CN101302271A - Preparation of potassium-containing super absorbent resin - Google Patents
Preparation of potassium-containing super absorbent resin Download PDFInfo
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- CN101302271A CN101302271A CNA2007100974367A CN200710097436A CN101302271A CN 101302271 A CN101302271 A CN 101302271A CN A2007100974367 A CNA2007100974367 A CN A2007100974367A CN 200710097436 A CN200710097436 A CN 200710097436A CN 101302271 A CN101302271 A CN 101302271A
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- potassium
- acrylic acid
- water
- vinylformic acid
- absorbent resin
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Abstract
The invention discloses a method for making kalium-containing super absorbent resin. The method comprises the following main technological processes that: acrylic acid is adopted to pass through a neutral aluminum oxide chromatographic column so as to remove polymerization inhibitor; a mixed solution of sodium hydroxide and potassium hydroxide and acrylic acid undergo neutralization reaction in ice-water bath, and potato starch is mixed with deionized water so as to carry out gelatinization; the neutralized acrylic acid and the salt solution of the acrylic acid are mixed with the gelatinized potato starch, and then initiator potassium persulphate is added in; the mixture is stirred evenly under the protection of nitrogen and then is heated by water bath so as to ensure that potato starch, acrylic acid and the salt of the acrylic acid undergo graft copolymerization reaction under the protection of nitrogen; finally, the mixture undergoes heat-preservation reaction and then is dried and crushed so as to obtain the kalium-containing super absorbent resin. The super absorbent resin made by the method has greatly increased water-absorbing capacity and contains kalium nutrient element as compared with similar products; moreover, the super absorbent resin plays an important role in soil water conservation, desert control and plant growth, etc. in arid areas.
Description
Technical field
The present invention relates to be used for the preparation method of the High hydrophilous resin of agricultural, forestry, livestock industry, gardening and daily necessities, referring in particular to yam starch, vinylformic acid is the preparation method that main raw material synthesizes the High hydrophilous resin that contains the potassium nutrition element.
Background technology
Water-absorbent that High hydrophilous resin is good and water-retentivity make it all obtain application in a lot of fields.Sanitary products such as disposable diaper are the Application Areass that High hydrophilous resin is developed the earliest, are still the maximum consumption market of High hydrophilous resin at present.High hydrophilous resin is joined in the soil, can change the crumb structure of soil, increase water-permeable, the ventilation property of soil, and the water that adds can be stored, keep at the moisture of arid area soil, the desert has tempting prospect aspect preventing and treating.Japan and France are used for the Middle East and North Africa with High hydrophilous resin now, implement the plan that the desert becomes the oasis.High hydrophilous resin is used for optical cable, cable, the entering of water in the time of can avoiding cable failure, aspect this year the growth rate of demand be 30%.
The preparation method of High hydrophilous resin is a lot, and synthesis material is abundant, and production technique is different.Though China has obtained certain achievement in the research of High hydrophilous resin, but with abroad compare, gap is also quite big, suction multiple as resin is low, salt resistant character is poor, low, the complex manufacturing of gel-strength, product cost after the suction are high, the performance of especially theoretical in suction, water-retaining agent and the research of application facet are also few, the kind of suitability for industrialized production manufacturer production and quantity are also fewer, have many need of work people deeply to do.We should give full play to China's starch, the abundant advantage of Mierocrystalline cellulose natural resource, produce the High hydrophilous resin of high-quality suitable China's national situation, lay the foundation for High hydrophilous resin becomes the third-largest agrochemicals of China and is applied to every field.
The High hydrophilous resin suction is extremely strong, and its suction back swelling is a gel, and when being subjected to the external force extruding, water also is difficult for running off, and has good water retention property.High hydrophilous resin is a kind of novel macromolecular material.High hydrophilous resin is born in the sixties in 20th century as a kind of functional high molecule material.Be described as one of new technology nineties in 20th century in Japan.Starch is one of raw material of synthesizing super absorbent resin preferably.At present, very fast with the development of starch synthetic High hydrophilous resin.Owing to have advantages such as the multiplying power of absorption height, speed be fast with the super-strong moisture absorbing of treated starch preparation, so treated starch has more wide application prospect in water-retaining agent.
Starch is a kind of natural high moleculer eompound of renewable, wide material sources.The graft copolymer of wetting ability vinyl monomers such as starch and vinyl cyanide, vinylformic acid, acrylamide is one of kind in the present High hydrophilous resin market.And because starch is cheap, biodegradability good, than synthesizing series remarkable advantages arranged on disposable Personal hygiene product market.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method who contains the potassium High hydrophilous resin, this preparation method is a main raw material with yam starch, vinylformic acid, Potassium Persulphate, sodium hydroxide and potassium hydroxide, warp is proportioning rationally, makes by certain production process to contain the potassium High hydrophilous resin.
The technical problem to be solved in the present invention is solved by following scheme: a kind of preparation method who contains the potassium High hydrophilous resin; it is characterized in that: the chromatographic column of vinylformic acid by neutral alumina separated or the method for underpressure distillation reaches and removes the wherein purpose of stopper; under the ice-water bath cooling; with total concn is that 25% sodium hydroxide and potassium hydroxide mixing solutions and vinylformic acid carry out neutralization reaction; vinylformic acid; the weight ratio of sodium hydroxide and potassium hydroxide is 1: 0.10-0.51: 0.01; yam starch and deionized water are with 1: the weight ratio of 4-6 is mixed; under 60 ℃-70 ℃, carry out gelatinization; vinylformic acid after the neutralization and the yam starch after salt and the gelatinization thereof are mixed; pasting potato starch wherein; sodium acrylate; potassium acrylate and acrylic acid weight ratio are 1: 0.24-1.19: 0.026: 0.80-0.07; the Potassium Persulphate that adds yam starch quality 1.0%-2.0% is made initiator; under nitrogen protection, stirred 0.5-1.0 hour; mixture is under agitation mixed; heat up gradually with heating in water bath afterwards and reach 90 ℃-100 ℃ until temperature; make yam starch and vinylformic acid and salt thereof carry out graft copolymerization; reaction process is carried out under nitrogen protection; and make mixture under 90 ℃ of-100 ℃ of conditions insulation reaction 1-2 hour; in 40 ℃-60 ℃ baking oven, dry to constant weight; pulverize, promptly get and contain the potassium High hydrophilous resin.
The advantage of invention is: 1, the performance of this product is fine, the highest suction amount of deionized water at 1000-1200 is doubly inhaled from the beginning the water yield and at 300-500 is doubly inhaled saline volume at 100-120 doubly, inhale the artificial urine amount at 120-145 doubly, corresponding absorbed dose is more than the twice of like product on the market.2, this product is raw material with the yam starch, because yam starch is different with other starch structure, making its water regain the highest is to be to occur in 30% o'clock at degree of neutralization, rather than occurs when higher degree of neutralization, so just is that this product further increases the nitrogen element and provides convenience.3, the raw material of producing this product is a yam starch, and it is the very large agricultural-food of the northern area of China output, and the promotion conference of this product expands out a new road for the deep processing of the northern area of China agricultural-food, thereby the peasant is increased income.4, contain the necessary for plant growth potassium element in this product, keeping as soil moisture is the product that kills two birds with one stone.5, the proportioning raw materials among the present invention, yam starch gelatinization point, initiator amount all have different significantly, specific as follows with the technology of other products: the proportioning of (1) reactant is meant the ratio of yam starch and acrylic acid quality.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 acrylic acid content, thereby influences the water absorbing properties of product.In addition, space steric effect and acrylic acid autohemagglutination phenomenon also can make the water-intake rate of product reduce in the graft copolymerization.Take all factors into consideration, final yam starch and vinylformic acid weight ratio are 1: 4-6.(2) gelatinization of starch is meant that starch under suitable temperature, swelling takes place in water, and division forms uniform pasty state solution.The too high meeting of temperature causes " wearing out ", is difficult for disperseing in water, and percentage of grafting is reduced, and water-retaining capacity descends; Temperature is crossed low then starch the gelatinization effect is not taken place.The gelatinization point that yam starch relatively is fit to is 60 ℃-70 ℃.(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 1.0%-2.0% of starch quality.
Be mainly used in disposable personal hygiene article after this High hydrophilous resin is broken, can also be used for simultaneously some fields such as soil conservation aspect, because this High hydrophilous resin can also change the crumb structure of soil, increase water-permeable, the ventilation property of soil, and rainwater or irrigation water can be stored, therefore the moisture at arid area soil keeps, the desert can play very big effect aspect preventing and treating.
Description of drawings
Fig. 1 is preparation technology's schema of the present invention
Fig. 2 is that total degree of neutralization is the influence curve figure of the content of 93% o'clock potassium hydroxide to the product water-intake rate
Fig. 3 is degree of neutralization is inhaled the influence of deionized water rate to product a graphic representation
Fig. 4 is degree of neutralization is inhaled the influence of tap water rate to product a graphic representation
Fig. 5 is degree of neutralization is inhaled the influence of physiological saline rate to product a graphic representation
Fig. 6 is the graphic representation of rate of water absorption of the present invention
Fig. 7 is the graphic representation of High hydrophilous resin salt tolerance
Fig. 8 is that degree of neutralization is 30% the infrared spectrogram that contains the potassium High hydrophilous resin
With degree of neutralization is that 30% High hydrophilous resin is an example, via NEXUS
TM670FT-IRE.S.P type determination of infrared spectroscopy.
Main absorption peak (σ/the cm of IR spectrum
-1): 3455.40 (very strong), 2927.97,2855.45,2525.22,2166.34,1976.80,1719.13 (by force), 1568.15,1456.01,1412.91,1259.56,1163.44,1079.81,1021.37,922.77,803.41,764.36,613.86,575.25,514.20.Degree of neutralization is 30% the ultimate analysis data that contain the potassium High hydrophilous resin
With degree of neutralization is that 30% the High hydrophilous resin that contains potassium and nitrogen is an example, measures through German Elementar Vario EL III type ultimate analysis instrument, and the content of product is: N%=0.035; C%=42.69; H%=5.270.
Embodiment
Embodiment 1: weighing 4.7g sodium hydroxide and 0.4g potassium hydroxide, measure the 15.0ml deionized water, the sodium hydroxide and the potassium hydroxide mixing solutions (wherein the shared degree of neutralization of potassium hydroxide is 1.7%) of preparation 25%, under ice-water bath cooling and stirring condition, in and 30.0g (28.6ml) vinylformic acid.Take by weighing the 5.0g yam starch; measure the 25.0ml deionized water; mix under stirring; gelatinization in 65 ℃ of water-baths; be cooled to room temperature then, add 79.8mg Potassium Persulphate initiator and neutral vinylformic acid and acrylic acid solution, under nitrogen protection; stirring at room half an hour, it is mixed.Stir heating down, control rate of heating simultaneously, bath temperature is slowly raise, and react fully and carry out, when temperature reaches 80 ℃, stop to stir.After this heat up gradually, when bath temperature is 90 ℃-100 ℃, continues heating and make it, stop logical nitrogen, be cooled to room temperature this temperature range internal reaction 1-2 hour.Product is taken out, it is cut into fritter, in 40 ℃-60 ℃ baking oven, dry, pulverize to constant weight, promptly get degree of neutralization and be 30% contain the potassium High hydrophilous resin.
Embodiment 2: weighing 8.0g sodium hydroxide and 0.4g potassium hydroxide, measure the 25.0ml deionized water, the sodium hydroxide and the potassium hydroxide mixing solutions (wherein the shared degree of neutralization of potassium hydroxide is 1.7%) of preparation 25%, under ice-water bath cooling and stirring condition, in and 30.0g (28.6ml) vinylformic acid.Take by weighing the 5.0g yam starch; measure the 25.0ml deionized water; mix under stirring; gelatinization in 65 ℃ of water-baths; be cooled to room temperature then, add 81.2mg Potassium Persulphate initiator and neutral vinylformic acid and acrylic acid solution, under nitrogen protection; stirring at room half an hour, it is mixed.Stir heating down, control rate of heating simultaneously, bath temperature is slowly raise, and react fully and carry out, when temperature reaches 80 ℃, stop to stir.After this heat up gradually, when bath temperature is 90 ℃-100 ℃, continues heating and make it, stop logical nitrogen, be cooled to room temperature this temperature range internal reaction 1-2 hour.Product is taken out, it is cut into fritter, in 40 ℃-60 ℃ baking oven, dry, pulverize to constant weight, promptly get degree of neutralization and be 50% contain the potassium High hydrophilous resin.
Claims (1)
1; a kind of preparation method who contains the potassium High hydrophilous resin; it is characterized in that: vinylformic acid is separated by the chromatographic column of neutral alumina remove wherein stopper; under the ice-water bath cooling; with total concn is that 25% sodium hydroxide and potassium hydroxide mixing solutions and vinylformic acid carry out neutralization reaction; vinylformic acid; the weight ratio of sodium hydroxide and potassium hydroxide is 1: 0.10-0.51: 0.01; yam starch and deionized water are with 1: the weight ratio of 4-6 is mixed; under 60 ℃-70 ℃, carry out gelatinization; vinylformic acid after the neutralization and the yam starch after salt and the gelatinization thereof are mixed; pasting potato starch wherein; sodium acrylate; potassium acrylate and acrylic acid weight ratio are 1: 0.24-1.19: 0.026: 0.80-0.07; the Potassium Persulphate that adds yam starch quality 1.0%-2.0% is made initiator; under nitrogen protection, stirred 0.5-1.0 hour; mixture is under agitation mixed; heat up gradually with heating in water bath afterwards and reach 90 ℃-100 ℃ until temperature; make yam starch and vinylformic acid and salt thereof carry out graft copolymerization; reaction process is carried out under nitrogen protection; and make mixture under 90 ℃ of-100 ℃ of conditions insulation reaction 1-2 hour; in 40 ℃-60 ℃ baking oven, dry to constant weight; pulverize, promptly get and contain the potassium High hydrophilous resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100974367A CN101302271B (en) | 2007-05-11 | 2007-05-11 | Preparation of potassium-containing super absorbent resin |
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| CN2007100974367A CN101302271B (en) | 2007-05-11 | 2007-05-11 | Preparation of potassium-containing super absorbent resin |
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| CN101302271A true CN101302271A (en) | 2008-11-12 |
| CN101302271B CN101302271B (en) | 2011-11-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638459B (en) * | 2009-09-14 | 2010-11-17 | 内蒙古大学 | Method for preparing super absorbent resin with high potassium content by using carboxymethyl potato starch as raw material |
| CN111761898A (en) * | 2020-07-03 | 2020-10-13 | 泉州陶纪塑胶有限公司 | Medical packaging film and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046738C (en) * | 1996-12-26 | 1999-11-24 | 国内贸易部谷物油脂化学研究所 | Method for preparation of starch graft copolymer acrylic acid (acrylate) super water-absorbing agent |
| CA2532918C (en) * | 2003-07-25 | 2012-07-10 | Basf Aktiengesellschaft | Aqueous dispersions of hydrosoluble polymerisates of ethylenically unsaturated anionic monomers, method for the production and use thereof |
| CN1268661C (en) * | 2004-05-20 | 2006-08-09 | 合肥工业大学 | Starch high water absorption resin production process |
| US20060254738A1 (en) * | 2005-05-16 | 2006-11-16 | Anderson Kevin R | Cationic crosslinked starch containing compositions and use thereof |
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2007
- 2007-05-11 CN CN2007100974367A patent/CN101302271B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638459B (en) * | 2009-09-14 | 2010-11-17 | 内蒙古大学 | Method for preparing super absorbent resin with high potassium content by using carboxymethyl potato starch as raw material |
| CN111761898A (en) * | 2020-07-03 | 2020-10-13 | 泉州陶纪塑胶有限公司 | Medical packaging film and preparation method thereof |
| CN111761898B (en) * | 2020-07-03 | 2022-08-16 | 潮州市潮安区恒昌印制有限公司 | Medical packaging film and preparation method thereof |
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| CN101302271B (en) | 2011-11-30 |
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Granted publication date: 20111130 Termination date: 20130511 |