CN101440144A - Zwitterion association type high wate-absorption resin and preparing method thereof - Google Patents
Zwitterion association type high wate-absorption resin and preparing method thereof Download PDFInfo
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- CN101440144A CN101440144A CNA2008100463510A CN200810046351A CN101440144A CN 101440144 A CN101440144 A CN 101440144A CN A2008100463510 A CNA2008100463510 A CN A2008100463510A CN 200810046351 A CN200810046351 A CN 200810046351A CN 101440144 A CN101440144 A CN 101440144A
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Abstract
The invention relates to a zwitterionic associated-type super absorbent resin. The structure of zwitterionic associated-type super absorbent resin is linear polymers which repeatedly appear in a structure expressed by the following general formula and have the average molecular weight between 600 and 10,000,000. The zwitterionic associated-type super absorbent resin has the advantages of high water absorbency, fast water absorption, high strength, good salt tolerance, good long residual action, wider application range and lower use cost. The zwitterionic associated-type super absorbent resin can be used for agriculture, forestry, horticulture, medicine, health, industrial field, soil improvement, control on water loss, soil erosion and desertification, desert reformation, flood control, fire extinguishment, oil fields and the like, prolongs service life, reduces watering investment in manual work and time, and remarkably reduces use cost.
Description
Technical field
The present invention relates to a kind of Zwitterion association type high wate-absorption resin and preparation method thereof.
Background technology
(Super Absorbent Polymer, SAP), process develops perfect half a century High hydrophilous resin gradually as water-holding agent.At present, nearly 30 countries have been widely used in High hydrophilous resin multiple fields such as industry, agricultural, building, gardening, health.Many developed countries begin to promote with regard to big area the seventies.China agricultural scientific research personnel almost carry out the applied research of " High hydrophilous resin " synchronously with the world, obtained the extensive application achievement, many chemical scientific research mechanisms and enterprise get involved this emerging industry one after another, make China's High hydrophilous resin research and application, have obtained develop rapidly.In the recent period, the development of China's High hydrophilous resin and application have started new climax, and the Chinese government has also set up 863 projects " development of Multifunction water-holding agent series product and industrialization development " problem.But the polyacrylic acid super absorbent resin that this class is general does not have good suction salt outlet capacity, can't play a role in the practical application in a lot of places, and its major cause has:
(1), the suction multiple is not high, suction (deionized water) multiple of at present general acrylic acid or the like super absorbent resin is 300～500 times;
(2), gel-strength is bad, the gel after the suction is promptly broken under slight external force effect, the back gel dispersion is long-pending to diminish through using repeatedly, runs off easily;
(3), salt tolerance is poor, water absorbing properties obviously reduces along with the increase of salt concn in the solution, is common phenomenon, in 0.9% salt solution, the suction multiple can be reduced to and have only 30-60 doubly significantly by about 400 times in the deionized water, has reduced by ten times approximately;
(4), fall short of work-ing life, though the data propaganda has the life-span of 2-3 in soil, this class super absorbent resin poor stability, water conservation validity and gel-strength (life-span) are not high, so that can be ineffective under saline and alkaline high condition;
(5) in use, long-term a large amount of the use contains disadvantageous, the labile sodium-ion type super absorbent resin of plant and soil product, causes P in soil H value to raise, and Soil structure destroys, and influences the plant root growth and the gas permeability of soil.
At present, both at home and abroad mainly to be divided into starch by raw material sources be that High hydrophilous resin (starch-grafted propylene is fine, starch grafted acrylate, starch graft acrylic acid amine), cellulose-based High hydrophilous resin, synthetic resins are High hydrophilous resin three major types series to High hydrophilous resin, but these resins all await continuing researchdevelopment.
Summary of the invention
Technical problem to be solved by this invention be carry a kind of water absorbent rate height, absorption speed is fast, intensity is high, the Zwitterion association type high wate-absorption resin of good salt tolerance, environment-protecting asepsis, preserve moisture and fertility and preparation method thereof.
The present invention addresses the above problem the technical scheme that is adopted: Zwitterion association type high wate-absorption resin, its structure are that molecular-weight average that the repeated structure of following general formula performance occurs being formed is 600～10,000,000 linear polymerization body.
Institute of the present invention synthetic Zwitterion association type high wate-absorption resin, it is the simple approach that the traditional use vinylformic acid of change and acrylamide copolymerization under the effect of linking agent synthesize the negatively charged ion cross-linked polymer, in molecular chain, introduce anionic monomer and cationic monomer simultaneously, and adopt the novel associating monomer and the linking agent of a small amount of (about 1-3%) to carry out copolymerization, obtain Zwitterion association type high wate-absorption resin.On the one hand, owing to contain negatively charged ion and positively charged ion simultaneously on the fractionated polymer subchain, thereby has a stronger wetting ability, strengthened water-absorbent, cationic existence has simultaneously strengthened the adsorption of Zwitterion association type high wate-absorption resin molecular chain and soil particle (the aquation rear surface contains negatively charged ion) again, performance suppresses the aquation and the dispersion of soil particle, this is the Another reason of " protecting soil " function, and this adsorption makes Zwitterion association type high wate-absorption resin and soil particle form an integral body, helps the permanently effective of Zwitterion association type high wate-absorption resin.On the other hand, owing to used the acting in conjunction of linking agent and associating monomer, the former is cross-linked to form reticulated structure by covalent linkage by the water-soluble polymers molecular chain, gel after keeping absorbing water has certain shape and intensity (being chemically crosslinked), the latter then is an intensity of further having strengthened gel by the non covalent bond effect of hydrophobic association, and reduced dependence (being physical crosslinking) to chemically crosslinked than conventional art, form physics and chemically crosslinked dual function, therefore, the intensity of Zwitterion association type high wate-absorption resin gel, water absorbent rate and salt tolerance all increase substantially, and can reduce comprehensive cost on using.
Greater than 1000 gram water/gram resins, greater than 500 gram water/gram resins, the water regain of the sodium chloride solution to 0.9% restrains water/gram resins greater than 100 to described Zwitterion association type high wate-absorption resin to the water regain of tap water to the water regain of deionized water.Wherein 0.9% sodium chloride solution is meant sodium-chlor is dissolved in the deionized water, and sodium chloride concentration is 0.9% solution.
By the water-absorbing resin of method for preparing, be to adopt " suction filtration method " to measure its every gram resin water regain.Water regain to deionized water is calculated with following formula:
Every gram resin water regain Q=(m
2-m
1)/m
1
Wherein: Q-every gram resin water regain (g/g);
m
2Sample mass (g) behind-absorption deionized water,
m
1The quality of-sample (g).
Water regain measuring method for the sodium chloride solution of tap water and 0.9% is the same.
A kind of preparation method of above-mentioned Zwitterion association type high wate-absorption resin, comprise the steps: the first step: Acrylic Acid Monomer is neutralized to 70～80% degree of neutralization with alkaline solution after, add synthetic good associating monomer, cationic monomer, acrylamide, anionic monomer, Acrylic Acid Monomer formation hybrid reaction system, and add the water mixing, form the hybrid reaction system; Material beyond dewatering in the mixed system accounts for 50%～65% of hybrid reaction system total mass; In the mixed system by the total mass of associating monomer, cationic monomer, acrylamide, anionic monomer, Acrylic Acid Monomer, associating monomer accounts for 3～5% of total mass, cationic monomer diallyldimethylammonChloride Chloride accounts for 5～7% of total mass, acrylamide monomer accounts for 3～5% of total mass, anionic monomer acrylic acid potassium accounts for 65～70% of total mass, and Acrylic Acid Monomer accounts for 15～17% of total mass; Second step: after in above-mentioned hybrid reaction system, adding the linking agent copolymerization, add initiator, form the hybrid reaction system; The 3rd step: insulation reaction is incubated 4～6 hours, 50～65 ℃ of temperature of reaction controls; The 4th step: reaction obtains Zwitterion association type high wate-absorption resin after finishing after granulation, drying, pulverizing.
Particularly, described associating monomer is an associating monomer octadecyl dimethyl-allyl ammonium chloride; Cationic monomer and negatively charged ion unit are respectively dimethyl diallyl ammonium chloride and potassium acrylate; Described linking agent copolymerization process has physics and chemistry is dual crosslinked; Described linking agent is formaldehyde, glycerine, allylic additional crosslinker, and wherein linking agent shared mass percent in reaction system is 0.04～0.06%; Described initiator is the redox system initiator, or azo-initiator.Wherein initiator shared mass percent in reaction system is 1～2%; Described initiator is Potassium Persulphate or sodium bisulfite or Diisopropyl azodicarboxylate; Described alkaline solution is NaOH solution, KOH solution, and wherein the mass percent concentration of alkaline solution is 10～15%.
To sum up, the invention has the beneficial effects as follows:
1, water absorbent rate height: the suction multiple of Zwitterion association type high wate-absorption resin of the present invention is: deionized water 900-1500 times, 0.9% salt solution 100-150 doubly; Water absorbent rate all exceeds more than 1 times than conventional products;
2, absorption speed is fast: owing to contain a large amount of hydrophilic radicals in the Zwitterion association type high wate-absorption resin molecule, these hydrophilic radicals are met hydrolytic dissociation, and the water-retaining capacity of Zwitterion association type high wate-absorption resin is strengthened, and absorption speed is accelerated.Show that by test Zwitterion association type high wate-absorption resin 5min can inhale about 800 times of deionized waters, can reach 74.9% of suction saturation capacity;
3, intensity height: exist physics and chemistry dual crosslinked between molecular chain, both kept high water absorbent rate, strengthened the intensity of water-holding agent gel again;
4, good salt tolerance: adopt the copolymerization of nonionic and different kinds of ions suction group to synthesize water-holding agent, particularly adopted the association group of good salt tolerance, strengthened the salt tolerance of water-holding agent gel greatly; 0.9% salt solution is absorbed multiplying power can reach 150 times, and usually crosslinked salt polyacrylate to the absorption multiplying power of salt solution be 30-60 doubly;
5, long-lasting good: Zwitterion association type high wate-absorption resin has long-term effectiveness, and the shelf-time of dry powder is greater than 1 year, and the gel water that can absorb water repeatedly-discharge has the long-lasting 3-5 of reaching in the soil;
6, vinylformic acid sylvite commonly used substituted the sodium salt of traditional product during products production constituted, and therefore can avoid soil is caused acidifying and hardens, and the while has suitably increased potash fertilizer for soil;
7, safety and environmental protection: synthetic by multistage initiation insulation, so conversion rate of products height, remaining AM monomer few (＜0.01%), good stability does not have any toxicity to plant, soil organic matter, underground water, and product is through after recycling for a long time, can between under the various factors effect, decompose, and main degradation production is a potassium acrylate, can be used as a kind of potash fertilizer and is absorbed by crop, can not cause secondary pollution to soil and environment.
8, range of application is wider, and use cost is lower.Can be used for agricultural gardening, medical and health, industrial circle, improve the soil, prevention soil and water loss and desertification, desert, flood control, fire extinguishing, oil field etc.Prolong work-ing life, and deduction and exemption are watered and dropped into artificial and time, significantly reduce use cost.
Embodiment
Embodiment 1
A kind of Zwitterion association type high wate-absorption resin and preparation method thereof comprises the steps:
The first step: Acrylic Acid Monomer is neutralized to 70～80% degree of neutralization with alkaline solution after, add synthetic good associating monomer octadecyl dimethyl-allyl ammonium chloride and cationic monomer diallyldimethylammonChloride Chloride, anionic monomer acrylic acid potassium and Acrylic Acid Monomer and form the hybrid reaction system, and add water and mix, form the hybrid reaction system, the material in the mixed system except water accounts for 50%～65% of hybrid reaction system total mass.Wherein, in the system by the total mass of associating monomer octadecyl dimethyl-allyl ammonium chloride and cationic monomer diallyldimethylammonChloride Chloride, anionic monomer acrylic acid potassium and Acrylic Acid Monomer, the mass percent that associating monomer octadecyl dimethyl-allyl ammonium chloride accounts for total mass is 3～5%, for example can be 3%, 4%, 5%; The mass percent that cationic monomer diallyldimethylammonChloride Chloride accounts for total mass is 5～7%, for example can be 5%, 6%, 7%; The mass percent that acrylamide monomer accounts for total mass is 3～5%, for example can be 3%, 4%, 5%; The mass percent that anionic monomer acrylic acid potassium accounts for total mass is 65～70%, for example can be 65%, 68%, 70%; The mass percent that Acrylic Acid Monomer accounts for total mass is 15～17%, for example can be 15%, 16%, 17%.After the linking agent copolymerization, dual crosslinked by physics and chemistry, add linking agent glycerine, form the hybrid reaction system.
Second step: insulation reaction.Be incubated 4～6 hours, for example can be 4 hours, 5 hours, 6 hours; 50 ℃～65 ℃ of temperature of reaction controls for example can be 50 ℃, 55 ℃, 60 ℃, 65 ℃.
The 3rd step: reaction obtains Zwitterion association type high wate-absorption resin after finishing after granulation, drying, pulverizing.
What in this example, alkaline solution can be in NaOH solution, the KOH solution is a kind of; Linking agent can be in formaldehyde, glycerine, the allylic additional crosslinker a kind of; Initiator type can be in redox system initiator (Potassium Persulphate and sodium bisulfite), the azo-initiator (as Diisopropyl azodicarboxylate) a kind of.
Embodiment 2
A kind of Zwitterion association type high wate-absorption resin according to the described method preparation of embodiment, this resin restrains water/gram resins to the water regain of deionized water greater than 1000, water regain to tap water restrains water/gram resins greater than 500, and the water regain of the sodium chloride aqueous solution to 0.9% is greater than 100 gram water/gram resins.
This Zwitterion association type high wate-absorption resin, its structure are that molecular-weight average that the repeated structure of following general formula performance occurs being formed is 600～1,000 ten thousand linear polymerization body.
Embodiment 3
The preparation of Zwitterion association type high wate-absorption resin and water absorbing properties:
1, takes by weighing vinylformic acid 90g, measure 6mol/L NaOH solution 175mL, both neutralization and cool to room temperature.
2, take by weighing 12g associating monomer octadecyl dimethyl-allyl ammonium chloride, 21g cationic monomer diallyldimethylammonChloride Chloride, 10g monomer acrylamide, and 0.04g linking agent glycerine, add 115ml water, fully stirring and dissolving adds the vinylformic acid neutralizer then.
3, add Potassium Persulphate 0.2g, sodium bisulfite 0.2g and cause, 65 ℃ of reaction 4h after the product cooling, through granulation, drying, pulverizing, get the fine particulate Zwitterion association type high wate-absorption resin.
The product that makes in the present embodiment (water-absorbing resin) is a particulate state, measures its every gram resin with " suction filtration method " and inhales deionized water 1120 grams, inhales tap water 580 grams, inhales 0.9% sodium chloride aqueous solution 112 grams.
Embodiment 4
The preparation of Zwitterion association type high wate-absorption resin and water absorbing properties:
1, takes by weighing vinylformic acid 90g, measure 6mol/L KOH solution 155mL, both neutralization and cool to room temperature.
2, take by weighing 4g associating monomer octadecyl dimethyl-allyl ammonium chloride, 12g cationic monomer diallyldimethylammonChloride Chloride, 8g monomer acrylamide, and 0.04g linking agent formaldehyde, add 115ml water, fully stirring and dissolving adds the vinylformic acid neutralizer then.
3, add Diisopropyl azodicarboxylate 0.2g, cause, 55 ℃ of reaction 6h, after the product cooling, through granulation, drying, pulverizing, the fine particulate Zwitterion association type high wate-absorption resin.
The product that makes in the present embodiment (water-absorbing resin) is a particulate state, measures its every gram resin with " suction filtration method " and inhales deionized water 1126 grams, inhales tap water 593.5 grams, inhales 0.9% sodium chloride aqueous solution 113.2 grams.
In the above example resulting super absorbent resin fat prod reached have the water absorbent rate height, absorption speed is fast, intensity is high, the purpose of good salt tolerance, environment-protecting asepsis, preserve moisture and fertility.Greater than 1000 gram water/gram resins, greater than 500 gram water/gram resins, the water regain of the sodium chloride aqueous solution to 0.9% restrains water/gram resins greater than 100 to this resin to the water regain of tap water to the water regain of deionized water.Suction (deionized water) multiple with respect at present general acrylic acid or the like super absorbent resin is 300～500 times, and its soaking effect significantly strengthens.
Claims (10)
1, Zwitterion association type high wate-absorption resin, its structure are that molecular-weight average that the repeated structure of following general formula performance occurs being formed is 600～1,000 ten thousand linear polymerization body.
2, Zwitterion association type high wate-absorption resin according to claim 1, it is characterized in that, described Zwitterion association type high wate-absorption resin restrains water/gram resins to the water regain of deionized water greater than 1000, water regain to tap water restrains water/gram resins greater than 500, and the water regain of the sodium chloride solution to 0.9% is greater than 100 gram water/gram resins.
3, the preparation method of the described Zwitterion association type high wate-absorption resin of a kind of claim 1 is characterized in that, comprises the steps:
The first step: Acrylic Acid Monomer is neutralized to 70～80% degree of neutralization with alkaline solution after, add synthetic good associating monomer, cationic monomer, acrylamide, anionic monomer, Acrylic Acid Monomer formation hybrid reaction system, and add the water mixing, form the hybrid reaction system; Material beyond dewatering in the mixed system accounts for 50%～65% of hybrid reaction system total mass; In the mixed system by the total mass of associating monomer, cationic monomer, acrylamide, anionic monomer, Acrylic Acid Monomer, associating monomer accounts for 3～5% of total mass, cationic monomer diallyldimethylammonChloride Chloride accounts for 5～7% of total mass, acrylamide monomer accounts for 3～5% of total mass, anionic monomer acrylic acid potassium accounts for 65～70% of total mass, and Acrylic Acid Monomer accounts for 15～17% of total mass;
Second step: after in above-mentioned hybrid reaction system, adding the linking agent copolymerization, add initiator, form the hybrid reaction system;
The 3rd step: insulation reaction is incubated 4～6 hours, 50～65 ℃ of temperature of reaction controls;
The 4th step: reaction obtains Zwitterion association type high wate-absorption resin after finishing after granulation, drying, pulverizing.
4, the preparation method of Zwitterion association type high wate-absorption resin according to claim 3 is characterized in that, associating monomer is an associating monomer octadecyl dimethyl-allyl ammonium chloride.
5, the preparation method of Zwitterion association type high wate-absorption resin according to claim 3 is characterized in that, cationic monomer and negatively charged ion unit are respectively dimethyl diallyl ammonium chloride and potassium acrylate.
6, the preparation method of Zwitterion association type high wate-absorption resin according to claim 3 is characterized in that, described linking agent copolymerization process has physics and chemistry is dual crosslinked.
7, the preparation method of Zwitterion association type high wate-absorption resin according to claim 3, it is characterized in that, described linking agent is formaldehyde, glycerine, allylic additional crosslinker, and wherein linking agent shared mass percent in reaction system is 0.04～0.06%.
8, the preparation method of Zwitterion association type high wate-absorption resin according to claim 3, it is characterized in that, described initiator is the redox system initiator, or azo-initiator, and wherein initiator shared mass percent in reaction system is 1～2%.
9, the preparation method of Zwitterion association type high wate-absorption resin according to claim 8 is characterized in that, described initiator is Potassium Persulphate or sodium bisulfite or Diisopropyl azodicarboxylate.
10, the preparation method of Zwitterion association type high wate-absorption resin according to claim 3 is characterized in that, described alkaline solution is NaOH solution, KOH solution, and wherein the mass percent concentration of alkaline solution is 10～15%.
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| CN102358771A (en) * | 2011-08-05 | 2012-02-22 | 北京爱普聚合科技有限公司 | Temperature resistant, non-crosslinked and biodegradable gel leak-stopping agent and preparation method thereof |
| CN103666435A (en) * | 2012-09-05 | 2014-03-26 | 梁辉 | Reversible crosslinking low-damage fracturing fluid thickening agent and production method thereof |
| CN105384882A (en) * | 2015-12-24 | 2016-03-09 | 山西农业大学 | Oxidized peat fulvic acid composite water retaining agent and preparation method thereof |
| CN107189016A (en) * | 2017-06-07 | 2017-09-22 | 中国科学院生态环境研究中心 | The technique that waste or used plastics prepare the super absorbent material of both sexes |
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2008
- 2008-10-23 CN CNA2008100463510A patent/CN101440144A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102352232A (en) * | 2011-08-05 | 2012-02-15 | 北京爱普聚合科技有限公司 | Temperature-resistant and salt-resistant polymer clean fracturing fluid thickening agent and preparation method thereof |
| CN102358771A (en) * | 2011-08-05 | 2012-02-22 | 北京爱普聚合科技有限公司 | Temperature resistant, non-crosslinked and biodegradable gel leak-stopping agent and preparation method thereof |
| CN102352232B (en) * | 2011-08-05 | 2013-08-07 | 北京爱普聚合科技有限公司 | Temperature-resistant and salt-resistant polymer clean fracturing fluid thickening agent and preparation method thereof |
| CN103666435A (en) * | 2012-09-05 | 2014-03-26 | 梁辉 | Reversible crosslinking low-damage fracturing fluid thickening agent and production method thereof |
| CN105384882A (en) * | 2015-12-24 | 2016-03-09 | 山西农业大学 | Oxidized peat fulvic acid composite water retaining agent and preparation method thereof |
| CN107189016A (en) * | 2017-06-07 | 2017-09-22 | 中国科学院生态环境研究中心 | The technique that waste or used plastics prepare the super absorbent material of both sexes |
| CN114853529A (en) * | 2022-04-20 | 2022-08-05 | 深圳市芭田生态工程股份有限公司 | Soil loosening water-saving liquid fertilizer and preparation method and application thereof |
| CN114853529B (en) * | 2022-04-20 | 2024-03-26 | 深圳市芭田生态工程股份有限公司 | Soil loosening water-saving liquid fertilizer and preparation method and application thereof |
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Open date: 20090527 |