CN1580088A - Starch high water absorption resin production process - Google Patents
Starch high water absorption resin production process Download PDFInfo
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- CN1580088A CN1580088A CN 200410044870 CN200410044870A CN1580088A CN 1580088 A CN1580088 A CN 1580088A CN 200410044870 CN200410044870 CN 200410044870 CN 200410044870 A CN200410044870 A CN 200410044870A CN 1580088 A CN1580088 A CN 1580088A
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Abstract
This invention refers to the manufacturing engineering of amylaceous rosin with high water absorption. The inventing engineering is as follows: mix the amylum with water at 1:3 or so, add an amount of hydrochloric acid for acidolysis, then add little sodium hydroxide solution and sodium carbonate solution to it, add initiator, crosslinking agent and so on in turn, dry and get the product after smashing it. Compared with the former method, this method reduces the dosage of gelatinized water greatly, also decreases the drying time as well as increases the production efficiency, removes the steps of heating and aerating N2 and reduces the production cost greatly. The product is characterized with high water-absorbing capacity, high water-intake rate and easy biodegradation, emits innocuous material and can be used widely in the fields of agriculture and sanitation.
Description
Technical field
The present invention relates to a kind of producing and manufacturing technique of starch based High hydrophilous resin.
Background technology
Sixties end, the what is called " High hydrophilous resin (Super AbsorbentPolymer) " that water regain reaches self hundred times occurred, to be laboratory, the USDA north in 1969 be hydrolyzed starch-acrylonitrile graft copolymer to High hydrophilous resin the earliest obtains.Various types of High hydrophilous resins have appearred after this, they can absorb self hundred times to several thousand times water, and pressurization also is difficult to water sepn is come out, and becomes good water-absorbing-retaining material, all has purposes widely in many fields such as industry, agricultural, daily life, health cares.
High hydrophilous resin generally can be divided into synthetic resin, starch based and cellulose family.The synthetic resin production technique is simple, steadily and be easy to carry out, but water-intake rate is low, is difficult to biological degradation; Though but the cellulose family biodegrade, water-intake rate is lower; The hydrolyzate High hydrophilous resin water-intake rate of starch-grafted polyacrylonitrile is big, biodegradable, but complex manufacturing, remaining monomer is poisonous; The starch grafted polyacrylamide water-retaining capacity is big, readily biodegradable, but rate of water absorption is slow.These High hydrophilous resins are difficult in hygiene article sector and obtain to use widely.
The synthesis preparation method of high water-absorbent starch graft copolymers is normally: the mixed of earlier starch and water being pressed about 1: 10, under 75～95 ℃ temperature, heat gelatinization 15～30min then, its objective is that the macromolecular chain in order to make starch fully stretches, be convenient to catalyzer and carry out graft reaction with contacting of each position of monomer and its.Add monomer then, under suitable initiation conditions, carry out graft polymerization reaction.The temperature of graft polymerization reaction generally is controlled between 30～50 ℃, and temperature is too high, is easy to generate more homopolymer.In the starch-grafted process, for preventing entrained air, oxidizing reaction takes place, reaction process need be filled N all the time
2Gas shiled.This has improved the High hydrophilous resin production cost to a certain extent.
What the initiator of graft polymerization early used is ceric ammonium nitrate, Ce
4+Under acidic conditions, cause vinyl monomer graft polymerization on starch, can obtain high efficiency graft product.Though high-energy radiation also can the initiation grafting polymerization, in actual industrial production, it is practical more that initiator seems, is convenient to popularize.
The vinyl monomer of graft polymerization, basically all be have soluble in water, or the process hydrolysis reaction can produce the organic molecule of hydrophilic radical, mainly contain vinyl cyanide, acrylic or methacrylic acid (salt or ester), acrylamide, had the sulfonic group monomer to participate in the report that graft copolymer can improve the suction multiple greatly in recent years again.Utilize vinyl cyanide grafting on starch to prepare water-absorbing resin, need make not hydrophilic itrile group become hydrophilic carboxyl and amide group in hydrolysis under the alkaline condition.And then carry out suitable crosslinking reaction and become water-absorbing resin.
Crosslinked about grafts, though method is a lot, it is crosslinked that remaining of more generally using utilizes linking agent to carry out, employed linking agent has usually can participate in polymeric diene class, for example divinylbenzene, bisacrylamide etc.
The present invention is intended to, and provides that a kind of production technique is simple, the producing and manufacturing technique of low cost of manufacture, starch based High hydrophilous resin that the products obtained therefrom water-retaining capacity is big.
Concrete realization above-mentioned purpose processing method of the present invention comprises following operation:
The producing and manufacturing technique of starch based High hydrophilous resin is characterized in that:
A, at normal temperatures with 5g starch and water by 1: 2.5-1: 4 mixed is even;
The hydrochloric acid soln of 0.2～0.5mol/L of B, adding 5%, acidolysis 1～2 hour;
C, to add concentration then in system be 40% sodium hydroxide solution 2ml and yellow soda ash 1.06g, stirs;
D, add Potassium Persulphate 0.06g, vinylformic acid 20ml, glycerine solution 0.2-0.4ml and 40% sodium hydroxide solution 18ml successively again, stirred 5 minutes
E, send into baking oven, dry under 70 ℃ of temperature, pulverize and promptly get starch graft polyacrylic acid superabsorbent, the water-intake rate of gained High hydrophilous resin can reach 800～1000 times.
Described 1.06g yellow soda ash adds in the material that adds behind the 3ml water wiring solution-forming after the acidolysis.
The present invention is in using the process of acid treated starches, acid acts on glycosidic link and makes the starch molecule hydrolysis, because the influence of starch granules crystalline texture becomes crystalline structure via hydrogen bonded between amylose molecule, difficulty is infiltrated in acid, its α-1,4 glycosidic links are difficult for by acid hydrolysis, and α-1,4 glycosidic link, the α-1 of the amylopectin molecule of amorphous domain in the particle, 6 keys are more easily infiltrated by acid, and hydrolysis takes place.Thereby starch can disintegrate down the starch side chain through suitable acidolysis from main chain, thereby increased the terminal number of starch chain, makes that graft reaction is easier to carry out.
In addition, add an amount of yellow soda ash in the grafting process, it and vinylformic acid reaction generate CO
2Bubble makes the High hydrophilous resin short texture, and specific surface area increases, and has improved rate of water absorption.
The inventive method is compared with original method, has significantly reduced on the one hand the consumption (the former is 3 times of amount of starch, and the latter is 10 times of amount of starch) of gelatinization water, has not only saved water resources, and has reduced drying time, has improved production efficiency; Heating and logical N have been saved on the other hand
2The step of gas reduces greatly to the requirement of reactor, and this has not only reduced production cost, and makes the easier realization of production of High hydrophilous resin.The consumption of acidolysis degree and linking agent has influenced the gel-strength and the water-intake rate of High hydrophilous resin, and the present invention is an initiator with Potassium Persulphate cheap and easy to get on the industrial production, and glycerine is linking agent, can make product be applicable to different occasions.Add the rate of water absorption that an amount of yellow soda ash has obviously improved High hydrophilous resin, overcome the slow deficiency of traditional product suction.Synthetic starch graft acrylic acid High hydrophilous resin of the present invention, production technique is simple, water-retaining capacity is big, rate of water absorption is high, is easy to biological degradation and nontoxic, has purposes widely at agricultural, health field.
Concrete embodiment
Below by embodiment, the present invention is described in further detail.
Embodiment:
Specific embodiment is:
In agitator, 5g starch and 15ml distilled water are mixed the hydrochloric acid soln of 0.2～0.5mol/L of adding 5%, acidolysis at normal temperatures 1～2 hour;
Add concentration then and be 40% sodium hydroxide solution 2ml and yellow soda ash 1.06g in system, wherein yellow soda ash adds 3ml water wiring solution-forming, stirs;
Then, add Potassium Persulphate 0.06g, vinylformic acid 20ml, glycerine solution 0.2～0.4ml and 40%NaOH solution 18ml successively, stir 5min, send into 70 ℃ of baking ovens, the oven dry back is pulverized and is promptly got starch graft polyacrylic acid superabsorbent.
Claims (2)
1, the producing and manufacturing technique of starch based High hydrophilous resin is characterized in that:
A, at normal temperatures with 5g starch and water by 1: 2.5-1: 4 mixed is even;
The hydrochloric acid soln of 0.2～0.5mol/L of B, adding 5%, acidolysis 1～2 hour;
C, to add concentration then in system be 40% sodium hydroxide solution 2ml and yellow soda ash 1.06g, stirs;
D, add Potassium Persulphate 0.06g, vinylformic acid 20ml, glycerine solution 0.2-0.4ml and 40% sodium hydroxide solution 18ml successively again, stirred 5 minutes
E, send into baking oven, dry under 70 ℃ of temperature, pulverize and promptly get starch graft polyacrylic acid superabsorbent, the water-intake rate of gained High hydrophilous resin can reach 800～1000 times.
2, the producing and manufacturing technique of starch based High hydrophilous resin according to claim 1 is characterized in that: described 1.06g yellow soda ash adds in the material that adds behind the 3ml water wiring solution-forming after the acidolysis.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410044870 CN1268661C (en) | 2004-05-20 | 2004-05-20 | Starch high water absorption resin production process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410044870 CN1268661C (en) | 2004-05-20 | 2004-05-20 | Starch high water absorption resin production process |
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| CN1580088A true CN1580088A (en) | 2005-02-16 |
| CN1268661C CN1268661C (en) | 2006-08-09 |
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| CN 200410044870 Expired - Fee Related CN1268661C (en) | 2004-05-20 | 2004-05-20 | Starch high water absorption resin production process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302270B (en) * | 2007-05-11 | 2010-05-26 | 内蒙古大学 | Preparation of nitrogen-containing super absorbent resin |
| CN101891829A (en) * | 2010-07-08 | 2010-11-24 | 广西大学 | Acid hydrolysis modified starch and method for preparing same |
| CN102093513A (en) * | 2010-12-20 | 2011-06-15 | 昆明理工大学 | Method for preparing absorbent resin by grafting acrylic acid with potato starch |
| CN101302271B (en) * | 2007-05-11 | 2011-11-30 | 内蒙古大学 | Preparation of potassium-containing super absorbent resin |
| CN101845123B (en) * | 2009-03-25 | 2011-12-21 | 青岛生物能源与过程研究所 | Method for preparing bio-based inorganic compound type water absorbent material |
| CN110387013A (en) * | 2019-01-28 | 2019-10-29 | 山东农业大学 | Low temperature rapid polymerization type starch base super absorbent polymer and preparation method thereof |
-
2004
- 2004-05-20 CN CN 200410044870 patent/CN1268661C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302270B (en) * | 2007-05-11 | 2010-05-26 | 内蒙古大学 | Preparation of nitrogen-containing super absorbent resin |
| CN101302271B (en) * | 2007-05-11 | 2011-11-30 | 内蒙古大学 | Preparation of potassium-containing super absorbent resin |
| CN101845123B (en) * | 2009-03-25 | 2011-12-21 | 青岛生物能源与过程研究所 | Method for preparing bio-based inorganic compound type water absorbent material |
| CN101891829A (en) * | 2010-07-08 | 2010-11-24 | 广西大学 | Acid hydrolysis modified starch and method for preparing same |
| CN101891829B (en) * | 2010-07-08 | 2012-07-04 | 广西大学 | Acid hydrolysis modified starch and method for preparing same |
| CN102093513A (en) * | 2010-12-20 | 2011-06-15 | 昆明理工大学 | Method for preparing absorbent resin by grafting acrylic acid with potato starch |
| CN102093513B (en) * | 2010-12-20 | 2012-10-31 | 昆明理工大学 | Method for preparing absorbent resin by grafting acrylic acid with potato starch |
| CN110387013A (en) * | 2019-01-28 | 2019-10-29 | 山东农业大学 | Low temperature rapid polymerization type starch base super absorbent polymer and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1268661C (en) | 2006-08-09 |
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Granted publication date: 20060809 |