CN101205413A - Method for preparing degradable high water-absorbing resin by using ultrasonic wave - Google Patents
Method for preparing degradable high water-absorbing resin by using ultrasonic wave Download PDFInfo
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Abstract
The invention discloses a preparation method of a degradable super absorbent resin by using ultrasonic wave. Based on ultrasonic treatment technology, the invention adopts a new synthesis technology to prepare the degradable super absorbent resin. The invention is realized through the following procedures: 1. modification treatment of corn stalks; 2. ultrasonic treatment of the corn stalks; and 3. preparation of the super absorbent resin. The invention applies the ultrasonic treatment technology into the absorbent resin preparation, and greatly shortens the reaction time; after treatment, the solution polymerization occurs immediately at high temperature; the invention has simple preparation technology without nitrogen protection, and the prepared products have good water-absorption capacity. The products can improve water conditions of the soil, can be degraded into organic fertilizer, and improve crop growth environment, which is suitable for agricultural extension and utilization.
Description
Technical field
The present invention relates to a kind of ultrasonication technology of utilizing, the technology of efficient production degradable high water-absorbing resin belongs to polymeric material field.
Background technology
3,334 ten thousand hectares of the long-term maize plantings of China calculate by per hectare 6000-7500 kilogram stalk, can produce stalk 2000～2,500 hundred million kilogram every year; After the annual vast rural area autumn harvest, a large amount of maize straws digest nowhere, or burn, or only as fuel, the maize straw that is thick on the ground had both polluted environment, caused significant wastage again.Contain in the maize straw effective ingredients such as a large amount of sugars, robust fibre, protein and multiple in, trace element, belong to a kind of in the agricultural solid residue, also be a kind of renewable resources.But the maize straw Mierocrystalline cellulose is not gone up substantially and is utilized effectively at present, has both caused the resource significant wastage, again environment is polluted.From Sustainable utilization of resources, protection environment and biocompatible and Biodegradable characteristics, people have expressed very big expectation for the utilization of regeneration stalk cellulose.By the stalk cellulose recycling, development environment close friend's green product has become the hot fields in Green Chemistry, the chemical research.
Eighties of last century seventies, the U.S. has developed starch-Graft Copolymerization of Cellulose type super absorbent resin.The Sanyo of Japan in 1975 changes into and has developed starch acrylamide acid graft copolymer, and product entered people market in 1978.In recent years, China researches and develops super absorbent resin, makes super absorbent resin form the situation that develops rapidly.Super absorbent resin mainly comprises two classes, and a class is based on natural polymer, for example starch and Mierocrystalline cellulose, the preparation of graft modification technology, this class water-absorbing resin cost is low, and degradable; Another kind of is the synthetic macromolecule preparation, the cost height, and be difficult for degraded.Therefore, utilize natural resource exploitation degradable absorbent resin to become the focus of recent research.
Its principle of Graft Copolymerization of Cellulose type super absorbent resin mainly is that Mierocrystalline cellulose is carried out modification, and the high-hydroscopicity compound of vinylformic acid and its esters and crosslinked obtains super absorbent resin in the grafting.The Zhou Ming of Southwest Petroleum Institute petroleum engineering institute is super absorbent resin synthetic of initiator with the ceric ammonium nitrate interim report of " Southwest Petroleum Institute journal " the 25th volume the 5th, and has studied its reaction mechanism.The Liu Shujuan of Qingdao University of Science and Technology has reported that the heterogeneous grafting of Mierocrystalline cellulose prepares high-absorbent material in the hydrogen peroxide/water system in that " elastomerics " the 13rd volume the 2nd is interim, and has studied its reaction mechanism.
Cellulosic intramolecularly in the maize straw and intermolecularly exist a large amount of hydrogen bonds, the complicacy of while Mierocrystalline cellulose aggregated structure and the high-crystallinity that has, make Mierocrystalline cellulose low to the accessibility of reagent, the dissolving difficulty, the homogeneity of reactivity worth and chemical reaction is poor, and this directly has influence on the use properties of cellulosics.This just need carry out pre-treatment to it.For example, people such as the Yang Huiqun of Huabei Polytechnical College have reported on " Huabei Polytechnical College journal " the 23rd the 1st phase of volume and have utilized swollen quick-fried technology that maize straw is carried out pre-treatment, have destroyed the structure of cellulosic molecule crystallizing field, have improved the accessibility of reagent greatly.The Li Li of Shenyang Institute of Technology " fine chemistry industry " calendar year 2001 the 6th the interim technology of utilizing maize straw to prepare carboxymethyl cellulose of having reported.
But present stage, the synthetic method of report mostly needed nitrogen protection, and higher to equipment requirements, preparation and time of drying are long; And the super absorbent resin raw material is starch mostly at present, or the Mierocrystalline cellulose that extracts in the balloonflower root cotton fiber, it is comparatively complicated to need high temperature and product to collect as the polymerization process of a kind of derivatived cellulose water-absorbing resin of Chinese patent 01145399.0 report, and preparation technology is loaded down with trivial details; Chinese patent 90105865.3 report utilize the starch High hydrophilous resin that the grafted propylene nitrile makes under the condition of nitrogen protection, need to use under the hot conditions alkali soapization, these have all improved the cost of water-absorbing resin, have limited its promotion and application to a certain extent.
Traditional method prepares water-absorbing resin, needs high temperature, nitrogen protection and mechanical stirring during gelatinization, and polymerization time long production efficient is low, and cost is higher relatively.Yet there are no the technology report that ultrasonic wave is used for the absorbent resin preparation, ultrasonic wave is applied to chemical reaction as a kind of new form of energy and receives people's concern just day by day.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin; reactions steps has been simplified in preparation, has reduced the reaction requirement, can finish reaction under the condition of inert-free gas protection; shorten polymerization time, improved production efficiency greatly.
The present invention is based on the ultrasonication technology, adopt a kind of new synthesis technique to prepare a kind of degradable super absorbent resin.It may further comprise the steps:
1. the modification of maize straw: under the room temperature, maize straw is ground into powder, crosses 80～200 mesh sieve; Get mass fraction and be 10～50 parts of corn stalk powders and 100～200 parts of ethanol, 20～100 parts of concentration and be 50% NaOH deionized water solution, behind 25～40 ℃ of following stirring reaction 1～2h, add 15～70 parts of Mono Chloro Acetic Acids and 45 parts of dehydrated alcohols, at 60～80 ℃ of following stirring reaction 1～2h.With in the reaction solution and after, filter, be 80%～90% ethanolic soln washing and filtering with concentration, drying obtains the maize straw powder of modification.
2. the ultrasonication of maize straw: get the maize straw powder of the modification of 2 parts of steps 1, add in 30 parts～100 parts deionized waters it is fully dissolved, and, form the modified fibre cellulose solution with ultrasonication 4～7 minutes.Under the room temperature, with 0.1～0.2 part of ceric ammonium nitrate and 0.225～0.64 part of HNO
3Be dissolved in 5 parts the water, join in the modified fibre cellulose solution.Being mixed with degree of neutralization with NaOH is 60%～85% acrylate solution, get 15～40 parts of these solution and 0.045～0.255 part of N, the N-methylene-bisacrylamide mixes, and this solution is joined in the modified fibre cellulose solution, continues to use ultrasonication 1～2 minute;
3. the preparation of super absorbent resin: 4 parts of concentration of adding are 2～5% K in the mixing solutions that obtains of step 2
2S
2O
8The aqueous solution reacted 30～60 minutes in 60～100 ℃ of baking ovens, up to gel formation.Gel product is dried to constant weight in 40～70 ℃ of baking ovens after methyl alcohol soaks 7～12h, obtain super absorbent resin of the present invention after the pulverizing.
Take by weighing the 1g toner in beaker, the water that adds capacity is saturated to its suction; Use 100 order nylon net filters, back water-absorbing resin quality is filtered in weighing.Utilize formula to calculate
Water absorbent rate=(suction back weight-example weight)/example weight
The water-intake rate of product that the present invention after tested produces is inhaled the tap water rate at 200～300g/g at 600～850g/g.
Sodium hydroxide among the present invention, available hydrogen potassium oxide, sodium bicarbonate or ammoniacal liquor substitute.Need in the reaction system monomer acrylate concentration is controlled at 10%～25%,, thereby reduced water absorbent rate and water retention capacity if monomer concentration crosses low then its crosslinking degree is not enough; If monomer concentration is too high, then cause gelation process too fast, monomer crosslinked not thorough, cause waste; The used linking agent N of system, the amount of N-methylene-bisacrylamide should be controlled at about 6.5% of modified-cellulose, and this is that polymkeric substance fails to form effective three-dimensional structure because work as dosage of crosslinking agent more after a little while, so water-absorbent is not high, and cross-linking monomer also can be partially soluble in water owing to the polymerization degree is low; And when dosage of crosslinking agent was too high, the cross-linking set in the polymer network was too much, caused the cross-linking density increase to make the micropore in the cross-linked network structure dwindle, and can't hold water molecules, so water-intake rate also can descend.
Characteristics of the present invention are:
The present invention compares in the preparation of water-absorbing resin ultrasonic applications with traditional method, simplified reactions steps, has reduced the reaction requirement; under the condition of inert-free gas protection, can finish reaction; shorten polymerization time, only needed 1 hour can finish polyreaction, improved production efficiency greatly.Do not have thermograde in the reaction process, react even polymerization process environmentally safe, and resin low cost, degradable and good water absorption that ultrasonic applications is made in the novel method of water-absorbing resin.Step of the present invention is simple, and mild condition is with low cost and realized the resource conversion of agricultural wastes.
The source of raw material is a kind of of agricultural solid residue among the present invention, and price is extremely cheap, and system finally reaches acid base equilibrium, can not cause any pollution to environment.Processing to maize straw is succinctly convenient, solid content height in the reaction system, and manufacture craft is simple.The ultrasonication technology is applied to the water-absorbing resin preparation, has shortened the reaction times greatly, handle the directly high temperature polymerization of back solution, preparation technology is simple, need not nitrogen protection; Prepared product water-retaining capacity is strong.Product can improve the moisture condition of soil, and can be biodegradable into fertilizer, improves crop growth environment, is suitable for the agricultural extension utilization.
Prepared super absorbent resin can be used in the agricultural, its usage is the soil of granting plant root after it is pulverized, reduce the soil transpiration, reduce the loss and the seepage of moisture, make full use of moisture, when precipitation content is high, absorb redundant moisture, offer the necessary moisture of plant in the time of arid again, the balance of regulating the content of water in the soil.Through after certain usage period, can be degraded by microorganisms, turn fertilizer into for plant, be used to improve the crop planting environment, especially in the arid area, can not cause any pollution to environment.A large amount of depleted maize straws that this material makes full use of, with low cost, effect is obvious.
Result of use:
One, reduces the soil transpiration, reduce the loss and the seepage of moisture, make full use of moisture, when precipitation content is high, absorb redundant moisture, offer the necessary moisture of plant in the time of arid again, the balance of regulating the content of water in the soil;
Two, through after certain usage period, can be degraded by microorganisms, can not cause any pollution environment.A large amount of depleted maize straws that this material makes full use of, with low cost, effect is obvious.
Advance of the present invention show following some:
1. reaction need not protection of inert gas, and is simple to equipment requirements;
2. do not have thermograde, side reaction is few;
3. the ultrasonic irradiation method is applied to the water-absorbing resin preparation, has shortened the reaction times greatly;
4. the maize straw earlier stage processing method is simple and easy to do;
5. have degradation property, degraded product helps plant-growth;
6. raw material sources are wide, and are with low cost, promote in China easily.
Embodiment
Embodiment 1
1. maize straw modification:
The maize straw of getting mass fraction and be 2 parts is ground into powder (room temperature), crosses 80 mesh sieve.15 parts of ethanol, 2 parts of NaOH and 2 parts of deionized waters, stirring reaction added 2.5 parts of Mono Chloro Acetic Acids and 5 parts of dehydrated alcohols after 1 hour under 30 degree, and stirring reaction is 1 hour under 70 degree.With in the reaction solution and after, filter, with the filtration of 80% washing with alcohol, drying obtains the maize straw powder of modification.
2. the ultrasonication of maize straw:
Get the maize straw powder of the modification of 2 parts of steps 1, join in the beaker that fills 50 parts of deionized waters, dissolving, and with ultrasonication 4～7 minutes, it is fully dissolved form the modified fibre cellulose solution.Under the room temperature, 0.135 part ceric ammonium nitrate is dissolved in 0.64 part of nitric acid HNO
3, in 5 parts of aqueous solution, join in the above-mentioned modified fibre cellulose solution; The mixture that with 32 parts of degree of neutralization is 70% acrylate solution and 0.225 part of N,N methylene bis acrylamide simultaneously also adds simultaneously.Continue to use ultrasonication 1 minute.
3. the preparation of super absorbent resin:
5 parts of concentration of adding are 3.5% K after mixing
2S
2O
8, after the preservative film sealing, put into 80 degree constant temperature ovens to gel formation; Product takes out back methyl alcohol and soaked 7～12 hours, dries in 60 ℃ of baking ovens, obtains water-absorbing resin of the present invention after the pulverizing.The product water-intake rate is 792g/g.
Embodiment 2
The preparation method is identical with embodiment 1, and the consumption of adjusting N,N methylene bis acrylamide is 0.176 part, can obtain the product that water-intake rate is 844g/g.
Embodiment 3
The preparation method is identical with embodiment 1, and using 24 parts of degree of neutralization is 70% acrylate solution, obtains the product that water-intake rate is 736g/g.
Embodiment 4
The preparation method is identical with embodiment 1, gets 2 parts of modified powders and is dissolved in 30 parts of deionized waters, and using 20 parts of degree of neutralization is that 75% acrylate solution and the consumption of adjusting N,N methylene bis acrylamide are 0.176 part, can obtain the product that water-intake rate is 769g/g.
Embodiment 5
The preparation method is identical with embodiment 1, gets 2 parts of modified powders and is dissolved in 20 parts of deionized waters, and using 18 parts of degree of neutralization is 75% acrylate solution, and the consumption of adjusting N,N methylene bis acrylamide is 0.134 part, can obtain the product that water-intake rate is 796g/g.
The comparative example
With embodiment 4, but do not use the ultrasonic wave effect, stirring is fully dissolved it.Obtain the product that water-intake rate is 631g/g.
Comparison example shows that under the situation of no ultrasonic wave effect, the resin gel time is long, needs 45 minutes～60 minutes can form gel in 80 ℃ of baking ovens, and embodiment 3 can form gel at 15 minutes～20 minutes; And the product water absorbent rate that does not have the ultrasonic wave effect is low; And when the vinylformic acid consumption is high, and when dosage of crosslinking agent was less relatively, the water-intake rate of product was higher.
Claims (6)
1. a method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin is characterized in that: (1). the modification of maize straw; (2). the ultrasonication of maize straw; (3). the preparation of super absorbent resin;
The modification of described maize straw: under the room temperature, maize straw is ground into powder, cross 80～200 mesh sieve, get mass fraction and be 10～50 parts of corn stalk powders and 100～200 parts of ethanol, 20～100 parts of concentration and be 50% NaOH deionized water solution, behind 25～40 ℃ of following stirring reaction 1～2h, add 15～70 parts of Mono Chloro Acetic Acids and 45 parts of dehydrated alcohols, at 60～80 ℃ of following stirring reaction 1～2h, with in the reaction solution and after, filter, with concentration is 80%～90% ethanolic soln washing and filtering, and drying obtains the maize straw powder of modification;
The ultrasonication of described maize straw: get the maize straw powder of the modification of 2 parts of steps 1, add 30 parts～100 parts deionized waters it is fully dissolved, and, form the modified fibre cellulose solution with ultrasonication 4～7 minutes; Under the room temperature, with 0.1～02 part of ceric ammonium nitrate and 0.225～0.64 part of HNO
3Be dissolved in 5 parts the water, join in the modified fibre cellulose solution, being mixed with degree of neutralization with NaOH is 60%～85% acrylate solution, get 15～40 parts of these solution and 0.045～0.255 part of N, the N-methylene-bisacrylamide mixes, this solution is joined in the modified fibre cellulose solution, continue to use ultrasonication 1～2 minute;
The preparation of described super absorbent resin: 4 parts of concentration of adding are 2～5% K in the mixing solutions that obtains of step 2
2S
2O
8The aqueous solution reacted 30～60 minutes in 60～100 ℃ of baking ovens, up to gel formation.Gel product is dried to constant weight in 40～70 ℃ of baking ovens after methyl alcohol soaks 7～12h, obtain absorbent resin of the present invention after the pulverizing.
2. a kind of method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin according to claim 1, it is characterized in that: the consumption of described N,N methylene bis acrylamide is 0.176 part, obtains the product that water-intake rate is 844g/g.
3. a kind of method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin according to claim 1 is characterized in that: using 24 parts of degree of neutralization is 70% acrylate solution, obtains the product that water-intake rate is 736g/g.
4. a kind of method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin according to claim 1: it is characterized in that: get 2 parts of modified powders and be dissolved in 30 parts of deionized waters, to use 20 parts of degree of neutralization be 75% acrylate solution and adjust N, the consumption of N-methylene-bisacrylamide is 0.176 part, obtains the product that water-intake rate is 769g/g.
5. a kind of method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin according to claim 1, it is characterized in that: get 2 parts of modified powders and be dissolved in 20 parts of deionized waters, using 18 parts of degree of neutralization is 75% acrylate solution, and adjustment N, the consumption of N-methylene-bisacrylamide is 0.134 part, obtains the product that water-intake rate is 796g/g.
6. a kind of method of utilizing ultrasonic wave to prepare degradable high water-absorbing resin according to claim 1 is characterized in that: described sodium hydroxide solution, and can use potassium hydroxide, sodium bicarbonate or ammoniacal liquor to substitute.
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| CN101974133A (en) * | 2010-10-30 | 2011-02-16 | 绥化学院 | Method of preparing biodegradable super absorbent resin by using eggshell membrane |
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| CN101870623A (en) * | 2009-04-25 | 2010-10-27 | 刘利军 | Nitrogenous super absorbent resin fertilizer and preparation method thereof |
| CN101871188A (en) * | 2009-04-25 | 2010-10-27 | 刘利军 | Slow-release, anti-drought and salt-tolerant lawn paper and preparation method thereof |
| CN101871189B (en) * | 2009-04-25 | 2014-05-21 | 黑龙江笃信农业高科有限公司 | Nutritive absorbent resin seedling raising paper and preparation method thereof |
| CN101974133B (en) * | 2010-10-30 | 2012-04-18 | 绥化学院 | Method of preparing biodegradable super absorbent resin by using eggshell membrane |
| CN101974133A (en) * | 2010-10-30 | 2011-02-16 | 绥化学院 | Method of preparing biodegradable super absorbent resin by using eggshell membrane |
| CN102504110A (en) * | 2011-10-21 | 2012-06-20 | 吉林农业大学 | Method for preparing high absorbent resin material with fungus chaff |
| CN103113511A (en) * | 2013-03-14 | 2013-05-22 | 安徽省煤炭科学研究院 | Preparation method of high molecular material coolant |
| WO2015155336A1 (en) * | 2014-04-11 | 2015-10-15 | Kleinhout Arend | Drastic reduction of viscosity in biomass |
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| US11198764B2 (en) | 2014-04-11 | 2021-12-14 | Arend Kleinhout | Drastic reduction of viscosity in biomass |
| CN105504315A (en) * | 2015-12-03 | 2016-04-20 | 西北工业大学 | Preparation method and application of all-component straw hydrogel |
| CN105504315B (en) * | 2015-12-03 | 2018-05-04 | 西北工业大学 | A kind of preparation method and applications of stalk full constituent hydrogel |
| CN108558337A (en) * | 2018-01-24 | 2018-09-21 | 绥中大地丰源建材有限公司 | The modified method for preparing organic active concrete is improved using mud |
| CN108558337B (en) * | 2018-01-24 | 2020-12-29 | 绥中大地丰源建材有限公司 | Method for preparing organic active concrete by improving and modifying sludge |
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