CN102219880B - Method for synthesizing super absorbent resin with starch grafted acrylic acid - Google Patents
Method for synthesizing super absorbent resin with starch grafted acrylic acid Download PDFInfo
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- CN102219880B CN102219880B CN2011101335367A CN201110133536A CN102219880B CN 102219880 B CN102219880 B CN 102219880B CN 2011101335367 A CN2011101335367 A CN 2011101335367A CN 201110133536 A CN201110133536 A CN 201110133536A CN 102219880 B CN102219880 B CN 102219880B
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Abstract
The invention relates to a method for synthesizing super absorbent resin with starch grafted acrylic acid. The method is characterized by comprising the steps of: adding 8-15 percent starch emulsion and acrylic acid with 70-90 percent neutralization degree into a reaction kettle to form aqueous phase, wherein the starch emulsion and acrylic acid are in a weight ration of 7-9:1; adding liquid paraffin wax according to oil-water ration of 0.8-1.6:1, and Span-80 and Tween-80 for mixed use with addition amount of 10-35 percent oil-water total amount, wherein the mass ratio leads the HLB (Hydrophile-Lipophile Balance) to be within 5.83-13.47; stirring for 30-50 minutes on the conditions of nitrogen and no oxygen as well as 45-65 DEG C; then sequentially adding ammonium persulphate with 2.5-3.5 percent of starch amount and N,N'-methylenebisacrylamide, reacting for 1.5-3 hours on the conditions of no oxygen and stirring, carrying out demulsication and extraction filtering with absolute ethyl alcohol; washing the product respectively with alcohol and acetone, carrying out vacuum drying to constant weight at 40-80 DEG C, drying and sieving; and quantitively weighing product in a Soxhlet extractor, extracting for 12-24 hours by taking acetone as solvent, and drying to constant weight in a hot air drying oven. The use of the method simplifies reaction process, leads to high water absorption multiplying power of products, fast speed, good water retention and multiplexing properties and safety.
Description
Technical field
The invention belongs to the functional high molecule material technical field, relate to a kind of preparation method who is prone to biolytic super absorbent resin.
Background technology
Super absorbent resin (Super Adsorbent Resin is called for short SAR) claim again (Super Adsorbent Polymer is called for short SAP) be have higher water absorption can and the general name of the high molecular polymer of water retention property, be a kind of water swelling type high molecular polymer that contains strongly hydrophilic group such as carboxyl, hydroxyl and have certain degree of crosslinking.It is water insoluble, also is insoluble to organic solvent, has unique suction and water retention property, possesses the advantage of macromolecular material simultaneously.It can absorb and keep the moisture of hundreds of times of sole masses and even thousands of times, is a kind of novel functional high molecule material.This type material has that capacity is big, rate of water absorption is fast, water retention capacity is strong and high-performance such as nonpoisonous and tasteless, and general water-absorbing material hardly matches.
Starch-grafted class super absorbent resin is big except that the capacity with general SAR, absorption speed reaches the advantages such as water retention capacity is strong soon, also has biodegradability, is considered to a kind of environment-friendly material.Utilize green starting material cheap, the renewable resources synthesized degradable, develop the novel process that super absorbent resin is produced, reduce the production cost of super absorbent resin, become the direction of the research and development of super absorbent resin.
The good characteristic of super absorbent resin has determined it to have broad application prospects.Special and the wide application field of super absorbent resin is the key of its successful development.It is main at present performance such as replying with its water-absorbent, water-retentivity and secondary to external world, and carries out the in the majority of application and development.Super absorbent resin successfully is applied to numerous areas such as Personal hygiene care products at present, like women use sanitary napkin, baby's paper nappy, old incontinence Paper nappies etc.Super absorbent resin also shows encouraging prospects in the application aspect the agronomy gardens, and the application of super absorbent resin helps water saving irrigation, reduces the plant mortality ratio, improves the soil fertilizer ability, improves crop percentage of germination etc.The application of super-strong moisture absorbing property resin aspect desertification control has beyond measure social benefit especially.In addition, super-strong moisture absorbing property resin is used at everyways such as industry, building, medicine, daily necessities, food, light industrys comparatively widely.
Summary of the invention
The object of the present invention is to provide a kind of is the preparation method of raw material synthesizing high-hydroscopicity resin with starch, can improve the defective of existing production technology through adopting reversed emulsion polymerization, with optimization production technology and the various performances that improve product.
The present invention realizes through following technical scheme.
In reaction kettle, adding concentration is the starch emulsion of 8-15%; Degree of neutralization is the acrylic acid solution of 70-90%; Acrylic acid solution and starch are that 7-9:1 forms water by mass ratio, and be 0.8-1.6 according to water oil ratio: 1 adds oil phase liquid paraffin body, the composite use of emulsifying agent Span-80 and Tween-80; Add-on is the 10-35% of profit total amount, and the mass ratio of Span-80 and Tween-80 is to make the HLB value of system between 5.83-13.47; In logical nitrogen anaerobic, temperature of reaction is to stir 30-50min under 45-65 ℃ the condition, makes it fully emulsified; The N of 0.8-1.0% of ammonium persulphate and amount of starch that adds the 2.5-3.5% of amount of starch then successively, N '-methylene-bisacrylamide, anaerobic, agitation condition be reaction 1.5-3h down, finish reaction after, use the absolute ethyl alcohol breakdown of emulsion, suction filtration; Product is used ethanol and washing with acetone respectively 2-3 time, to constant weight, after pulverizing and sieving, obtains thick graft resin in 40-80 ℃ of vacuum-drying again; Quantitatively take by weighing the grafting crude product in apparatus,Soxhlet's, make solvent with acetone, extracting 12-24h removes homopolymer, is dried to constant weight at hot air drier, gets pure graft copolymer.
Advantage of the present invention and effect.
1, the present invention adopts the raw material of starch as graft copolymerization, has made full use of the good characteristic that starch itself is had, for starch has been widened range of application and deep processing provides foundation.
2, the present invention utilizes reversed emulsion polymerization to prepare the starch graft acrylic acid super absorbent resin, this method with conventional water solution polymerization process relative, need not with after the starch pasting the reaction, saved great amount of time, simplified reaction process greatly.Simultaneously because reversed emulsion polymerization has a lot of advantages, thereby overcome traditional water solution method many defectives aborning, optimized and perfect production technique.
3, the prepared super absorbent resin of the present invention, inhaling the deionized water multiplying power is 1000-1600 g/g, and inhaling the tap water multiplying power is 700-1200 g/g, and inhaling the saline water multiplying power is 70-150 g/g.Water retention property and use properties is all better repeatedly, the product rate of water absorption is fast, and security is good, has no side effect.
Embodiment
The present invention will be described further through following examples.
Embodiment 1.
In four-hole boiling flask, add 2.0311 g canna starches, add the 20ml deionized water, for use.Accurately measure the 16ml acrylic acid solution in the beaker of 200ml, take by weighing NaOH6.5165g then, it is dissolved fully with zero(ppm) water; Be cooled to room temperature, add and be equipped with in acrylic acid beaker, stir; Make wherein with complete; Question response liquid is cooled to room temperature, joins in the four-hole boiling flask that milk of starch is housed, and constitutes the water in the reaction system.According to water oil ratio 1.2:1, add whiteruss 80g, emulsifying agent Span80 45g, Tween80 18g.In logical nitrogen anaerobic, temperature of reaction is under 55 ℃ the condition, stirs emulsion; Make it fully emulsified, form stable reversed-phase emulsion, add initiator ammonium persulfate 3.11ml (concentration is 0.05mol/L) behind 30 min; Linking agent N, N '-methylene-bisacrylamide 1.85ml (concentration is 0.1mol/L).Anaerobic, agitation condition finish reaction behind the reaction 2h down, use the absolute ethyl alcohol breakdown of emulsion, suction filtration.Product is used ethanol and washing with acetone respectively 2-3 time, to constant weight, after pulverizing and sieving, obtains thick graft resin in 75 ℃ of vacuum-dryings again.Quantitatively take by weighing the grafting crude product in apparatus,Soxhlet's, make solvent with acetone, extracting 24h removes homopolymer, is dried to constant weight at hot air drier, gets pure graft copolymer.Through test, the suction deionized water multiplying power of present embodiment gained resin is 1442g/g, and inhaling the tap water multiplying power is 1020 g/g, and inhaling the saline water multiplying power is 112 g/g.
Embodiment 2.
In four-hole boiling flask, add 2.0253 g W-Gums, add the 20ml deionized water, for use.Accurately measure the 16ml acrylic acid solution in the beaker of 200ml, take by weighing NaOH 7.4539g then, it is dissolved fully with zero(ppm) water; Be cooled to room temperature, add and be equipped with in acrylic acid beaker, stir; Make wherein with complete; Question response liquid is cooled to room temperature, joins in the four-hole boiling flask that milk of starch is housed, and constitutes the water in the reaction system.According to water oil ratio 1.2:1, add whiteruss 95g, emulsifying agent Span80 54g, Tween80 22g.In logical nitrogen anaerobic, temperature of reaction is under 50 ℃ the condition, stirs emulsion; Make it fully emulsified, form stable reversed-phase emulsion, add initiator ammonium persulfate 3.60ml (concentration is 0.05mol/L) behind 30 min; Linking agent N, N '-methylene-bisacrylamide 1.88ml (concentration is 0.1mol/L).Anaerobic, agitation condition finish reaction behind the reaction 2h down, use the absolute ethyl alcohol breakdown of emulsion, suction filtration.Product is used ethanol and washing with acetone respectively 2-3 time, to constant weight, after pulverizing and sieving, obtains thick graft resin in 75 ℃ of vacuum-dryings again.Quantitatively take by weighing the grafting crude product in apparatus,Soxhlet's, make solvent with acetone, extracting 24h removes homopolymer, is dried to constant weight at hot air drier, gets pure graft copolymer.Through test, the suction deionized water multiplying power of present embodiment gained resin is 1136g/g, and inhaling the tap water multiplying power is 845g/g, and inhaling the saline water multiplying power is 89 g/g.
Embodiment 3.
In four-hole boiling flask, add 2.0311 g yam starchs, add the 20ml deionized water, for use.Accurately measure the 16ml acrylic acid solution in the beaker of 200ml, take by weighing NaOH 6.5165g then, it is dissolved fully with zero(ppm) water; Be cooled to room temperature, add and be equipped with in acrylic acid beaker, stir; Make wherein with complete; Question response liquid is cooled to room temperature, joins in the four-hole boiling flask that milk of starch is housed, and constitutes the water in the reaction system.According to water oil ratio 1.2:1, add whiteruss 80g, emulsifying agent Span80 45g, Tween80 18g.In logical nitrogen anaerobic, temperature of reaction is under 65 ℃ the condition, stirs emulsion; Make it fully emulsified, form stable reversed-phase emulsion, add initiator ammonium persulfate 3.11ml (concentration is 0.05mol/L) behind 30 min; Linking agent N, N '-methylene-bisacrylamide 1.85ml (concentration is 0.1mol/L).Anaerobic, agitation condition finish reaction behind the reaction 1.5h down, use the absolute ethyl alcohol breakdown of emulsion, suction filtration.Product is used ethanol and washing with acetone respectively 2-3 time, to constant weight, after pulverizing and sieving, obtains thick graft resin in 75 ℃ of vacuum-dryings again.Quantitatively take by weighing the grafting crude product in apparatus,Soxhlet's, make solvent with acetone, extracting 24h removes homopolymer, is dried to constant weight at hot air drier, gets pure graft copolymer.Through test, the suction deionized water multiplying power of present embodiment gained resin is 1256g/g, and inhaling the tap water multiplying power is 932g/g, and inhaling the saline water multiplying power is 95g/g.
Embodiment 4.
In four-hole boiling flask, add 2.0667 g pueraria starches, add the 20ml deionized water, for use.Accurately measure the 16ml acrylic acid solution in the beaker of 200ml, take by weighing NaOH 6.5258g then, it is dissolved fully with zero(ppm) water; Be cooled to room temperature, add and be equipped with in acrylic acid beaker, stir; Make wherein with complete; Question response liquid is cooled to room temperature, joins in the four-hole boiling flask that milk of starch is housed, and constitutes the water in the reaction system.According to water oil ratio 1.2:1, add whiteruss 85g, emulsifying agent Span80 48g, Tween80 19g.In logical nitrogen anaerobic, temperature of reaction is under 65 ℃ the condition, stirs emulsion; Make it fully emulsified, form stable reversed-phase emulsion, add initiator ammonium persulfate 2.71ml (concentration is 0.05mol/L) behind 30 min; Linking agent N, N '-methylene-bisacrylamide 2.36ml (concentration is 0.1mol/L).Anaerobic, agitation condition finish reaction behind the reaction 1.5h down, use the absolute ethyl alcohol breakdown of emulsion, suction filtration.Product is used ethanol and washing with acetone respectively 2-3 time, to constant weight, after pulverizing and sieving, obtains thick graft resin in 75 ℃ of vacuum-dryings again.Quantitatively take by weighing the grafting crude product in apparatus,Soxhlet's, make solvent with acetone, extracting 24h removes homopolymer, is dried to constant weight at hot air drier, gets pure graft copolymer.Through test, the suction deionized water multiplying power of present embodiment gained resin is 1006g/g, and inhaling the tap water multiplying power is 794g/g, and inhaling the saline water multiplying power is 74g/g.
Claims (1)
1. the method for the synthetic absorbent resin of a starch graft acrylic acid; It is characterized in that in reaction kettle, adding concentration is the canna starch emulsion of 8-15%; Degree of neutralization is the acrylic acid solution of 70-90%; Acrylic acid solution and starch are that 7-9:1 forms water by mass ratio, and be 0.8-1.6 according to water oil ratio: 1 adds oil phase liquid paraffin body, the composite use of emulsifying agent Span-80 and Tween-80; Add-on is the 10-35% of profit total amount, and the mass ratio of Span-80 and Tween-80 is to make the HLB value of system between 5.83-13.47; In logical nitrogen anaerobic, temperature of reaction is to stir 30-50min under 45-65 ℃ the condition, makes it fully emulsified; The N of 0.8-1.0% of ammonium persulphate and amount of starch that adds the 2.5-3.5% of amount of starch then successively, N '-methylene-bisacrylamide, anaerobic, agitation condition be reaction 1.5-3h down, finish reaction after, use the absolute ethyl alcohol breakdown of emulsion, suction filtration; Product is used ethanol and washing with acetone respectively 2-3 time, to constant weight, after pulverizing and sieving, obtains thick graft resin in 40-80 ℃ of vacuum-drying again; Quantitatively take by weighing the grafting crude product in apparatus,Soxhlet's, make solvent with acetone, extracting 12-24h removes homopolymer, is dried to constant weight at hot air drier.
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| CN2011101335367A CN102219880B (en) | 2011-05-23 | 2011-05-23 | Method for synthesizing super absorbent resin with starch grafted acrylic acid |
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| CN2011101335367A CN102219880B (en) | 2011-05-23 | 2011-05-23 | Method for synthesizing super absorbent resin with starch grafted acrylic acid |
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| CN102633943B (en) * | 2012-03-30 | 2014-11-05 | 广西大学 | Preparation method of starch super-absorbent resin |
| CN106008821A (en) * | 2016-05-31 | 2016-10-12 | 山东胜伟园林科技有限公司 | Method for carrying out raw soil greening on slight saline and alkaline land by using halophilic microorganism-containing water retaining agent |
| CN113480692A (en) * | 2021-06-28 | 2021-10-08 | 武汉海翎化学工业有限公司 | High-water-absorptivity polyacrylic resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025417A (en) * | 1996-02-28 | 2000-02-15 | Biotechnology Research & Development Corp. | Biodegradable polyester compositions with natural polymers and articles thereof |
| CN101045776A (en) * | 2007-04-20 | 2007-10-03 | 西北农林科技大学 | Method for synthesizing super absorbent resin from waxy wheat starch |
| CN101050252A (en) * | 2006-04-04 | 2007-10-10 | 台湾塑胶工业股份有限公司 | High water absorption resin, and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025417A (en) * | 1996-02-28 | 2000-02-15 | Biotechnology Research & Development Corp. | Biodegradable polyester compositions with natural polymers and articles thereof |
| CN101050252A (en) * | 2006-04-04 | 2007-10-10 | 台湾塑胶工业股份有限公司 | High water absorption resin, and preparation method |
| CN101045776A (en) * | 2007-04-20 | 2007-10-03 | 西北农林科技大学 | Method for synthesizing super absorbent resin from waxy wheat starch |
Non-Patent Citations (1)
| Title |
|---|
| 刘光畅 等.芭蕉芋淀粉的接枝共聚.《云南化工》.1995,(第3期), * |
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