CN102775557B - Method for preparing high-water-absorptivity resin from potato starch dextrin - Google Patents
Method for preparing high-water-absorptivity resin from potato starch dextrin Download PDFInfo
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- CN102775557B CN102775557B CN 201210296290 CN201210296290A CN102775557B CN 102775557 B CN102775557 B CN 102775557B CN 201210296290 CN201210296290 CN 201210296290 CN 201210296290 A CN201210296290 A CN 201210296290A CN 102775557 B CN102775557 B CN 102775557B
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Abstract
The invention discloses a method for preparing a high-water-absorptivity resin from potato starch dextrin, which comprises the following steps: while cooling in an ice water bath, carrying out neutralization reaction on a sodium (potassium) hydroxide solution and acrylic acid without polymerization inhibitor, mixing neutralized acrylic acid and salts thereof and potato starch dextrin, adding potassium persulfate and N,N'-methylenebiacrylamide, and evenly mixing for 1.0 hour; in a nitrogen atmosphere, heating in a water bath while stirring, stopping stirring when achieving a certain temperature, and keeping the temperature in a boiling water bath to react for 1-2 hours; and stopping introducing the nitrogen, taking out the product, cutting into dices, drying in a 40-60 DEG C oven to constant weight, and pulverizing to obtain the high-water-absorptivity resin prepared from potato starch dextrin. The high-water-absorptivity resin prepared by the method has the advantages of low cost and high water absorptivity, and has wide application prospects.
Description
Technical field
The present invention utilizes many-sided advantages such as yam starch dextrin solvability is good, preparation cost is low, and High hydrophilous resin synthesis technique prepared therefrom is simple, and cost is lower, and product performance are good.Relate to the method that yam starch dextrin graft acrylic acid and salt thereof prepare super absorbent resin.This series products is widely used in agricultural, and aspects such as forestry have vast market prospect.
Background technology
Super absorbent resin (Super Absorbent Resin, be called for short SAR) be a kind of typical functional high molecule material, it contains the strong hydrophilicity group, through appropriately crosslinked and have tridimensional network, both water insoluble organic solvents that also is insoluble to, the salt solution of hundred times of own wts and even hundreds of times be can absorb, " high water absorbency polymer ", " absorbent polymer material ", " super strength water absorbent " etc. are called usually again.Be widely used in a plurality of fields such as agricultural, gardens, civil construction, food-processing, petrochemical complex and health care.
Starch is that super absorbent resin has considerable effect as water-loss reducer of soil, modifying agent at aspects such as agricultural, forestry, gardening, it can strengthen the ability of soil suction and water conservation, improve the crumb structure of soil, thereby make loosing soil that the ventilation property of soil, the day and night temperature of soil are all improved.Also can increase soil fertility, strengthen the drought-resistant ability of plant.As water-loss reducer of soil, it can absorb a large amount of water when many water of soil, and can discharge water outlet when the soil lack of water, as forming a little reservoir at plant root, constantly supplies with the required moisture of plant.Significantly reduce the body surface moisture evaporation simultaneously, the direct effect of using farm crop is to improve the water-holding power of soil.
Starch is that the water sucting mechanism of SAP is because it has the hydrophilic interaction of hydrophile function, makes high score subnet bundle realize water absorption course by swelling, expansion and process of osmosis.In this process, the motion of water molecules is restricted, therefore can be as traditional water-absorbing material after the pressurization, and most of water is extruded, but has the ability of certain maintenance moisture.The unique characteristic of this super absorbent resin be placed on can absorb in the water hundred times to thousands of times to the water of itself quality and not dissolved.
Though SAP has particular performances, SAP yet has the SAP water-retaining capacity height of some shortcomings that are difficult to avoid such as ionic but salt tolerance is poor, and absorption speed is slower; The SAP absorption speed of non-ionic type is very fast, and salt tolerance also better but water-retaining capacity is lower; The High hydrophilous resin that water regain the is big back intensity that then absorbs water is low, and the high water-retaining agent of suction back intensity then water regain is low etc.Suchlike problem brings many obstacles for its exploitation and application. thus develop that synthetic method is simple, cheap, the SAP of superior performance and environmental protection is the key that is applied to sanitary product, agricultural and desertification control.The present invention is intended to: utilize the resolvability of yam starch dextrin, yam starch dextrin and vinylformic acid and salt thereof are carried out the reaction of graft copolymerization, the High hydrophilous resin low with simple synthesis technique preparation cost, that performance is good.
Summary of the invention
It is the method for feedstock production High hydrophilous resin with the yam starch dextrin that the technical problem to be solved in the present invention provides a kind of, this preparation method is with yam starch dextrin, vinylformic acid, Potassium Persulphate, sodium hydroxide (potassium), N, N '-methylene-bisacrylamide is raw material, through reasonable proportioning, make High hydrophilous resin by certain technical process.
Technical problem of the present invention is solved by following scheme: a kind of is the method for feedstock production super absorbent resin with the yam starch dextrin; it is characterized in that: under the ice-water bath cooling; carry out neutralization reaction with sodium hydroxide (potassium) solution and the vinylformic acid of removing stopper; the weight ratio of vinylformic acid and sodium hydroxide be 6-18:0.67-6.00(when with in the potassium hydroxide and the time; the weight ratio of vinylformic acid and potassium hydroxide is 6-18:0.93-8.40); with vinylformic acid and the salt thereof after the neutralization; the yam starch dextrin; Potassium Persulphate; N; N ＇-methylene-bisacrylamide; a certain amount of deionized water mixes; stirred 1.0 hours; yam starch dextrin wherein; vinylformic acid; Potassium Persulphate; N; N ＇-methylene-bisacrylamide; the weight ratio of the total deionized water of system is 1:2-6:0.010-0.023:0.0027-0.0067:10.0-23.3; under protection of nitrogen gas; heating in water bath also stirs; stop when reaching certain temperature stirring; insulation is 1-2 hour in boiling water bath; after stop logical nitrogen; product is taken out; cut into fritter; in 40 ℃-60 ℃ baking oven, dry to constant weight; pulverize, namely get the High hydrophilous resin that the yam starch dextrin is raw material.
Technique scheme described a kind of be the method for feedstock production High hydrophilous resin with the yam starch dextrin, wherein a certain amount of deionized water is dissolving yam starch dextrin, Potassium Persulphate, N, the amount of deionized water that N ＇-methylene-bisacrylamide is used.
Technique scheme described a kind of be the method for feedstock production High hydrophilous resin with the yam starch dextrin, wherein the total deionized water of system is dissolving yam starch dextrin, Potassium Persulphate, N, the total amount of the amount of deionized water that N ＇-methylene-bisacrylamide is used and preparation sodium hydroxide or the used deionized water of potassium hydroxide.
Technique scheme described a kind of be yam starch dextrin in the method for feedstock production High hydrophilous resin, vinylformic acid, Potassium Persulphate, N with the yam starch dextrin, the weight ratio of N ＇-methylene-bisacrylamide, the total deionized water of system is 1:2-6:0.010-0.023:0.0027-0.0067:10.0-23.3, the preferred 1:3-5:0.0133-0.0200:0.0033-0.0050:16.7-23.3 of said ratio.
Advantage of the present invention is: 1, this invention has been saved the gelatinization step of starch in the traditional method in technology.Because this product is to be raw material with the yam starch dextrin, and this raw material just has good solvability in cold water.2, the starting raw material of production dextrin is yam starch, and it is the very large agricultural-food of the northern area of China output, and the promotion conference of this technology expands out a new road for the deep processing of the northern area of China agricultural-food, thereby the peasant is increased income.3, in this invention desired raw material proportioning, dextrin and acrylic acid proportioning are at 1:3, and be low than the vinylformic acid consumption of like product, makes the relative like product of cost reduce greatly, and performance is than commercially available prod height, and high water absorption reaches 1880g/g.
Super absorbent resin of the present invention is mainly used in water-loss reducer of soil, modifying agent, has considerable effect at aspects such as agricultural, forestry, gardening, it can strengthen the ability of soil suction and water conservation, improve the crumb structure of soil, thereby make loosing soil that the ventilation property of soil, the day and night temperature of soil are all improved.Because product price ratio height of the present invention can be widely used in each side such as agricultural, forestry.
Description of drawings
Fig. 1 is the synthesis process flow diagram of High hydrophilous resin
Fig. 2 is that dosage of crosslinking agent is to the influence curve (acrylate is sodium salt) of High hydrophilous resin water-intake rate
Fig. 3 is that initiator amount is to the influence curve (acrylate is sodium salt) of High hydrophilous resin water-intake rate
Fig. 4 is that the system Total Water is to the influence curve (acrylate is sodium salt) of High hydrophilous resin water-intake rate
Fig. 5 is that yam starch dextrin and vinylformic acid mass ratio are to the influence curve (acrylate is sodium salt) of High hydrophilous resin water-intake rate
Fig. 6 is that acrylic acid degree of neutralization is to the influence curve (acrylate is sodium salt) of High hydrophilous resin water-intake rate
Fig. 7 is that dosage of crosslinking agent is to the influence curve (acrylate is sylvite) of High hydrophilous resin water-intake rate
Fig. 8 is that initiator amount is to the influence curve (acrylate is sylvite) of High hydrophilous resin water-intake rate
Fig. 9 is that the system Total Water is to the influence curve (acrylate is sylvite) of High hydrophilous resin water-intake rate
Figure 10 is that yam starch dextrin and vinylformic acid mass ratio are to the influence curve (acrylate is sylvite) of High hydrophilous resin water-intake rate
Figure 11 is that acrylic acid degree of neutralization is to the influence curve (acrylate is sylvite) of High hydrophilous resin water-intake rate
Figure 12 is that degree of neutralization is the infrared spectrogram (acrylate is sodium salt) of 30% High hydrophilous resin
Figure 13 is that degree of neutralization is the infrared spectrogram (acrylate is sylvite) of 30% High hydrophilous resin
Embodiment
Embodiment 1: weighing 1.5g sodium hydroxide, measure the 30.0ml deionized water, be mixed with sodium hydroxide solution, under ice-water bath cooling and stirring condition, in and 9.0g(8. 6ml) vinylformic acid.Take by weighing 3.0g yam starch dextrin, 40.00mg Potassium Persulphate, 20.00mgN, N ＇-methylene-bisacrylamide, measure the deionized water of 20.0ml, all join in the reactor, and the vinylformic acid that will make and sodium salt solution thereof are poured in the reactor, in stirring at room 1.0h, it is mixed.Under protection of nitrogen gas, stir, heat, control rate of heating simultaneously, bath temperature is slowly raise, graft copolymerization is fully carried out, after graft copolymerization begins, stop to stir.After this heat up gradually, after the water boiling in reaching water-bath, continue heating and make it at this temperature range internal reaction 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, dry in 40 ℃ of-60 ℃ of baking ovens, namely get in the sodium hydroxide and acrylic acid degree of neutralization is 30% High hydrophilous resin through pulverizing, water regain reaches 1310g/g.
Embodiment 2: weighing 1.5g sodium hydroxide, measure the 30.0ml deionized water, be mixed with sodium hydroxide solution, under ice-water bath cooling and stirring condition, in and 9.0g(8. 6ml) vinylformic acid.Take by weighing 3.0g yam starch dextrin, 40.00mg Potassium Persulphate, 13.00mgN, N ＇-methylene-bisacrylamide is measured the deionized water of 20.0ml, all add in the reactor, and the vinylformic acid that will make and sodium salt solution thereof pour reactor into, in stirring at room 1.0h, it mixed.Under protection of nitrogen gas, stir, heat, control rate of heating simultaneously, bath temperature is slowly raise, graft copolymerization is fully carried out, after graft copolymerization begins, stop to stir.After this heat up gradually, after the boiling of the water in the water-bath, continue heating and make it at this temperature range internal reaction 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, dry in 40 ℃ of-60 ℃ of baking ovens, namely get in the sodium hydroxide and acrylic acid degree of neutralization is 40% High hydrophilous resin through pulverizing, water regain reaches 1270g/g.
Embodiment 3: weighing 3.5g sodium hydroxide, measure the 30.0ml deionized water, be mixed with sodium hydroxide solution, under ice-water bath cooling and stirring condition, in and 9.0g(8. 6ml) vinylformic acid.Take by weighing 3.0g yam starch dextrin, 40.00mg Potassium Persulphate, 20.00mgN, N ＇-methylene-bisacrylamide is measured the deionized water of 20.0ml, all add in the reactor, and the vinylformic acid that will make and sodium salt solution thereof pour reactor into, in stirring at room 1.0h, it mixed.Under protection of nitrogen gas, stir, heat, control rate of heating simultaneously, bath temperature is slowly raise, graft copolymerization is fully carried out, after graft copolymerization begins, stop to stir.After this heat up gradually, after the boiling of the water in the water-bath, continue heating and make it at this temperature range internal reaction 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, dry in 40 ℃ of-60 ℃ of baking ovens, namely get in the sodium hydroxide and acrylic acid degree of neutralization is 70% High hydrophilous resin through pulverizing, water regain reaches 1170g/g.
Embodiment 4: weighing 3.5g potassium hydroxide, measure the 30.0ml deionized water, be mixed with potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 15.0g(14. 3ml) vinylformic acid.Take by weighing 3.0g yam starch dextrin, 40.00mg Potassium Persulphate, 20.00mgN, N ＇-methylene-bisacrylamide is measured the deionized water of 20.0ml, all add in the reactor, and the vinylformic acid that will make and potassium salt soln thereof pour reactor into, in stirring at room 1.0h, it mixed.Under protection of nitrogen gas, stir, heat, control rate of heating simultaneously, bath temperature is slowly raise, graft copolymerization is fully carried out, after graft copolymerization begins, stop to stir.After this heat up gradually, after the boiling of the water in the water-bath, continue heating and make it at this temperature range internal reaction 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, dry in 40 ℃ of-60 ℃ of baking ovens, namely get in the potassium hydroxide and acrylic acid degree of neutralization is 30% High hydrophilous resin through pulverizing, water regain reaches 1200g/g.
Embodiment 5: weighing 2.1g potassium hydroxide, measure the 30.0ml deionized water, be mixed with potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 9.0g(8.6ml) vinylformic acid.Take by weighing 3.0g yam starch dextrin, 40.00mg Potassium Persulphate, 20.00mgN, N ＇-methylene-bisacrylamide is measured the deionized water of 20.0ml, all add in the reactor, and the vinylformic acid that will make and potassium salt soln thereof pour reactor into, in stirring at room 1.0h, it mixed.Under protection of nitrogen gas, stir, heat, control rate of heating simultaneously, bath temperature is slowly raise, graft copolymerization is fully carried out, after graft copolymerization begins, stop to stir.After this heat up gradually, after the boiling of the water in the water-bath, continue heating and make it at this temperature range internal reaction 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, dry in 40 ℃ of-60 ℃ of baking ovens, namely get in the potassium hydroxide and acrylic acid degree of neutralization is 30% High hydrophilous resin through pulverizing, this product water regain reaches 1380g/g.
Embodiment 6: weighing 1.4g potassium hydroxide, measure the 30.0ml deionized water, be mixed with potassium hydroxide solution, under ice-water bath cooling and stirring condition, in and 9.0g(8.6ml) vinylformic acid.Take by weighing 3.0g yam starch dextrin, 40.00mg Potassium Persulphate, 20.00mgN, N ＇-methylene-bisacrylamide is measured the deionized water of 20.0ml, all add in the reactor, and the vinylformic acid that will make and potassium salt soln thereof pour reactor into, in stirring at room 1.0h, it mixed.Under protection of nitrogen gas, stir, heat, control rate of heating simultaneously, bath temperature is slowly raise, graft copolymerization is fully carried out, after graft copolymerization begins, stop to stir.After this heat up gradually, after the boiling of the water in the water-bath, continue heating and make it at this temperature range internal reaction 1-2h, stop logical nitrogen, be cooled to room temperature.Product is taken out, it is cut into fritter, dry in 40 ℃ of-60 ℃ of baking ovens, namely get in the potassium hydroxide and acrylic acid degree of neutralization is 20% High hydrophilous resin through pulverizing, water regain reaches 1100g/g.
Claims (3)
1. one kind is the method for feedstock production High hydrophilous resin with the yam starch dextrin; it is characterized in that: preparation sodium hydroxide or potassium hydroxide solution; under the ice-water bath cooling; remove the vinylformic acid of stopper with the sodium hydroxide for preparing or potassium hydroxide solution neutralization; wherein the weight ratio of vinylformic acid and sodium hydroxide is 6-18:0.67-6.00; when with in the potassium hydroxide and during vinylformic acid; the weight ratio of vinylformic acid and potassium hydroxide is 6-18:0.93-8.40; with vinylformic acid and the salt thereof after the neutralization; the yam starch dextrin; Potassium Persulphate; N; N ＇-methylene-bisacrylamide; a certain amount of deionized water mixes; stirred 1.0 hours; yam starch dextrin wherein; vinylformic acid; Potassium Persulphate; N; N ＇-methylene-bisacrylamide; the weight ratio of the total deionized water of system is 1:2:0.0133-0.0200:0.0033-0.0050:16.7-23.3; under protection of nitrogen gas; heating in water bath also stirs; stop when reaching certain temperature stirring; insulation is 1-2 hour in boiling water bath; stop logical nitrogen then; product is taken out; cut into fritter; in 40 ℃-60 ℃ baking oven, dry to constant weight, pulverize, namely be able to the High hydrophilous resin that the yam starch dextrin is raw material.
According to claim 1 described a kind of be the method for feedstock production High hydrophilous resin with the yam starch dextrin, wherein a certain amount of deionized water is dissolving yam starch dextrin, Potassium Persulphate, N, the deionized water total amount that N ＇-methylene-bisacrylamide is used.
According to claim 1 described a kind of be the method for feedstock production High hydrophilous resin with the yam starch dextrin, total amount of deionized water is for preparing sodium hydroxide or potassium hydroxide solution and dissolving yam starch dextrin, Potassium Persulphate, N, the total amount of the deionized water that N ＇-methylene-bisacrylamide is used.
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| CN104177545A (en) * | 2014-07-08 | 2014-12-03 | 内蒙古大学 | Method for preparing super absorbent resin through graft polymerization of hydrogen peroxide-oxidized potato starch |
| CN105884972A (en) * | 2014-11-06 | 2016-08-24 | 邹城市安德机械制修有限公司 | Method for preparing macromolecular water-absorbing resin by utilizing whole potato flour |
| CN109126008A (en) * | 2018-06-28 | 2019-01-04 | 南京理工大学 | Macromolecule water uptake resin and preparation method thereof suitable for extinguishing chemical |
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| EP1781709A4 (en) * | 2004-08-27 | 2011-07-06 | Absorbent Technologies Inc | Superabsorbent polymers in agricultural applications |
| CN101638456B (en) * | 2009-09-14 | 2011-06-22 | 内蒙古大学 | Method for preparing super absorbent resin with cross-linked structure by using potato starch as raw material |
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