CN105713138A - Method for preparing high-water-absorption resin by using carboxymethyl potato starch and hydrogen peroxide as raw materials by one-pot method - Google Patents
Method for preparing high-water-absorption resin by using carboxymethyl potato starch and hydrogen peroxide as raw materials by one-pot method Download PDFInfo
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- CN105713138A CN105713138A CN201510257511.6A CN201510257511A CN105713138A CN 105713138 A CN105713138 A CN 105713138A CN 201510257511 A CN201510257511 A CN 201510257511A CN 105713138 A CN105713138 A CN 105713138A
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Abstract
The invention discloses a method for preparing high-water-absorption resin by using carboxymethyl potato starch and hydrogen peroxide as raw materials by a one-pot method. The method is mainly characterized in that the carboxymethyl potato starch oxidized by the hydrogen peroxide is not required to be separated, washed or purified, the carboxymethyl potato starch oxidized by the hydrogen peroxide, acrylic acid for removing an inhibitor and sodium salt of the acrylic acid are heated in water bath under the protection effect of nitrogen, high-water-absorption resin is synthesized by the one-pot method, and the maximum water absorption of the optimal product in 5,000 times of deionized water reaches 3,600 g/g. The high-water-absorption resin has the advantages that the carboxymethyl potato starch oxidized by the hydrogen peroxide is not required to be separated, purified or washed like the traditional oxidized carboxymethyl potato starch; and an initiator is not required to be added, meanwhile, the synthesized high-water-absorption resin has relatively high water absorption and excellent performance, and therefore, the high-water-absorption resin synthesized by the method is simple in technological method, low in cost and easy to produce in a large scale and popularize.
Description
Technical field
The preparation method that the present invention relates to a kind of functional high molecule material High hydrophilous resin for fields such as agricultural gardening, physiological hygiene, daily-use chemical industry, building trade, environmental improvements, particularly relates to the method being primary raw material one pot process High hydrophilous resin with hydrogen peroxide, carboxymethyl potato starch, sodium hydroxide.
Background technology
Super absorbent resin is that it can absorb the water of own wt hundred times to several thousand times containing polar group the functional high molecule material with three-dimensional crosslinked network structure in molecule.High hydrophilous resin is used widely with the complexing power of its water absorption, water-retaining property, the responsiveness stimulated to external world and heavy metal ion, as physiological hygiene articles for use, defend and control sand, urban afforestation and agricultural and the field such as gardening have a wide range of applications.
Get more and more about the research of High hydrophilous resin at present, but water absorbent rate is not high, complex technical process, the problem that high in cost of production problem is always up making researcher puzzled, the polymerization of High hydrophilous resin needs the initiation of initiator, initiator mainly has free radical (azo and persulfate etc.) initiator and redox initiator two class, but the shortcoming of this two classes initiator is to introduce foreign ion, eventually affects the water absorption of High hydrophilous resin.Therefore, how just right these problems that solve are the emphasis instantly studied.
The application adopts hydrogen peroxide oxidation carboxymethyl potato starch and acrylic acid and the sodium salt one pot process High hydrophilous resin thereof of removing polymerization inhibitor first, traditional method is first to pass through with hydrogen peroxide oxidation carboxymethyl potato starch to separate, washing, the steps such as drying prepare oxidated carboxymethyl potato starch, make raw material with hydrogen peroxide oxidation carboxymethyl potato starch again and prepare High hydrophilous resin with monomer polymerization, the application eliminates the separation of oxidated carboxymethyl potato starch well, washing, the steps such as drying, and initiator need not be added, the product simultaneously prepared has higher water absorption, most high water absorption is up to 3600g/g.Therefore, present invention process is simple, and production cost is low, practical, has good application and popularization value.
Summary of the invention
The invention provides super absorbent resin fat prod that a kind of technique is simple, production cost is low, water absorbing capacity is strong and preparation method thereof.
Its method and step are as follows:
(1) carboxymethyl potato starch is mixed by the mass ratio of 1:4～12:0.06～0.6 with deionized water, hydrogen peroxide, at 30-60 DEG C, then aoxidize 0.5-3h；Weigh the acrylic acid of carboxymethyl potato starch quality 3～12 times, weigh the sodium hydroxide of quality 0.11-0.444 times of acrylic acid, with the above-mentioned sodium hydroxide of deionized water dissolving of NaOH mass 3～12 times；With in above-mentioned sodium hydroxide and acrylic acid under ice-water bath cools down.
(2) by the carboxymethyl potato starch solution after above-mentioned oxidation with in sodium hydroxide and after acrylic acid solution be sufficiently mixed, adding and make cross-linking agent containing N, the N ＇-methylene-bisacrylamide of carboxymethyl potato starch quality 0.04～0.24%, stirring is so as to uniformly, pass into nitrogen, it is slowly heated, makes temperature of reaction system be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain High hydrophilous resin.Best product in the deionized water of 5000 times most high water absorption up to 3600g/g.
As it has been described above, the alkali in the present invention and used by acrylic acid be sodium hydroxide, N, N ＇-methylene-bisacrylamide solution concentration be 2.5mg/ml.
Advantages of the present invention:
(1) carboxymethyl potato starch water solublity is strong, does not need gelatinization process in the preparation process of High hydrophilous resin；
(2) present invention adopts one kettle way to prepare High hydrophilous resin first, it is easy to operation, technique simple.
(3) without adding initiator and polymerizable, will not introducing impurity, cost is low.
(4) peroxide decomposition product is water, pollution-free, and product has excellent performance simultaneously.
Accompanying drawing explanation
Fig. 1 is the process chart of carboxymethyl potato starch synthesizing super absorbent resin
Fig. 2 is the hydrogen peroxide use influence curve to High hydrophilous resin water absorption
The oxidizing temperature of Fig. 3 carboxymethyl potato starch influence curve to High hydrophilous resin water absorption
The oxidization time of Fig. 4 carboxymethyl potato starch influence curve to High hydrophilous resin water absorption
Fig. 5 is parent and the monomer ratio influence curve to High hydrophilous resin water absorption
Fig. 6 is acrylic acid degree of neutralization influence curve to High hydrophilous resin water absorption
Fig. 7 is the dosage of crosslinking agent influence curve to High hydrophilous resin water absorption
Fig. 8 is the reaction system total Water influence curve to High hydrophilous resin water absorption
Fig. 9 is the result of orthogonal experiment.
Detailed description of the invention
Embodiment 1: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, add 5ml hydrogen peroxide at 50 DEG C, aoxidize 2h, measure 20g (19.1ml) acrylic acid, weigh NaOH5.6g and be dissolved in 20ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and sodium salt thereof and oxidation be sufficiently mixed uniformly, adding 4ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, being slowly heated and make system temperature be stepped up, reaction to be polymerized stops stirring after starting, and continues slowly to heat up, and is incubated 2h at 80 DEG C, product drying, pulverizes and obtains product, and the High hydrophilous resin water absorption obtained by the present embodiment is 2350g/g.
Embodiment 2: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, add 6ml hydrogen peroxide at 55 DEG C, aoxidize 2h, measure 20g (19.1ml) acrylic acid, weigh NaOH5.6g and be dissolved in 20ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 4ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2400g/g.
Embodiment 3: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 20g (19.1ml) acrylic acid, weigh NaOH5.6g and be dissolved in 20ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 4ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2650g/g.
Embodiment 4: synthesis condition is with embodiment 3, and institute, the difference is that weighing 8.4g sodium hydroxide, is dissolved in 40ml deionized water, measures 30g (28.7ml) acrylic acid, and the water absorption of the High hydrophilous resin obtained by the present embodiment is 3500g/g.
Embodiment 5: synthesis condition is with embodiment 3, and institute, the difference is that weighing 13.9g sodium hydroxide, is dissolved in 40ml deionized water, measures 50g (47.6ml) acrylic acid, and the water absorption of the High hydrophilous resin prepared by the present embodiment is 2300g/g.
Embodiment 6: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 0.5h, measure 20g (19.1ml) acrylic acid, weigh NaOH5.6g and be dissolved in 20ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 4ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2500g/g.
Embodiment 7: synthesis condition is with embodiment 3, and institute, the difference is that weighing 13.32g sodium hydroxide, is dissolved in 40ml deionized water, measures acrylic acid 30g (28.7ml).High hydrophilous resin water absorption obtained by the present embodiment is 2100g/g.
Embodiment 8: weigh 5g carboxymethyl potato starch and mix homogeneously with 60ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 30g (28.6ml) acrylic acid, weigh NaOH8.4g and be dissolved in 20ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 4ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2750g/g.
Embodiment 9: synthesis condition is with embodiment 8, and institute, the difference is that weighing 8.4g sodium hydroxide, is dissolved in 80ml deionized water, and the High hydrophilous resin water absorption prepared by the present embodiment is 2800g/g.
Embodiment 10: synthesis condition is with embodiment 8, and institute, the difference is that weighing 8.4g sodium hydroxide, is dissolved in 100ml deionized water, and the High hydrophilous resin water absorption prepared by the present embodiment is 3250g/g.
Embodiment 11: weigh 5g carboxymethyl potato starch and mix homogeneously with 20ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 20g (19.1ml) acrylic acid, weigh NaOH4.44g and be dissolved in 40ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 3.2ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2000g/g.
Embodiment 12: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 30g (28.7ml) acrylic acid, weigh NaOH5.56g and be dissolved in 50ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 3.2ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2450g/g.
Embodiment 13: weigh 5g carboxymethyl potato starch and mix homogeneously with 50ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 30g (28.7ml) acrylic acid, weigh NaOH10g and be dissolved in 40ml deionized water, with above-mentioned prepared NaOH solution ice-water bath cool down under in and acrylic acid, by in carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, adding 3.2ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 2800g/g.
Embodiment 14: through L9(34) orthogonal experiment obtains the optimum condition of synthesizing super absorbent resin, specific embodiment is as follows:
Weigh 5g carboxymethyl potato starch to mix homogeneously with 50ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 30g (28.7ml) acrylic acid, weigh NaOH10g and be dissolved in 50ml deionized water, by above-mentioned prepared NaOH solution under ice-water bath cools down in and acrylic acid, by carboxymethyl potato starch solution after the acrylic acid become reconciled and oxidation be sufficiently mixed uniformly, addition 4ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and obtain product.High hydrophilous resin water absorption obtained by the present embodiment is 3600g/g.
Claims (5)
1. the method preparing High hydrophilous resin with carboxymethyl potato starch and hydrogen peroxide for raw material one kettle way, is characterised by that its method and step are:
(1) carboxymethyl potato starch is mixed by the mass ratio of 1:4-12:0.06-0.6 with deionized water, hydrogen peroxide, and at 30-60 DEG C, aoxidize 0.5-3h；Weigh the acrylic acid of carboxymethyl potato starch quality 3-12 times, weigh the sodium hydroxide of quality 0.11-0.44 times of acrylic acid, with the above-mentioned sodium hydroxide of the deionized water dissolving of NaOH mass 3-12 times；With in above-mentioned sodium hydroxide and acrylic acid under ice-water bath cools down；(2) by the carboxymethyl potato starch solution after above-mentioned oxidation with in sodium hydroxide and after acrylic acid solution be sufficiently mixed, adding and make cross-linking agent containing N, the N ＇-methylene-bisacrylamide of carboxymethyl potato starch quality 0.04-0.24%, stirring is so as to uniformly, pass into nitrogen, it is slowly heated, makes temperature of reaction system be stepped up, after beginning to be polymerized, stop stirring, continue to be slowly heated, at 80 DEG C, be incubated 2h, drying, pulverize and obtain High hydrophilous resin；Obtain the most high water absorption in the deionized water of 5000 times of the product under optimum condition by orthogonal experiment and reach 3600g/g.
2., according to claims 1, each raw material and proportioning (in mass ratio) thereof are carboxymethyl potato starch: dissolve its deionized water: H2O2: acrylic acid: NaOH: dissolve its deionized water: N, N ＇-methylene-bisacrylamide=1:4-12:0.06-0.6:3-12:0.66-3.36:4-12:0.0004-0.0024.
3. according to claims 1, wherein with in NaOH and acrylic acid degree of neutralization be 20%, 30%, 40%, 50%, 60%, 70%, 80%.
4., according to claims 1, N, the concentration of N ＇-methylene-bisacrylamide solution is 2.5mg/L.
5., according to claims 1, the mass fraction of hydrogen peroxide is 30%.
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| CN1208047A (en) * | 1998-07-16 | 1999-02-17 | 中国科学院广州化学研究所 | Preparation of high-hydroscopicity material with carboxymethyl starch as raw material |
| WO1999042496A1 (en) * | 1998-02-21 | 1999-08-26 | Basf Aktiengesellschaft | Radio transmitting digital camera |
| CN101638460A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for preparing super absorbent resin by graft copolymerization reaction of carboxymethyl potato starch, acrylamide, acrylic acid and sodium salt thereof |
| 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 |
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- 2015-05-20 CN CN201510257511.6A patent/CN105713138A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999042496A1 (en) * | 1998-02-21 | 1999-08-26 | Basf Aktiengesellschaft | Radio transmitting digital camera |
| CN1208047A (en) * | 1998-07-16 | 1999-02-17 | 中国科学院广州化学研究所 | Preparation of high-hydroscopicity material with carboxymethyl starch as raw material |
| CN101638460A (en) * | 2009-09-14 | 2010-02-03 | 内蒙古大学 | Method for preparing super absorbent resin by graft copolymerization reaction of carboxymethyl potato starch, acrylamide, acrylic acid and sodium salt thereof |
| 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 |
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