, when but the acrylamide consumption is very few, the content that the High hydrophilous resin that makes contains covalent nitrogen is low excessively, take all factors into consideration, final yam starch and vinylformic acid and acrylamide mass ratio are 1: 3-5.25: 0.75-3, carboxymethyl potato starch and vinylformic acid, the acrylamide mass ratio is 1: 6-14: 8-12.The content of the consumption decision ionic nitrogen element of vinylformic acid, sodium hydroxide and ammoniacal liquor, the consumption of sodium hydroxide is few, then ammonia volume is many, and the High hydrophilous resin gel state that ammonia volume makes when too much is poor, take all factors into consideration, the mass ratio of final yam starch and ammoniacal liquor is 1: 0.24-2.53, the mass ratio 1 of carboxymethyl potato starch and ammoniacal liquor: 0.44-3.50.(2) because yam starch water-soluble relatively poor, so do not add linking agent when being raw material with it.When being raw material with the carboxymethyl potato starch, select N for use, N '-methylene-bisacrylamide is a linking agent, can make High hydrophilous resin form bigger network on the one hand after adding linking agent, help increasing water-intake rate, on the other hand, can increase the density of hydrophilic radical again, help the raising of water-intake rate equally.The effect of linking agent is to make to form certain degree of crosslinking between the macromolecular chain of the multipolymer of carboxymethyl potato starch graft acrylic acid etc., makes the polymer formation fenestral fabric, thereby forms bigger three-dimensional suction space.When dosage of crosslinking agent increases, polymkeric substance internal crosslinking dot density increases, the molecular resin chain-unfolding is restricted, network expansion difficulty during water absorption and swelling, the amount that can hold water reduces, the High hydrophilous resin water-intake rate reduces, and therefore adopting dosage of crosslinking agent is the 0.005%-0.05% of carboxymethyl potato starch quality.(3) initiator concentration increases, and the free radical number increases in the system, has accelerated the speed of graft polymerization reaction, and the also corresponding increase of percentage of grafting is so water-intake rate increases; But initiator is excessive, and the polyradical of crossing of generation easily causes chain transfer and chain termination reaction, and percentage of grafting is descended, be that grafted chain is difficult for increasing, polymericular weight is less, and reactive force is also little between macromole, under the water molecules effect, can be partly dissolved, cause water-intake rate to descend.Therefore adopting initiator amount is the 1.5%-1.9% of yam starch quality, and initiator amount is the 1.00%-2.00% of carboxymethyl potato starch quality.
Description of drawings
Fig. 1 is to be the process flow sheet that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin with the yam starch
Fig. 2 is to be the process flow sheet that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin with the carboxymethyl potato starch
Fig. 3 is that degree of neutralization is to being the graphic representation that feedstock production contains covalent type and the influence of ionic nitrogen element High hydrophilous resin suction deionized water rate with the yam starch
Fig. 4 is that degree of neutralization is to being the graphic representation that feedstock production contains covalent type and the influence of ionic nitrogen element High hydrophilous resin suction tap water rate with the yam starch
Fig. 5 is that degree of neutralization is 30% to be the graphic representation that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin rate of water absorption with the yam starch
Fig. 6 is that degree of neutralization is 30% to be the graphic representation that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin salt tolerance with the yam starch
Fig. 7 is that degree of neutralization is to being the influence curve that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin suction deionized water rate with the carboxymethyl potato starch
Fig. 8 is that degree of neutralization is to being the influence curve that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin suction tap water rate with the carboxymethyl potato starch
Fig. 9 is to be the rate of water absorption graphic representation that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin with the carboxymethyl potato starch
Figure 10 is to be the salt tolerance graphic representation that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin with the carboxymethyl potato starch
Figure 11 is to be the absorbency ability histogram that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin with the carboxymethyl potato starch
Figure 12 is to be the infrared spectra that feedstock production contains covalent type and ionic nitrogen element High hydrophilous resin with the carboxymethyl potato starch
Embodiment
Embodiment 4,5,6 is for being the High hydrophilous resin that feedstock production contains covalent type and ionic nitrogen element with the carboxymethyl potato starch.
Embodiment 1: take by weighing 3.8g sodium hydroxide, measure the 11.4ml deionized water, be mixed with sodium hydroxide solution, be cooled to room temperature, under ice-water bath cooling in and 21.5g remove the vinylformic acid of stopper, make vinylformic acid and sodium salt solution thereof.Make acrylamide solution with 10.0ml deionized water dissolving 7.5g acrylamide.The deionized water that takes by weighing 5.0g yam starch and 10.0ml under agitation heats gelatinization.Yam starch after the gelatinization, 86mg Potassium Persulphate initiator, the vinylformic acid that has made and sodium salt solution thereof and acrylamide soln are stirred 0.5h under room temperature, it is mixed.Stir heating down, the control rate of heating slowly raises bath temperature, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization.Continue to heat up gradually, after the water boiling, continue heating and make it under the boiling water bath heating, react 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, in baking oven, dry, pulverize, soaked 1-2 days with 12.0g ammoniacal liquor (massfraction is 25%), elimination free ammoniacal liquor, with the dehydrated alcohol segregation, dried naturally under the room temperature 1-2 days again, then product is dried in baking oven to constant weight, pulverize, promptly get degree of neutralization (in the sodium hydroxide with acrylic acid per-cent) 30% contain covalent type and ionic nitrogen element High hydrophilous resin.The suction deionized water rate of product is 2200g/g.
Embodiment 2: take by weighing 2.4g sodium hydroxide, measure the 7.2ml deionized water, be mixed with sodium hydroxide solution, be cooled to room temperature, under ice-water bath cooling in and 21.5g remove the vinylformic acid of stopper, make vinylformic acid and sodium salt solution thereof.Other experiment conditions are identical with embodiment 1, obtain degree of neutralization (in the sodium hydroxide and acrylic acid per-cent) 20% contain covalent type and ionic nitrogen element High hydrophilous resin.The suction deionized water rate of product is 1600g/g.
Embodiment 3: take by weighing 4.8g sodium hydroxide, measure the 14.4ml deionized water, be mixed with sodium hydroxide solution, be cooled to room temperature, under ice-water bath cooling in and 21.5g remove the vinylformic acid of stopper, make vinylformic acid and sodium salt solution thereof.Other experiment conditions are identical with embodiment 1, obtain degree of neutralization (in the sodium hydroxide and acrylic acid per-cent) 40% contain covalent type and ionic nitrogen element High hydrophilous resin.The suction deionized water rate of product is 1500g/g.
Embodiment 4: take by weighing 4.9g sodium hydroxide, measure the 35.0ml deionized water, be mixed with sodium hydroxide solution, be cooled to room temperature, under ice-water bath cooling in and 17.5g remove the vinylformic acid of stopper, make vinylformic acid and sodium salt solution thereof.Make acrylamide solution with 32.0ml deionized water dissolving 25.0g acrylamide.Take by weighing the 2.5g carboxymethyl potato starch, with carboxymethyl potato starch, 33mg Potassium Persulphate initiator, 0.8mgN, N '-methylene-bisacrylamide linking agent, the vinylformic acid that has made and sodium salt solution thereof and acrylamide soln stir 0.5h under room temperature, it is mixed.Stir heating down, the control rate of heating slowly raises bath temperature, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization.Continue to heat up gradually, after the water boiling, continue heating and make it under the boiling water bath heating, react 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, in baking oven, dry, pulverize, soaked 1-2 days with 8.0g ammoniacal liquor (massfraction is 25%), elimination free ammoniacal liquor, with dehydrated alcohol segregation, dried naturally under the room temperature 1-2 days again, then with product baking oven in dry to constant weight, pulverize, promptly get degree of neutralization (in the sodium hydroxide with acrylic acid per-cent) 50% contain covalent type and ionic nitrogen element High hydrophilous resin.The suction deionized water rate of product is 2500g/g.
Embodiment 5: take by weighing 3.9g sodium hydroxide, measure the 35.0ml deionized water, be mixed with sodium hydroxide solution, be cooled to room temperature, under ice-water bath cooling in and 17.5g remove the vinylformic acid of stopper, make vinylformic acid and sodium salt solution thereof.Other experiment conditions are identical with embodiment 4, obtain degree of neutralization (in the sodium hydroxide and acrylic acid per-cent) 40% contain covalent type and ionic nitrogen element High hydrophilous resin.The suction deionized water rate of product is 2400g/g.
Embodiment 6: take by weighing 5.8g sodium hydroxide, measure the 35.0ml deionized water, be mixed with sodium hydroxide solution, be cooled to room temperature, under ice-water bath cooling in and 17.5g remove the vinylformic acid of stopper, make vinylformic acid and sodium salt solution thereof.Other experiment conditions are identical with embodiment 4, obtain degree of neutralization (in the sodium hydroxide and acrylic acid per-cent) 60% contain covalent type and ionic nitrogen element High hydrophilous resin.The suction deionized water rate of product is 1800g/g.
The infrared spectra of High hydrophilous resin uses NEXUSTM 670FT-IR E.S.P type infrared spectrometer, is measured by University of the Inner Mongol.Main absorption peak (the cm of the IR spectrum of embodiment 4 products
-1): 3428cm
-1Stack for-OH stretching vibration and N-H stretching vibration; At 2948cm
-1There is the asymmetrical stretching vibration peak of C-H at the place; 1662cm
-1Be C=O stretching vibration peak in the acid amides; At 1297cm
-1The place is C-N stretching vibration peak, 1564cm
-1The place is COO-key asymmetrical stretching vibration peak in the carboxylate radical; At 1412cm
-1The place is the symmetrical stretching vibration peak of COO-key in the carboxylate radical.The ultimate analysis data of product: measure through German Elementar Vario ELIII type ultimate analysis instrument, the constituent content of embodiment 1 product is: C%=38.61, H%=6.829, N%=8.303, the constituent content of embodiment 4 products is: C%=41.17, H%=7.113, N%=11.01.
Claims (4)
1. the preparation method who contains covalent type and ionic nitrogen element High hydrophilous resin, it is characterized in that: when being raw material with the yam starch, the mass ratio of yam starch and vinylformic acid, acrylamide, sodium hydroxide, ammoniacal liquor is 1: 3-5.25: 0.75-3: 0.168-2.624: 0.24-2.53, the mass ratio of yam starch and deionized water is 1: 4-6 carries out gelatinization, the persulphate that adds yam starch quality 1. 5%-1.9% is made initiator, and the highest suction amount of deionized water of prepared High hydrophilous resin is 2000-2200 times; When being raw material with the carboxymethyl potato starch, the mass ratio of carboxymethyl potato starch and vinylformic acid, acrylamide, sodium hydroxide, ammoniacal liquor is 1: 6-14: 8-12: 0.39-3.34: 0.44-3.50, the persulphate that adds carboxymethyl potato starch quality 1.00%-2.00% is the N of initiator, 0.005%-0.05%, N ＇-methylene-bisacrylamide is made linking agent, and the highest suction amount of deionized water of prepared High hydrophilous resin is 2400-2500 times.
2. according to the described preparation method who contains covalent type and ionic nitrogen element High hydrophilous resin of claim 1, it is characterized in that: when being raw material with the yam starch, acrylic acid degree of neutralization of prepared High hydrophilous resin is between 20%-40%; When being raw material with the carboxymethyl potato starch, acrylic acid degree of neutralization of prepared High hydrophilous resin is between 35%-50%.
3. according to the described preparation method who contains covalent type and ionic nitrogen element High hydrophilous resin of claim 1, it is characterized in that: when being raw material with the yam starch, the consumption of initiator persulphate is with respect to the 1.6%-1.8%(weight of yam starch) between; When being raw material with the carboxymethyl potato starch, the consumption of initiator persulphate is with respect to the 1.00%-1.52%(weight of carboxymethyl potato starch) between.
4. according to the described preparation method who contains covalent type and ionic nitrogen element High hydrophilous resin of claim 1, it is characterized in that: when being raw material, do not add linking agent with the yam starch; When being raw material with the carboxymethyl potato starch, linking agent N, the consumption of N ＇-methylene-bisacrylamide is with respect to the 0.016%-0.032%(weight of carboxymethyl potato starch) between.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007087359A2 (en) * | 2006-01-25 | 2007-08-02 | Absorbent Technologies, Inc. | Methods for producing superabsorbent polymers for use in agricultural applications |
| CN101638457A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for preparing super absorbent resin containing covalent nitrogen by using potato starch as raw material |
| CN101696313A (en) * | 2009-10-26 | 2010-04-21 | 昆明理工大学 | Method for preparing starch/acrylamide grafted copolymer by high-energy ray |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007087359A2 (en) * | 2006-01-25 | 2007-08-02 | Absorbent Technologies, Inc. | Methods for producing superabsorbent polymers for use in agricultural applications |
| CN101638457A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for preparing super absorbent resin containing covalent nitrogen by using potato starch as raw material |
| CN101696313A (en) * | 2009-10-26 | 2010-04-21 | 昆明理工大学 | Method for preparing starch/acrylamide grafted copolymer by high-energy ray |
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