CN101985488A - Method for preparing double-matrix nitrogen and potassium-containing super absorbent resin from carboxymethyl starch and phosphate starch serving as raw materials - Google Patents
Method for preparing double-matrix nitrogen and potassium-containing super absorbent resin from carboxymethyl starch and phosphate starch serving as raw materials Download PDFInfo
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- CN101985488A CN101985488A CN 201010501310 CN201010501310A CN101985488A CN 101985488 A CN101985488 A CN 101985488A CN 201010501310 CN201010501310 CN 201010501310 CN 201010501310 A CN201010501310 A CN 201010501310A CN 101985488 A CN101985488 A CN 101985488A
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Abstract
The invention provides a method for preparing double-matrix nitrogen and potassium-containing super absorbent resin from carboxymethyl starch and phosphate starch serving as raw materials. By performing grafting copolymerization on the carboxymethyl starch, the phosphate starch, acrylic acid and potassium salt thereof, acrylamide and the like, the double-matrix nitrogen and potassium-containing super absorbent resin is prepared by the method. Production is performed by an aqueous solution polymerization method, so that the synthesis process is simple, and energy consumption is low; and products are easy to degrade, do not pollute the environment, contain nitrogen, phosphorus and potassium which are needed by plants during growth, and can be widely applied to the fields such as agriculture, forestry, gardening, prevention and control of desertification and the like.
Description
Technical field
The present invention relates to a kind of High hydrophilous resin and preparation method thereof, especially relating to a kind of is the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production with carboxymethyl starch and phosphate ester starch, and product mainly is applicable to aspects such as agroforestry, gardening and desertification control.
Background technology
High hydrophilous resin (Super Absorbent Polymer is called for short SAP) is a kind of the have excellent water-absorbent and new functional macromolecule material of water-retentivity, can absorb the water of own wt hundred times or thousands of times and swelling is gel, water can not separated out yet under the pressure of certain limit, can recover its water absorbing properties again after the resin gel thing drying after the suction, thereby important use is all arranged in a lot of fields.As being applied to baby's paper nappy, sanitary napkin, medicament slow release material etc. aspect the medical and health, in industry and construction industry the waterproof etc. that blocks water as oil-water separating agent, siccative, deodorizing composition, cable and tunnel construction, on agricultural as soil improvement, desert afforestation, soil-less culture medium, drought-resistant water-preserving, agriculture chemical slowly-releasing, food and fruit freshness preserving material etc.Super absorbent resin in various fields, has especially become indispensable functional materials at aspects such as farming, woods, gardening and medical sanitaries with its high-performance.The birth of High hydrophilous resin makes the desert become the oasis and becomes a reality.
Along with the Application Areas of High hydrophilous resin is constantly expanded, common High hydrophilous resin can not satisfy application requiring on performance, and the High hydrophilous resin that R and D can be satisfied the specified property requirement has become current focus.The particularly application aspect farming, woods and gardening presses for the practical more multifunctional type High hydrophilous resin of development, as contains novel super absorbent resins such as plant-growth nutritive element, plant-growth regulator, slow release fertilizer.
Summary of the invention
The objective of the invention is to prepare the super absorbent resin fat prod that use in fields such as a kind of suitable agricultural, forestry, gardening and desertification control.
The invention provides a kind of is the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production with carboxymethyl starch and phosphate ester starch, and this method is to be that parent graft copolymerization vinylformic acid and sylvite thereof, acrylamide obtain two nitrogenous and potassium High hydrophilous resins of parent with carboxymethyl starch and phosphate ester starch.
Technical scheme of the present invention is as follows: under the ice-water bath cooling and stirring, remove the vinylformic acid of stopper with the potassium hydroxide solution neutralization, obtain vinylformic acid and potassium salt soln thereof, then with acrylamide soln, carboxymethyl starch and phosphate ester starch mix, stir 0.5-1.0h, reactant is mixed, add initiator persulphate and linking agent N at last, N '-methylene-bisacrylamide solution, stir 0.5-1.0h under the room temperature, wherein carboxymethyl starch and phosphate ester starch, acrylamide, vinylformic acid, potassium hydroxide, persulphate, N, N '-methylene-bisacrylamide, the mass ratio of total deionized water is 1: 0.05-20.00: 2-14: 6.00-23.33: 0.93-12.72: 0.0367-0.0567: 0.0020-0.0067: 33.33-53.33, feed nitrogen afterwards and slowly heating in water-bath, make it react 1h down at 60-80 ℃, continue to heat up, in boiling water bath, be incubated 1-2h again, stop logical nitrogen, be cooled to room temperature, product is taken out, oven dry is pulverized, and sieves, promptly getting acrylic acid degree of neutralization is the nitrogenous and potassium High hydrophilous resin of two parents of 20%-70%, and the water absorbent rate of products obtained therefrom is 850-1700 times.
Carboxymethyl starch described in the technique scheme is carboxymethyl potato starch, carboxymethyl W-Gum and carboxymethyl tapioca (flour), phosphate ester starch is phosphoric acid ester yam starch, phosphoric acid ester W-Gum and phosphoric acid ester tapioca (flour), preferred carboxymethyl potato starch and phosphoric acid ester yam starch.
The described acrylic acid degree of neutralization of scheme is 20%-70%, and it can be 20%, 30%, 40%, 50%, 60%, 70%, preferred 30%-50%.
The preferred Potassium Persulphate of the described initiator persulphate of scheme, ammonium persulphate.
The consumption of the described initiator persulphate of scheme is the 3.67%-5.67% of carboxymethyl starch quality, preferred 4.00%-5.00%.
The described linking agent N of scheme, the consumption of N '-methylene-bisacrylamide is the 0.20%-0.67% of carboxymethyl starch quality, preferred 0.25%-0.47%.
The described total deionized water of scheme is dissolved hydrogen potassium oxide, acrylamide and N, the deionized water total amount that N '-methylene-bisacrylamide is used.
Advantage of the present invention is as follows:
(1) used carboxymethyl starch and the phosphate ester starch of the present invention, meeting cold water is swellable, hot gelatinization operation when having omitted traditional technology use starch has been simplified production technique greatly, has shortened the production time.
(2) the prepared product of the present invention contains the required nitrogen of plant-growth, phosphorus, potassium element, and plant-growth is had certain promoter action.
(3) the prepared product of the present invention is degraded environmentally safe easily.
(4) the present invention adopts water solution polymerization process production, and synthesis technique is simple, and energy consumption is low, and the no three wastes produce, and help industrialization production.
Description of drawings
Fig. 1 is preparation technology's schema of product
Fig. 2 is the influence curve of the mass ratio of phosphoric acid ester yam starch and carboxymethyl potato starch to High hydrophilous resin suction multiple
Fig. 3 is the influence curve of the mass ratio of vinylformic acid and acrylamide to High hydrophilous resin suction multiple
Fig. 4 is the influence curve of the mass ratio of monomer (vinylformic acid and acrylamide) and parent (carboxymethyl potato starch and phosphoric acid ester yam starch) to High hydrophilous resin suction multiple
Fig. 5 is linking agent N, and N '-methylene-bisacrylamide consumption is to the influence curve of High hydrophilous resin suction multiple
Fig. 6 is the influence curve of acrylic acid degree of neutralization to High hydrophilous resin suction multiple
Fig. 7 is the influence curve of initiator amount to High hydrophilous resin suction multiple
Fig. 8 is the infrared spectrogram of embodiment 14 products
Embodiment
Embodiment 1: with 25.0ml deionized water dissolving 7.0g potassium hydroxide, under the ice-water bath cooling and stirring, in and 22.5g (21.4ml) vinylformic acid; With 42.0ml deionized water dissolving 7.5g acrylamide; With in the vinylformic acid and the potassium salt soln thereof of becoming reconciled mix with the dissolved acrylamide soln, add 1.5g carboxymethyl potato starch and 1.5g phosphoric acid ester yam starch, stir 0.5h, after mixing, adding 70mg Potassium Persulphate and 3ml concentration is the N of 1mg/ml, N '-methylene-bisacrylamide solution, stir 0.5h under the room temperature, feed nitrogen then and begin slowly heating in water-bath, make it react 1.0h down at 60-75 ℃, continue to heat up, in boiling water bath, be incubated 1.5h again, stop logical nitrogen, be cooled to room temperature, product is taken out, oven dry is pulverized, and sieves, promptly get the nitrogenous and potassium High hydrophilous resin of two parents, the suction multiple of present embodiment products obtained therefrom is 1590 times.
Embodiment 2: experiment condition is with embodiment 1, and different is to add 2.4g carboxymethyl potato starch and 0.6g phosphoric acid ester yam starch, and the suction multiple of present embodiment products obtained therefrom is 1700 times.
Embodiment 3: experiment condition is with embodiment 1, and different is to add 2.0g carboxymethyl potato starch and 1.0g phosphoric acid ester yam starch, and the suction multiple of present embodiment products obtained therefrom is 1620 times.
Embodiment 4: experiment condition is with embodiment 1, and different is to add 1.0g carboxymethyl potato starch and 2.0g phosphoric acid ester yam starch, and the suction multiple of present embodiment products obtained therefrom is 1450 times.
Embodiment 5: experiment condition is with embodiment 1, and different is to add 0.6g carboxymethyl potato starch and 2.4g phosphoric acid ester yam starch, and the suction multiple of present embodiment products obtained therefrom is 1250 times.
Embodiment 6: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 7.5g potassium hydroxide, under the ice-water bath cooling and stirring, in and 24g (22.9ml) vinylformic acid; With 42.0ml deionized water dissolving 6.0g acrylamide, the suction multiple of present embodiment products obtained therefrom is 1630 times.
Embodiment 7: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 7.8g potassium hydroxide, under the ice-water bath cooling and stirring, in and 25g (23.8ml) vinylformic acid; With 42.0ml deionized water dissolving 5.0g acrylamide, the suction multiple of present embodiment products obtained therefrom is 1590 times.
Embodiment 7: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 5.6g potassium hydroxide, under the ice-water bath cooling and stirring, in and 18g (17.1ml) vinylformic acid; With 42.0ml deionized water dissolving 6.0g acrylamide, the suction multiple of present embodiment products obtained therefrom is 1550 times.
Embodiment 8: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 6.3g potassium hydroxide, under the ice-water bath cooling and stirring, in and 20.25g (19.3ml) vinylformic acid; With 42.0ml deionized water dissolving 6.75g acrylamide, the suction multiple of present embodiment products obtained therefrom is 1600 times.
Embodiment 9: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 7.7g potassium hydroxide, under the ice-water bath cooling and stirring, in and 24.75g (23.4ml) vinylformic acid; With 42.0ml deionized water dissolving 8.25g acrylamide, the suction multiple of present embodiment products obtained therefrom is 1590 times.
Embodiment 10: experiment condition is with embodiment 1, and different is that adding 4ml concentration is the N of 1mg/ml, N '-methylene-bisacrylamide solution, and the suction multiple of present embodiment products obtained therefrom is 1560 times.
Embodiment 11: experiment condition is with embodiment 1, and different is that adding 5ml concentration is the N of 1mg/ml, N '-methylene-bisacrylamide solution, and the suction multiple of present embodiment products obtained therefrom is 1670 times.
Embodiment 12: experiment condition is with embodiment 1, and different is that adding 6ml concentration is the N of 1mg/ml, N '-methylene-bisacrylamide solution, and the suction multiple of present embodiment products obtained therefrom is 1540 times.
Embodiment 13: experiment condition is with embodiment 1, and different is to add the 65mg Potassium Persulphate, and the suction multiple of present embodiment products obtained therefrom is 1540 times.
Embodiment 14: experiment condition is with embodiment 1, and different is to add the 75mg Potassium Persulphate, and the suction multiple of present embodiment products obtained therefrom is 1590 times.
Embodiment 15: experiment condition is with embodiment 1, and different is to add the 80mg Potassium Persulphate, and the suction multiple of present embodiment products obtained therefrom is 1570 times.
Embodiment 16: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 5.25g potassium hydroxide, under the ice-water bath cooling and stirring, in and 22.5g (21.4ml) vinylformic acid, the suction multiple of present embodiment products obtained therefrom is 1530 times.
Embodiment 17: experiment condition is with embodiment 1, and different is with 25.0ml deionized water dissolving 8.75g potassium hydroxide, under the ice-water bath cooling and stirring, in and 22.5g (21.4ml) vinylformic acid, the suction multiple of present embodiment products obtained therefrom is 1570 times.
The infrared spectra of embodiment 14 products is by NEXUS
TM670FT-IR E.S.P type determination of infrared spectroscopy, main absorption peak: 3455cm
-1Stretching vibration absorption peak for-OH; 3127cm
-1Stretching vibration absorption peak for-NH; 2847cm
-1Be CH
2Stretching vibration absorption peak with CH; 1667cm
-1Stretching vibration absorption peak for acid amides C=O; 1633cm
-1Be COO
-The asymmetrical stretching vibration absorption peak; 1402cm
-1Be COO
-The symmetrical stretching vibration absorption peak.Measure through German Elementar Vario ELIII type ultimate analysis instrument, the constituent content of embodiment 14 products is: C%=38.34, H%=5.263, N%=2.601.
Claims (8)
1. with carboxymethyl starch and phosphate ester starch the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production, it is characterized in that: under the ice-water bath cooling and stirring, remove the vinylformic acid of stopper with the potassium hydroxide solution neutralization, obtain vinylformic acid and potassium salt soln thereof, then with acrylamide soln, carboxymethyl starch and phosphate ester starch mix, stir 0.5-1.0h, reactant is mixed, add initiator persulphate and linking agent N at last, N '-methylene-bisacrylamide solution, stir 0.5-1.0h under the room temperature, wherein carboxymethyl starch and phosphate ester starch, acrylamide, vinylformic acid, potassium hydroxide, persulphate, N, N '-methylene-bisacrylamide, the mass ratio of total deionized water is 1: 0.05-20.00: 2-14: 6.00-23.33: 0.93-12.72: 0.0367-0.0567: 0.0020-0.0067: 33.33-53.33, feed nitrogen afterwards and slowly heating in water-bath, make it react 1h down at 60-80 ℃, continue to heat up, in boiling water bath, be incubated 1-2h again, stop logical nitrogen, be cooled to room temperature, product is taken out, oven dry, pulverize, sieve, promptly getting acrylic acid degree of neutralization is the nitrogenous and potassium High hydrophilous resin of two parents of 20%-70%, and the water absorbent rate of products obtained therefrom is 850-1700 times.
2. according to claim 1, with carboxymethyl starch and phosphate ester starch is the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production, and it is characterized in that: described carboxymethyl starch is carboxymethyl potato starch, carboxymethyl W-Gum and carboxymethyl tapioca (flour).
3. according to claim 1, with carboxymethyl starch and phosphate ester starch is the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production, and it is characterized in that: described phosphate ester starch is phosphoric acid ester yam starch, phosphoric acid ester W-Gum and phosphoric acid ester tapioca (flour).
4. according to claim 1, with carboxymethyl starch and phosphate ester starch is the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production, and it is characterized in that: described carboxymethyl starch and phosphate ester starch are carboxymethyl potato starch and phosphoric acid ester yam starch.
5. according to claim 1, be the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production with carboxymethyl starch and phosphate ester starch, it is characterized in that: described acrylic acid degree of neutralization is 30%-50%.
6. according to claim 1, be the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production with carboxymethyl starch and phosphate ester starch, it is characterized in that: described initiator persulphate is Potassium Persulphate, ammonium persulphate.
7. according to claim 1, be the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production with carboxymethyl starch and phosphate ester starch, it is characterized in that: the consumption of described initiator persulphate is the 4.00%-5.00% of carboxymethyl starch quality.
8. according to claim 1, with carboxymethyl starch and phosphate ester starch is the method for the nitrogenous and potassium High hydrophilous resin of the two parents of feedstock production, it is characterized in that: described linking agent N, the consumption of N '-methylene-bisacrylamide are the 0.25%-0.47% of carboxymethyl starch quality.
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| CN2010105013103A CN101985488B (en) | 2010-10-09 | 2010-10-09 | Method for preparing double-matrix nitrogen and potassium-containing super absorbent resin from carboxymethyl starch and phosphate starch raw materials |
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| CN2010105013103A CN101985488B (en) | 2010-10-09 | 2010-10-09 | Method for preparing double-matrix nitrogen and potassium-containing super absorbent resin from carboxymethyl starch and phosphate starch raw materials |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663036A (en) * | 2017-10-19 | 2018-02-06 | 姜向军 | A kind of preparation method of anti-freezing type economization agent for concrete |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040224021A1 (en) * | 2003-04-25 | 2004-11-11 | Hossein Omidian | Formation of strong superporous hydrogels |
| CN101638458A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for preparing super absorbent resin by using carboxymethyl potato starch as raw material |
| CN101638461A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for synthesizing super absorbent resin containing phosphorus and nitrogen by graft copolymerization reaction of potato starch organic phosphate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040224021A1 (en) * | 2003-04-25 | 2004-11-11 | Hossein Omidian | Formation of strong superporous hydrogels |
| CN101638458A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for preparing super absorbent resin by using carboxymethyl potato starch as raw material |
| CN101638461A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for synthesizing super absorbent resin containing phosphorus and nitrogen by graft copolymerization reaction of potato starch organic phosphate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663036A (en) * | 2017-10-19 | 2018-02-06 | 姜向军 | A kind of preparation method of anti-freezing type economization agent for concrete |
| CN107663036B (en) * | 2017-10-19 | 2020-02-04 | 浙江龙游通衢建材有限公司 | Preparation method of anti-freezing concrete shrinkage reducing agent |
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