CN101974129B - Process formula for preparing potassium and nitrogen-containing super absorbent resin by using phosphoric ester of potato starch as raw material - Google Patents
Process formula for preparing potassium and nitrogen-containing super absorbent resin by using phosphoric ester of potato starch as raw material Download PDFInfo
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- CN101974129B CN101974129B CN201010501001A CN201010501001A CN101974129B CN 101974129 B CN101974129 B CN 101974129B CN 201010501001 A CN201010501001 A CN 201010501001A CN 201010501001 A CN201010501001 A CN 201010501001A CN 101974129 B CN101974129 B CN 101974129B
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Abstract
The invention discloses a process formula for preparing potassium and nitrogen-containing super absorbent resin by using phosphoric ester of potato starch as a raw material. The product is prepared by using the phosphoric ester of potato starch as the raw material, wherein the phosphoric ester of potato starch is soluble in water. Compared with a formula using starch as the raw material, the formula has the advantages of avoiding gelatinization and simplifying the preparation process greatly. The super absorbent resin prepared according to the formula has the advantages of high water-absorbing and water-holding capacity, better mildew-resistant effect and higher gel strength compared with products of the same kind. Meanwhile, the super absorbent resin prepared according to the formula has both potassium and nitrogen elements needed by plants for growth, and has a great significance for combating drought and protecting the seedlings, increasing yield and harvest, promoting plant growth in soil in drought regions and the like.
Description
Technical field
The present invention relates to a kind of is the technical recipe that the main raw material preparation contains the High hydrophilous resin of potassium and nitrogen element with potato starch phosphate, vinylformic acid, acrylamide, potassium hydroxide.The present invention is under the prerequisite of raw material synthetic High hydrophilous resin water-intake rate with the starch-phosphate keeping or being higher than in the past, synthesized contain simultaneously plant-growth the High hydrophilous resin of essential potassium element and nitrogen element, its application prospect will be more wide, especially at agriculture field, as aspects such as seed pelleting, keeping crop seedling from drought, soil improvements.
Background technology
Drought and water shortage and Soil degradation are the important factors of restriction China agricultural sustainable development.According to investigations, the rainfall of semiarid zone, northwest is in the utilization in farmland, and evaporation of soil moisture waste moisture is maximum, generally accounts for the 55%-65% of annual precipitation.In the part of plant utilization precipitation, invalid transpiration accounts for more than 95% of plant utilization moisture again.The average annual precipitation deficit 400mm in the area of present China 45%, irrigated farmland lack of water billion cubic meter more than 300.In recent years, along with global warming, the arid aggravation, arid area constantly enlarges, and particularly most of area, China south in this year suffers drought, farm crop in poor harvest or total crop failure in various degree.Therefore, conserve water and soil and resisting drought saving water has become the face the future inevitable choice of sustainable development of China's agricultural.Reducing evaporation of soil moisture and reduce the crop transpiration, is the central task that improves the farmland water use efficiency.
The application of High hydrophilous resin is the chemical rapidly water-saving technology of development in recent years.It is a kind of high molecular polymer with super-strong moisture absorbing water retention capacity.It can absorb the pure water of hundred times of self tuples even thousands of times rapidly and absorbent function is repeatedly arranged, and the hydrogel after the suction can slowly discharge moisture and be made for the thing utilization.Simultaneously, High hydrophilous resin can strengthen soil water-retaining, and the structure of improving the soil reduces the soil moisture nutrient loss, improves water and fertilizer utilization, has advantages such as purposes is wide, less investment, instant effect, is widely used and development prospect at aspects such as agriculture productions.
The patent and the bibliographical information of present domestic research STARCH GRAFT POLYMER SUPER ABSORBENT RESIN emerge in an endless stream, and the suction of product and water retention property are also very excellent, but from suitability for industrialized production and angle of practical application, still have many problems.Low as the gel-strength after the suction, the gel in the edatope of complexity after poor, the suction of the salt tolerance of High hydrophilous resin is because the existence of starch skeleton causes gel easily to go mouldy, thereby loses water retention capacity etc.The objective of the invention is at above problem, the characteristic of starch is started with from change polymkeric substance, with potato starch phosphate and vinylformic acid and sylvite thereof, acrylamide, add a certain amount of linking agent, a kind of novel super absorbent resin has been synthesized in graft polymerization, and its water-retaining capacity and water retention property are strong, gel-strength good, the anti-mildew sex change can by force and contain required potassium element of plant-growth and nitrogen element.Having overcome starch to a certain extent is the above problem that High hydrophilous resin exists.
Summary of the invention
It is the method that feedstock production contains potassium and nitrogen element High hydrophilous resin with the potato starch phosphate that the technical problem to be solved in the present invention provides a kind of, this preparation method is with potato starch phosphate, vinylformic acid, acrylamide, potassium hydroxide, N, N '-methylene-bisacrylamide and persulphate etc. are raw material, through reasonable proportioning, make High hydrophilous resin by certain technological process.
Technical problem of the present invention is solved by following scheme: be the technical recipe that feedstock production contains potassium and nitrogen element High hydrophilous resin with the potato starch phosphate, it is characterized in that: carry out neutralization reaction with potassium hydroxide solution and the vinylformic acid of removing stopper, the mass ratio of potato starch phosphate and monomer (comprising vinylformic acid and acrylamide), potassium hydroxide is 1: 13-16: 2.2-5.3, the mass ratio of vinylformic acid and acrylamide are 1: 0.17-1.Vinylformic acid and potassium salt soln thereof after acrylamide soln, the neutralization are mixed with potato starch phosphate, the persulphate that adds potato starch phosphate quality 2.2%-3.4% is the N of initiator, 0.04%-0.24%, N '-methylene-bisacrylamide is made linking agent, make mixture under agitation mix 0.5-1h, heating up gradually with heating in water bath afterwards reaches 65 ℃-80 ℃ until temperature, makes potato starch phosphate and acrylamide, vinylformic acid and sylvite thereof carry out graft copolymerization.Reaction process is carried out under nitrogen protection, and is incubated 1.5h under the boiling water bath condition, dries in baking oven afterwards, pulverizes, and promptly gets High hydrophilous resin.
Technique scheme is described, and the vinylformic acid degree of neutralization of prepared High hydrophilous resin is 30%-60%, and its degree of neutralization can be 30%, 35%, 40%, 45%, 50%, 55%, 60%.The preferred 30%-50% of degree of neutralization, most preferably 35%-45%.
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 2.2%-3.4% (weight) with respect to the consumption of potato starch phosphate, preferred 2.4%-3.2% (weight), most preferably 2.6%-3.0% (weight).
Technique scheme is described, linking agent N, and N '-methylene-bisacrylamide is 0.04%-0.24% (weight) with respect to the consumption of potato starch phosphate, preferred 0.04%-0.2% (weight), most preferably 0.04%-0.12% (weight).
Technique scheme is described, and the suction amount of deionized water of prepared High hydrophilous resin at 1300-1500 doubly.
Advantage of the present invention is: 1, the performance of this product is fine, inhale amount of deionized water doubly at 1300-1500, inhale from the beginning the water yield doubly at 400-500, inhale saline volume doubly at 80-100, inhale artificial urine 60-80 doubly, inhale artificial blood 100-150 doubly, compare with like product on the market, inhaling the pure water amount is about its twice.2, this product employing potato starch phosphate of swellable in cold water is a raw material, having saved is gelatinization step in the raw material synthesizing super absorbent resin with starch, avoided generation because of gelatinization condition improper wastage of material that causes of control and waste product, fundamentally simplified synthesis technique, improve combined coefficient, reduced production cost.3, contain necessary for plant growth nitrogen, phosphorus and potassium element in this product, both can be used for soil moisture and keep, can increase the nutritive ingredient of soil again, have important use in fields such as farming, woods and gardening and be worth.4, the proportioning raw materials among the present invention, acrylic acid degree of neutralization, dosage of crosslinking agent, initiator amount etc. all have different significantly, specific as follows with the technical recipe of other products: the proportioning raw materials among (1) the present invention is meant the ratio of the ratio (monomer mass comprises the quality sum of vinylformic acid and acrylamide) of potato starch phosphate and monomeric quality and vinylformic acid and the quality of acrylamide.Proportioning raw materials is one of important factor that influences water-intake rate.This is how many direct molecular weight that influence graftomer because of monomer content, thereby influences the water absorbing properties of product.In addition, the ratio of vinylformic acid and acrylamide has a direct impact water-intake rate and product nitrogen content, the acrylamide consumption is too much, because amide group is poorer than carboxylated hydrophilic, thereby the High hydrophilous resin water-intake rate that causes making descends, but the acrylamide consumption is very few, the High hydrophilous resin nitrogen content that makes is low excessively, take all factors into consideration, final potato starch phosphate and monomeric mass ratio are 1: 13-16, the mass ratio of vinylformic acid and acrylamide are 1: 0.17-1.(2) acrylic acid degree of neutralization is the important factor that influences High hydrophilous resin water-intake rate and gel state, directly has influence on the height of High hydrophilous resin potassium content simultaneously.Consider that from reaction kinetics polymerizing acrylic acid is subjected to the influence of pH value of solution value very big, is in the pH value at 2.4 o'clock, rate constant of polymerisation is about 5.8 * 106 (s-l), and when the pH value was 7.2, rate of polymerization descended 20 times approximately.Therefore low excessively as if degree of neutralization, in the reaction system-COOH content is higher, and polyreaction is wayward, and self-crosslinking easily takes place in the reaction process, forms highly cross-linked low-molecular weight polymer, so water-intake rate is lower.When degree of neutralization increases, in the reaction system-the COOH major part is converted into-COOK, and-COOK is difficult for taking place self-crosslinking reaction, alleviated speed of response, degree of crosslinking is reduced, thereby water-intake rate is higher.But degree of neutralization is too high, in the resin-COOK content increases, and polymkeric substance wetting ability variation and cause water-intake rate to reduce.Take all factors into consideration, finally choosing degree of neutralization is 30%-60%.(3) select N for use, N '-methylene-bisacrylamide is a linking agent, can make High hydrophilous resin form bigger network behind the adding linking agent on the one hand, 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 the certain degree of crosslinking of formation between the macromolecular chain of potato starch phosphate grafted propylene acid copolymer, makes the polymer formation fenestral fabric, thereby forms bigger three-dimensional suction space.When dosage of crosslinking agent increased, polymkeric substance internal crosslinking dot density increased, and the molecular resin chain-unfolding is restricted, network expansion difficulty during water absorption and swelling, and the amount that can hold water reduces, and the High hydrophilous resin water-intake rate reduces.Therefore adopting dosage of crosslinking agent is the 0.04%-0.24% of potato starch phosphate quality.(4) 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 2.0%-3.4% of potato starch phosphate
With the potato starch phosphate is the super absorbent resin that feedstock production contains potassium and nitrogen element, it not only has very high water regain, and contain necessary for plant growth nitrogen, phosphorus and potassium element, it is applied to agriculture field widely, can solve the problem of lack of water arid area proportion of crop planting lack of water and fertilizer, have huge social benefit and economic benefit.
Description of drawings
Fig. 1 is the process flow sheet of High hydrophilous resin
Fig. 2 is the influence curve of potato starch phosphate and monomer mass comparison High hydrophilous resin water-intake rate
Fig. 3 is vinylformic acid and the acrylamide mass ratio influence curve to the High hydrophilous resin water-intake rate
Fig. 4 is the influence curve of acrylic acid degree of neutralization to the High hydrophilous resin water-intake rate
Fig. 5 is the influence curve of initiator amount to the High hydrophilous resin water-intake rate
Fig. 6 is the influence curve of dosage of crosslinking agent to the High hydrophilous resin water-intake rate
Fig. 7 is the salt tolerance curve of High hydrophilous resin
Fig. 8 is the rate of water absorption curve of High hydrophilous resin
Fig. 9 is the liquid absorption of High hydrophilous resin in different liqs
Figure 10 is the infrared spectrogram of specific embodiment 4 High hydrophilous resins
Embodiment
Embodiment 1: weighing 7.9g potassium hydroxide, measure the 30.0ml deionized water, the preparation potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 25.3g remove the vinylformic acid of stopper.Take by weighing the 8.4g acrylamide, it is dissolved with the 40.0ml deionized water.With in the vinylformic acid of becoming reconciled and good acrylamide soln and the 2.5g potato starch phosphate of dissolving under room temperature, stir 0.5h, it is mixed.Add 70mg Potassium Persulphate initiator, 2.0mgN, N '-methylene-bisacrylamide stirs heating down, controls rate of heating simultaneously, and bath temperature is slowly raise, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization begins.After this heat up gradually, after reaching water-bath ebullient temperature, continue heating and make it, stop logical nitrogen, be cooled to room temperature at this temperature range internal reaction 1.5h.Product is taken out, get the white granular High hydrophilous resin after drying, the pulverizing.The suction deionized water rate of this product is 1310g/g.
Embodiment 2: weighing 8.2g potassium hydroxide, measure the 30.0ml deionized water, the preparation potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 26.2g remove the vinylformic acid of stopper.Take by weighing the 8.8g acrylamide, it is dissolved with the 40.0ml deionized water.With in the vinylformic acid of becoming reconciled and good acrylamide soln and the 2.5g potato starch phosphate of dissolving under room temperature, stir 0.5h, it is mixed.Add 70mg Potassium Persulphate initiator, 2.0mgN, N '-methylene-bisacrylamide stirs heating down, controls rate of heating simultaneously, and bath temperature is slowly raise, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization begins.After this heat up gradually, after reaching water-bath ebullient temperature, continue heating and make it, stop logical nitrogen, be cooled to room temperature at this temperature range internal reaction 1.5h.Product is taken out, get the white granular High hydrophilous resin after drying, the pulverizing.The suction deionized water rate of this product is 1350g/g.
Embodiment 3: weighing 8.5g potassium hydroxide, measure the 30.0ml deionized water, the preparation potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 27.2g remove the vinylformic acid of stopper.Take by weighing the 9.1g acrylamide, it is dissolved with the 40.0ml deionized water.With in the vinylformic acid of becoming reconciled and good acrylamide soln and the 2.5g potato starch phosphate of dissolving under room temperature, stir 0.5h, it is mixed.Add 70mg Potassium Persulphate initiator, 2.0mgN, N '-methylene-bisacrylamide stirs heating down, controls rate of heating simultaneously, and bath temperature is slowly raise, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization begins.After this heat up gradually, after reaching water-bath ebullient temperature, continue heating and make it, stop logical nitrogen, be cooled to room temperature at this temperature range internal reaction 1.5h.Product is taken out, get the white granular High hydrophilous resin after drying, the pulverizing.The suction deionized water rate of this product is 1320g/g.
Embodiment 4: weighing 8.7g potassium hydroxide, measure the 30.0ml deionized water, the preparation potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 28.0g remove the vinylformic acid of stopper.Take by weighing the 7.0g acrylamide, it is dissolved with the 40.0ml deionized water.With in the vinylformic acid of becoming reconciled and good acrylamide soln and the 2.5g potato starch phosphate of dissolving under room temperature, stir 0.5h, it is mixed.Add 70mg Potassium Persulphate initiator, 2.0mgN, N '-methylene-bisacrylamide stirs heating down, controls rate of heating simultaneously, and bath temperature is slowly raise, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization begins.After this heat up gradually, after reaching water-bath ebullient temperature, continue heating and make it, stop logical nitrogen, be cooled to room temperature at this temperature range internal reaction 1.5h.Product is taken out, get the white granular High hydrophilous resin after drying, the pulverizing.The suction deionized water rate of this product is 1500g/g.
Embodiment 5: weighing 9.1g potassium hydroxide, measure the 30.0ml deionized water, the preparation potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 29.2g remove the vinylformic acid of stopper.Take by weighing the 5.8g acrylamide, it is dissolved with the 40.0ml deionized water.With in the vinylformic acid of becoming reconciled and good acrylamide soln and the 2.5g potato starch phosphate of dissolving under room temperature, stir 0.5h, it is mixed.Add 70mg Potassium Persulphate initiator, 2.0mgN, N '-methylene-bisacrylamide stirs heating down, controls rate of heating simultaneously, and bath temperature is slowly raise, and graft copolymerization is fully carried out, and stops to stir after graft copolymerization begins.After this heat up gradually, after reaching water-bath ebullient temperature, continue heating and make it, stop logical nitrogen, be cooled to room temperature at this temperature range internal reaction 1.5h.Product is taken out, get the white granular High hydrophilous resin after drying, the pulverizing.The suction deionized water rate of this product is 1470g/g.
Embodiment 6: acrylic acid potassium hydroxide consumption that neutralizes is 7.6g, and other experiment conditions are identical with the condition of embodiment 4, and the suction deionized water rate of product is 1470g/g.
Embodiment 7: acrylic acid potassium hydroxide consumption that neutralizes is 9.8g, and other experiment conditions are identical with the condition of embodiment 4, and the suction deionized water rate of product is 1435g/g.
Embodiment 8: initiator amount is 65mg, and other experiment conditions are identical with the condition of embodiment 4, and the suction deionized water rate of product is 1440g/g.
Embodiment 9: initiator amount is 75mg, and other experiment conditions are identical with the condition of embodiment 4, and the suction deionized water rate of product is 1440g/g.
Embodiment 10: dosage of crosslinking agent is 1.0mg, and other experiment conditions are identical with the condition of embodiment 4, and the suction deionized water rate of product is 1430g/g.
Embodiment 11: dosage of crosslinking agent is 3.0mg, and other experiment conditions are identical with the condition of embodiment 4, and the suction deionized water rate of product is 1440g/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.Product with embodiment 4 is an example, the main absorption peak of IR spectrum: 3447cm
-1Stretching vibration absorption peak for-OH; 3132cm
-1Stretching vibration absorption peak for NH; 1633cm
-1Folded honeybee for the asymmetrical stretching vibration absorption peak of acid amides C=O stretching vibration absorption peak and carboxylate salt COO-; 1400cm
-1Symmetrical stretching vibration peak for carboxylate salt COO-.Measure through German Elementar Vario ELIII type ultimate analysis instrument, carbon, hydrogen and the nitrogen element content of embodiment 4 products are respectively: C%=39.55, H%=5.316, N%=2.712.Potassium element content through atomic absorption spectroscopy determination embodiment 1 product is: K%=13.11.
Claims (5)
1. with the potato starch phosphate method that feedstock production contains potassium and nitrogen element High hydrophilous resin; it is characterized in that: under the ice-water bath cooling; carry out neutralization reaction with potassium hydroxide solution and the vinylformic acid of removing stopper; wherein potato starch phosphate and vinylformic acid; the mass ratio of potassium hydroxide is 1: 7-11.7: 2.2-5.3; the mass ratio of vinylformic acid and acrylamide is 1: 0.17-1; with acrylamide soln; vinylformic acid after the neutralization and sylvite thereof and potato starch phosphate mix; the Potassium Persulphate that adds potato starch phosphate quality 2.2%-3.4% is made initiator; the N of 0.04%-0.24%; N '-methylene-bisacrylamide is made linking agent; stirred 0.5-1.0 hour; mixture is under agitation mixed; then under nitrogen protection; heating in water bath also stirs; stop when reaching certain temperature stirring; in boiling water bath insulation reaction 1-2 hour; stop logical nitrogen then; product is taken out; cut into fritter; in 40 ℃-60 ℃ baking oven, dry; pulverize, promptly get and contain potassium and nitrogen element High hydrophilous resin, the suction amount of deionized water of obtained High hydrophilous resin be 1300-1500 doubly.
2. according to claim 1 is the method that feedstock production contains potassium and nitrogen element High hydrophilous resin with the potato starch phosphate, it is characterized in that: the grafting parent of employing is a potato starch phosphate, be that yam starch is handled through Phosphation, the grafted monomer of employing is the mix monomer of vinylformic acid and acrylamide.
3. according to claim 1 is the method that feedstock production contains potassium and nitrogen element High hydrophilous resin with the potato starch phosphate, it is characterized in that: the vinylformic acid degree of neutralization optimal conditions of prepared High hydrophilous resin is between 35%-45%.
4. according to claim 1 is the method that feedstock production contains potassium and nitrogen element High hydrophilous resin with the potato starch phosphate, it is characterized in that: initiator potassium persulfate with respect to the optimal conditions of potato starch phosphate consumption in 2.6%-3.0% (weight).
5. according to claim 1 is the method that feedstock production contains potassium and nitrogen element High hydrophilous resin with the potato starch phosphate, it is characterized in that: linking agent N, N '-methylene-bisacrylamide with respect to the optimal conditions of potato starch phosphate consumption between 0.04%-0.12% (weight).
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| CN103613709B (en) * | 2013-09-30 | 2015-09-16 | 内蒙古大学 | With yam starch xanthate for the resin dedicated method of Material synthesis Adsorption of Heavy Metal Ions |
| CN107641173B (en) * | 2017-10-01 | 2020-06-05 | 桂林理工大学 | Preparation method of crosslinked AA/AM grafted esterified cyanoethyl cassava starch |
| CN108276514B (en) * | 2018-01-03 | 2020-03-24 | 中国化学赛鼎宁波工程有限公司 | Preparation method of super absorbent resin |
| CN115317844B (en) * | 2022-08-31 | 2024-01-26 | 四川省林业科学研究院 | Fireproof composition and preparation method thereof |
| CN115317843B (en) * | 2022-08-31 | 2024-01-19 | 四川省林业科学研究院 | Fire extinguishing agent for forest fire prevention and preparation method thereof |
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| CN101638461B (en) * | 2009-09-14 | 2011-01-05 | 内蒙古大学 | Method for synthesizing super absorbent resin containing phosphorus and nitrogen by graft copolymerization reaction of potato starch organic phosphate |
| CN101691416B (en) * | 2009-09-14 | 2011-01-05 | 内蒙古大学 | Method for preparing super absorbent resin with cross-linked structure from potato starch phosphate graft co-polymeric acrylic acid and sodium salt thereof |
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