CN102702425B - Salt-tolerant cationic super-absorbent resin and preparation method and application of salt-tolerant cationic super-absorbent resin - Google Patents
Salt-tolerant cationic super-absorbent resin and preparation method and application of salt-tolerant cationic super-absorbent resin Download PDFInfo
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- CN102702425B CN102702425B CN201210160691.2A CN201210160691A CN102702425B CN 102702425 B CN102702425 B CN 102702425B CN 201210160691 A CN201210160691 A CN 201210160691A CN 102702425 B CN102702425 B CN 102702425B
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Abstract
The invention discloses a cationic super-absorbent resin and a preparation method of the cationic super-absorbent resin. The super-absorbent resin forms a three-dimensional network skeleton mainly containing a cationic group by introducing acrylamide, tertiary amine cationic monomer and quaternary ammonium salt cationic monomer. The preparation method comprises the following steps: adding the acrylamide, the tertiary amine monomer, the quaternary ammonium salt monomer, deionized water, a cross-linking agent and an initiator solution to a reactor by a certain ratio, introducing nitrogen to protect and starting agitation, heating and warming the mixture to 30-95 DEG C so as to carry out polymerization reaction for 0.5-3.0 hours. The cationic super-absorbent resin has excellent water absorbability, salt resistance, gel strength and repeated water absorbability, and above all, the defect that anionic super-absorbent resin easily shrinks in a saline environment containing high-valence metal ions is effectively overcome. The cationic super-absorbent resin is suitable for wide popularization and development in agriculture, also can be used for adsorbing the saline solution such as urine, blood and the like in the field of medical health.
Description
Technical field
The present invention relates to cationic High hydrophilous resin of a kind of salt resistance and preparation method thereof and application.
Background technology
High hydrophilous resin (Superabsorbent Polymers is called for short " SAP "), is commonly called as water-holding agent, refers to the polymer substance that water-retaining capacity is strong especially.High hydrophilous resin rapidly hundred times of specific absorption self tuples even the deionized water, decades of times of thousands of times to saliferous moisture nearly a hundred times.High hydrophilous resin has excellent water absorbing properties, water retention property and water absorbing properties repeatedly, is therefore widely used in promoting plant root system development in agricultural field, improves transplant seedlings surviving rate, preserve moisture and fertility, increasing both production and income, the aspect such as check winds and fix drifting sand.There is in addition the ability of certain absorption salt solution due to High hydrophilous resin, be therefore also widely used in medicine and hygiene fields.
What in practical application at present, use was the most extensive, output is maximum is polyacrylic acid (salt) class High hydrophilous resin, is mainly divided into synthetic class and grafting class.Synthetic class is to realize High hydrophilous resin prepared by copolymerization by vinylformic acid (salt) and other monomer as acrylamide etc., this class High hydrophilous resin preferably can obtaining thering is high-gel strength under processing condition, the product of strong water retention capacity, high water absorbing capacity and strong saline-alkaline tolerance.Grafting class is to carry out copolymerzation with cross-linking by vinylformic acid (salt) with natural macromolecular materials such as starch to react, the High hydrophilous resin preparing, and its water absorbing properties is poor, but cost is lower.
The group that plays water sorption in polyacrylic acid (salt) class High hydrophilous resin structure is mainly anionic group (this class High hydrophilous resin is called as anionic High hydrophilous resin), for example carboxylate radical-COO
-.In the process of anionic High hydrophilous resin water suction, anionic group gradually dissociation out, because it is fixed in the three-dimensional network skeleton of anionic High hydrophilous resin, therefore can repel mutually, thereby anionic High hydrophilous resin is expanded and further water suction, finally reach balance.But, in the actual application environment of High hydrophilous resin, often can run into salt ion, especially contain the saltwater environment of high volence metal ion, as the root exudates of plant secretion in the well water of irrigation use, soil.Especially high volence metal ion of the metal ion containing in these saltwater environments, as Ca
2+, Mg
2+deng, and anionic group generation sequestering action easily and in anionic High hydrophilous resin, make it that secondary crosslinking, network structure occur and tighten even disintegration, even lose its anti-salt property and water absorbing properties repeatedly thereby reduce, limited High hydrophilous resin popularization in actual applications.
There is at present a lot of research by introducing non-ionic monomer, anionic monomer, cationic monomer and the zwitterionic monomer with obvious anti-salt ion ability to improve its salt resistance and anti-high volence metal ion ability in polyacrylic acid (salt) super absorbent resin resin system, but prepared High hydrophilous resin is still keeping the anion frame of polyacrylic acid (salt) class High hydrophilous resin by this method, cannot avoid the high volence metal ion complexing in itself and environment and the network structure that causes tightens and the reduction of water absorbing properties.
Summary of the invention
The present invention is directed to the problem that anionic High hydrophilous resin exists in actual applications, cationic High hydrophilous resin of a kind of novel salt-resistant and preparation method thereof is provided.
The general structure of the cationic High hydrophilous resin of salt resistance provided by the present invention is suc as formula shown in I:
(formula I)
In formula I, the integer that n is 1-10; X represents halogen (comprising F, Cl, Br, I); Y can be NH or O; R
1, R
2, R
3, R
4, R
5, R
6, R
7can be the same or different, all can be hydrogen, alkyl, alkoxyl group, alkenyl, aryl etc.
Cationic High hydrophilous resin provided by the present invention is that having prepared in three-dimensional network skeleton is mainly the High hydrophilous resin of cation group by tertiary amines and two kinds of cationic monomers of quaternary ammonium salt are incorporated in polyacrylamide High hydrophilous resin.
This cationic High hydrophilous resin can repel the ionizable metal salt in extraneous water surrounding effectively, and owing to not containing anionic group in resin matrix, thereby effectively overcome the drawback that anionic High hydrophilous resin shrinks.
Above-mentioned cationic High hydrophilous resin specifically can prepare according to the method comprising the steps: under protection of inert gas; taking three kinds of monomer acrylamides, tertiary amines cationic monomer, quaternaries cation monomer as raw material; under the effect of initiator and linking agent, carry out cross-linking polymerization, obtain described cationic High hydrophilous resin.
Wherein, described quaternaries cation monomer, adopts the compound that contains quaternary ammonium salt group and carbon-to-carbon double bond, and its chemical structure of general formula is suc as formula shown in II:
(formula II)
Wherein, the integer that n is 1-10; X represents halogen (comprising F, Cl, Br, I); Y can be NH or O; R
1, R
2, R
3, R
4can be the same or different, all can be hydrogen, alkyl, alkoxyl group, alkenyl, aryl etc.
Described tertiary amines cationic monomer, adopts the compound that contains tertiary amine group and carbon-to-carbon double bond, and its chemical structure of general formula is suc as formula shown in III: *
(formula III)
Wherein, the integer that n is 1-10; Y can be NH or O; R
5, R
6with R
7can be the same or different, all can be hydrogen, alkyl, alkoxyl group, alkenyl, aryl etc.
Described linking agent has can make the monomer crosslinked function of the cationic High hydrophilous resin of three-dimensional net structure comparatively closely that becomes, and the present invention preferably adopts the neutral linking agent N,N methylene bis acrylamide (MBA) with saline-alkaline tolerance.
Described initiator is the polyreaction between trigger monomer effectively, and the present invention preferably adopts can produce after reaction decomposes and is beneficial to sylvite that plant absorbs or Potassium Persulphate or the ammonium persulphate of ammonium salt.
In aforesaid method, the mass ratio of three kinds of monomer acrylamides, tertiary amines cationic monomer, quaternaries cation monomer can be followed successively by (2.25-4.25): (2.25-2.55): (3.50-5.20).
The add-on of described linking agent is the 0.005-0.08wt% of three kinds of monomer total masses.
The add-on of described initiator is the 0.5-4.5wt% of three kinds of monomer total masses.
The temperature of reaction of described cross-linking polymerization is 30-95 DEG C, and the reaction times can be 0.5-3.0h.
The reaction solvent of described cross-linking polymerization is water, preferably deionized water.
Described rare gas element comprises the gas such as nitrogen, argon gas.
The cationic High hydrophilous resin of preparation according to the method described above, it can reach 200-800 doubly to the water-intake rate of deionized water, can reach 30-70 doubly, to containing 140-160mg/LCa to the water-intake rate of the 0.9wt%NaCl aqueous solution
2+and 40-60mg/LMg
2+the water-intake rate of tap water can reach 80-120 doubly.
Cationic High hydrophilous resin prepared by the present invention, compared with industrial polypropylene acid (salt) anionoid type High hydrophilous resin, even if soak 20h in tap water, still can not shrink phenomenon and anionic High hydrophilous resin shrinks up to 40-90%.This just shows that the prepared cationic High hydrophilous resin of the present invention has excellent anti-salt property, is suitable for popularization and development in actual applications.
Cationic High hydrophilous resin prepared by the present invention, in deionized water, the 0.9wt%NaCl aqueous solution and tap water, carrying out respectively the experiment of repetition water-intake rate finds: even if carry out repeating for five times water suction-dehydration experiment, prepared cationic High hydrophilous resin water-intake rate still can maintain the 20-70% of water-intake rate for the first time, and this shows that this cationic High hydrophilous resin has good repetition water-retaining capacity and gel stability.
Cationic High hydrophilous resin of the present invention has good water absorbing properties, anti-salt property, gel-strength and repetition water absorbing properties, the most important thing is that it has effectively overcome the defect that anionic High hydrophilous resin easily shrinks in the saltwater environment that contains high volence metal ion, be suitable for promoting widely and development in agricultural, also can be used in medicine and hygiene fields, the salts solution such as urine, blood being adsorbed.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the cationic High hydrophilous resin (b) prepared of polyacrylamide (a) and embodiment 1.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare cationic High hydrophilous resin
In reaction unit, pass into N
230min, then adds 25g deionized water, opens mechanical stirring; Take acrylamide 4.25g, dimethylamino-propyl acrylamide 2.25g, methylacryoyloxyethyl trimethylammonium ammonium iodide 3.50g, MBA 0.0005g add in reaction unit, continue stir and monomer all dissolved; Take Potassium Persulphate 0.05g and be dissolved in 5mL deionized water, all join in reaction system, and open heating, control 30 DEG C of temperature of reaction; After polymerization, continue reaction 30min, wash, dry, pulverize and to obtain faint yellow solid, be cationic High hydrophilous resin.
Fig. 1 is the infrared spectrogram of (a) polyacrylamide, (b) cationic High hydrophilous resin, as can be seen from the figure 952cm
-1, 1223cm
-1, 1138cm
-1having there is the charateristic avsorption band of salt ion group in place, shows that positively charged ion High hydrophilous resin successfully prepared.
It is 350.9g/g that this cationic High hydrophilous resin sucks ionized water rate, inhaling the 0.9wt%NaCl aqueous solution is 30.4g/g, inhaling tap water rate is 85.5g/g, repeat after water suction through five times, it sucks ionized water, inhales 0.9% physiological saline rate and inhales tap water and can reach respectively 123.7g/g, 15.0g/g and 8.5g/g.
Embodiment 2, prepare cationic High hydrophilous resin
In reaction unit, pass into N
230min, then adds 25g deionized water, opens mechanical stirring; Take acrylamide 3.75g, diethylaminoethyl methacrylate 2.35g, 3-acrylamide propyl trimethyl ammonium chloride 3.90g, MBA 0.0017g add in reaction unit, continue stir and monomer all dissolved; Take Potassium Persulphate 0.15g and be dissolved in 5mL deionized water, all join in reaction system, and open heating, control 50 DEG C of temperature of reaction; After polymerization, continue reaction 1.0h, wash, dry, pulverize and to obtain faint yellow solid, be cationic High hydrophilous resin.
It is 467.5g/g that this cationic High hydrophilous resin sucks ionized water rate, inhaling the 0.9wt%NaCl aqueous solution is 34.3g/g, inhaling tap water rate is 87.3g/g, repeat after water suction through five times, it sucks ionized water, inhales 0.9% physiological saline rate and inhales tap water and can reach respectively 187.6g/g, 19.5g/g and 10.4g/g.
Embodiment 3, prepare cationic High hydrophilous resin
In reaction unit, pass into N
230min, then adds 25g deionized water, opens mechanical stirring; Take acrylamide 3.25g, N, N dimethylamine base ethyl propenoate 2.45g, acrylyl oxy-ethyl-trimethyl salmiac 4.30g, MBA 0.0036g add in reaction unit, continue stir and monomer is all dissolved; Take Potassium Persulphate 0.25g and be dissolved in 5mL deionized water, all join in reaction system, and open heating, control 55 DEG C of temperature of reaction; After polymerization, continue reaction 1.0h, wash, dry, pulverize and to obtain faint yellow solid, be cationic High hydrophilous resin.
It is 514.4g/g that this cationic High hydrophilous resin sucks ionized water rate, inhaling the 0.9wt%NaCl aqueous solution is 37.0g/g, inhaling tap water rate is 94.2g/g, repeat after water suction through five times, it sucks ionized water, inhales 0.9% physiological saline rate and inhales tap water and can reach respectively 231.3g/g, 22.2g/g and 14.1g/g.
Embodiment 4, prepare cationic High hydrophilous resin
In reaction unit, pass into N
230min, then adds 25g deionized water, opens mechanical stirring; Take acrylamide 2.75g, dimethylamino-propyl Methacrylamide 2.50g, 3-Methacrylamide oxypropyl trimethyl ammonium chloride 4.75g, MBA 0.0069g add in reaction unit, continue stir and monomer all dissolved; Take Potassium Persulphate 0.35g and be dissolved in 5mL deionized water, all join in reaction system, and open heating, control 70 DEG C of temperature of reaction; After polymerization, continue reaction 1.5h, wash, dry, pulverize and to obtain faint yellow solid, be cationic High hydrophilous resin.
It is 623.8g/g that this cationic High hydrophilous resin sucks ionized water rate, inhaling the 0.9wt%NaCl aqueous solution is 40.3g/g, inhaling tap water rate is 100.6g/g, repeat after water suction through five times, it sucks ionized water, inhales 0.9% physiological saline rate and inhales tap water and can reach respectively 311.5g/g, 26.2g/g and 18.9g/g.
Embodiment 5, prepare cationic High hydrophilous resin
In reaction unit, pass into N
230min, then adds 25g deionized water, opens mechanical stirring; Take acrylamide 2.25g, dimethylaminoethyl methacrylate 2.55g, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 5.20g, MBA 0.008g add in reaction unit, continue stir and monomer all dissolved; Take Potassium Persulphate 0.45g and be dissolved in 5mL deionized water, all join in reaction system, and open heating, control 95 DEG C of temperature of reaction; After polymerization, continue reaction 3.0h, wash, dry, pulverize and to obtain faint yellow solid, be cationic High hydrophilous resin.
It is 698g/g that this cationic High hydrophilous resin sucks ionized water rate, inhaling the 0.9wt%NaCl aqueous solution is 46g/g, inhaling tap water rate is 113g/g, repeat after water suction through five times, it sucks ionized water, inhales 0.9% physiological saline rate and inhales tap water and can reach respectively 383.9g/g, 32.2g/g and 23.9g/g.
Claims (8)
1. general structure is suc as formula the cationic water-absorbing resin shown in I:
In formula I, the integer that n is 1-10; A, b, c, d, e, f are the repeating unit of monomer in macromolecular material, and braces represents that the structural unit in bracket is repeatably; X represents halogen; Y is NH or O; R
1, R
2, R
3, R
4, R
5, R
6, R
7identical or different, its be all selected from following any one: alkyl, alkoxyl group, alkenyl and aryl.
2. cationic water-absorbing resin according to claim 1, is characterized in that: described cationic water-absorbing resin has three-dimensional network skeleton structure.
3. the method for the cationic water-absorbing resin described in preparation claim 1 or 2, comprise the steps: under protection of inert gas, taking acrylamide monomer, quaternaries cation monomer, tertiary amines monomer as raw material, under the effect of initiator and linking agent, carry out cross-linking polymerization, obtain described cationic water-absorbing resin;
Described quaternaries cation monomer, its general structure is suc as formula shown in II:
In formula II, the integer that n is 1-10; X represents halogen; Y is NH or O; R
1, R
2, R
3, R
4identical or different, its be all selected from following any one: alkyl, alkoxyl group, alkenyl and aryl;
Described tertiary amines monomer, its general structure is suc as formula shown in III:
In formula III, the integer that n is 1-10; Y is NH or O; R
5, R
6, R
7identical or different, its be all selected from following any one: alkyl, alkoxyl group, alkenyl and aryl.
4. method according to claim 3, is characterized in that: described linking agent has can make the monomer crosslinked function of the cationic High hydrophilous resin of three-dimensional net structure comparatively closely that becomes; Described linking agent is specially N,N methylene bis acrylamide; Described initiator is Potassium Persulphate or ammonium persulphate.
5. according to the method described in claim 3 or 4, it is characterized in that: the mass ratio of described acrylamide monomer, tertiary amines monomer, quaternaries cation monomer is followed successively by (2.25-4.25): (2.25-2.55): (3.50-5.20).
6. according to the method described in claim 3 or 4, it is characterized in that: the add-on of described linking agent is the 0.005-0.08% of three kinds of monomer total masses; The add-on of described initiator is the 0.5-4.5% of three kinds of monomer total masses.
7. according to the method described in claim 3 or 4, it is characterized in that: the temperature of reaction of described cross-linking polymerization is 30-95 DEG C, the reaction times is 0.5-3.0h; The reaction solvent of described cross-linking polymerization is water.
8. the application of cationic water-absorbing resin in agricultural field or the application in medicine and hygiene fields described in claim 1 or 2.
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| JP6455065B2 (en) * | 2014-10-15 | 2019-01-23 | デクセリアルズ株式会社 | Water-absorbing polymer sheet |
| CN105384882B (en) * | 2015-12-24 | 2018-04-24 | 山西农业大学 | One kind oxidation peat fulvic acid compound water retaining agent and preparation method thereof |
| CN108998049B (en) * | 2018-07-25 | 2021-05-18 | 陕西科技大学 | Degradable natural high molecular compound coated humic acid sand-fixing agent and preparation method thereof |
| CN114478926B (en) * | 2022-03-17 | 2023-12-22 | 无锡中天固废处置有限公司 | Salt-resistant super absorbent resin of water hyacinth carboxymethyl cellulose and preparation method thereof |
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| CN101029109A (en) * | 2007-02-01 | 2007-09-05 | 江南大学 | Production of cationic microsphere with crosslinked swelling function |
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| CN101029109A (en) * | 2007-02-01 | 2007-09-05 | 江南大学 | Production of cationic microsphere with crosslinked swelling function |
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