CN104788619A - Star-netted organic-inorganic composite super absorbent and preparation method thereof - Google Patents
Star-netted organic-inorganic composite super absorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a star-netted organic-inorganic composite super absorbent and a preparation method thereof, and belongs to the field of novel materials. The star-netted organic-inorganic composite super absorbent comprises the following components in parts by weight: 30-50 parts of superfine silica solution or nano-silica, 10-20 parts of nano-titania, 40-100 parts of hydroxypropyl methyl cellulose, 20-30 parts of N-isopropylacrylamide, 0.02-0.3 part of a crosslinking agent and 0.4-1.2 parts of an initiator, wherein the solid content of the superfine silica solution is 10-30 wt%, and the grain size of nano-silica is 1-100 nm. The super absorbent prepared by the preparation method can be prepared according to the proportion at normal temperature, without adding other heating equipment, has stable and excellent water absorbing and holding properties and good salt tolerance, and can be widely used for preventing and controlling desertification in arid and semi-arid areas, agricultural planted crops, forest cultivated tree seedlings, pastoral planted grasslands and the like.
Description
Technical field
The present invention relates to a kind of soil, desert water-holding agent, be specifically related to one and there is star-like cancellated organic-inorganic compoiste super strength water absorbent and preparation method thereof, belong to field of new.
Background technology
China is one of country of lacking of water resources in the world, and Arid&semi-arid area area accounts for 47% of territory total area, wherein China arid Shao Shui area of having the territory of 45% to be in annual precipitation to be less than 400mm, and the shortage of annual irrigation water is also more than 3,000,000,000 m
3even if in the area that Precipitation of South China is more, also there is seasonal and regional lack of water.Drought and water shortage is the important factor of restriction China agricultural sustainable development, and along with global warming, arid aggravation, dry areas is also in continuous expansion.Therefore, how to improve Dryland, Inner Mongol soil drought resisting water retention capacity, improve water use efficiency, alleviating the extent of injury of arid to crop, to ensure that Stabilizing Grain Output increases production, is current key subjects urgently to be resolved hurrily.
Chemical water-saving technology utilizes chemical material or preparation by directly acting on plant or indirect action improves the water consumption characteristic of plant in soil, and then improve efficiency of water application.At present, a collection of novel, the multifunction water-saving material such as water-holding agent, soil-solidified-agent has been applied and has obtained good result in agricultural.
Water-holding agent is taked precautions against drought owing to having, drought resisting, water saving, raising fertilizer efficiency, improvement many-sided effect such as soil, volume increase, widespread use in various countries' agriculture production.Water-keeping material common in China's agriculture production has polyacrylate, polyacrylamide, humic acid, wilkinite etc. at present, wherein High hydrophilous resin (SAP) is a kind of new functional macromolecule material, it has the high absorbent function of the heavy hundreds of of specific absorption self to several thousand times of water, and water retention property is excellent, hydrogel is become, even if pressurization is also difficult to water to separate once water-swelling.High hydrophilous resin can reduce infiltration and the evaporation loss of soil moisture, extends the time that plant reaches wilting point, reduces irrigation frequency, improve the utilising efficiency of water resources.When arid occurs, High hydrophilous resin can along with the growth of plant moisture evapotranspiration the moisture of its inside of slow releasing, for plant normal growth, and having absorbent function repeatedly, is a kind of effective water-holding agent.
CN104263376A discloses a kind of novel soil compound water retaining agent, described compound water retaining agent comprises modified chitosan, modification marine alga, acrylamide, NVP, N, N '-methylene-bisacrylamide, 2-2-hydroxy-4-methylthio butyramide, ammonium persulphate, composite assistant, fermentation fertilizer, polynite, Xylo-Mucine, nanometer additive, calcium aluminate powder and Sodium salts humic acids, wherein the adding distilled water be mixed with 5-8wt% solution by taking soluble chitosan of modified chitosan, add waterside lichenin, stirring is warming up to 50-60 DEG C and mixes 5-10min, then isopropyl titanate is added, be warming up to 70-80 DEG C of stirring reaction 20-25min to obtain.By the suitable collocation of component, the optimized choice of processing step, water retention property obtains effective lifting.
CN1912006A discloses a kind of humic acid base superstrength water retaining agent and preparation method thereof, and it contains coal humic acid, vinylformic acid, industrial starch, linking agent, NaOH solution and Potassium Persulphate.With the higher coal of humic acids content for raw material extracts humic acids, humic acids and highly basic are reacted, form humate solution and with hydrophilic monomer and starch graft copolymer, keep bath temperature 60 DEG C to forming viscous gel shape product, water retention property obtains effective improvement.
CN102558618A discloses a kind of substrate water retaining agent, comprises additive and tackiness agent, and wherein additive selects one or more in Zulkovsky starch, bamboo charcoal powder, corn cob pyrolysis powder, and tackiness agent selects cyclodextrin and Xylo-Mucine.The substrate water retaining agent of this invention is prepared from by natural matter, and water absorption and swelling degree reaches 145-188%, is expanded to hydrogel after water suction, strengthens matrix water-retentivity, and can utilize for plant absorption by slow releasing moisture, the water conservation time is long, effective.
CN102585835A discloses a kind of water-loss reducer of soil utilizing the carbonizing production of agricultural crop straw to make, by the biological black wood charcoal that agricultural crop straw charing obtains, cross 60 mesh sieves, add water, mix, add PAM, mix, being dried to water ratio is that 10%-30% takes out, and is cut into the fragment of each about 0.3-0.5cm of length and width, then be dried to constant weight, namely obtain water-holding agent.The water-holding agent of this invention is cheap, and water retention property is stablized.
In prior art, use high molecular polymer water-retaining agent, there is degradation time long, and imbibition less stable, be difficult to obtain the higher product of over-all properties, especially salt tolerance can not ensure, limits the application of superabsorbent to a great extent.
Summary of the invention
The object of the invention is the technical problem for existing in prior art, there is provided a kind of absorb subsemimodule strong, the environmental protection organic-inorganic compoiste super strength water absorbent of good salt tolerance, inorganics is with a large amount of active groups, and there is unique space structure, by itself and synthetic organic polymers matrix compound tense, not only can improve the water absorbing and retaining properties of superabsorbent, salt tolerance, thermostability and reusing, and the production cost of superabsorbent can be reduced, solve the problem such as water retention property instability and salt tolerance difference.
For achieving the above object, the present invention takes following technical scheme:
A kind of star-like netted organic-inorganic compoiste super strength water absorbent, its raw material (weight part) composed as follows:
Wherein, described superfine silica sol is the parent of nano silicon, and its preparation method is: water glass is diluted water-soluble after, ultrasonic vibration 10-20min mixes, formed concentration be the water glass solution of 5wt%-40wt%; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2 ~ 1:3 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 20:1 ~ 40:1, removing impurity, obtains pretreated silicate solution; In amount of activated silicate solution, add alkaline solution, adjust ph be 9-10, normal after press control 70-85 DEG C reacting by heating 1-3 hour particle diameter be silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 10-30wt%, wherein silicon-dioxide particle diameter is between 1-100nm.Preferably, parts by weight shared by described superfine silica sol are 35-40, more preferably 35; Thickness of silica gel is 20wt%.In the present invention, superfine silica sol can be replaced the nano silicon that particle diameter is 1-100nm.
Preferably, parts by weight shared by Vltra tears are 70-90, more preferably 75.
Preferably, nano titanium oxide particle diameter is 5-50nm, and shared weight fraction is 15.
Preferably, described linking agent is N,N methylene bis acrylamide.
Preferably, described initiator is Potassium Persulphate and sodium sulphite anhydrous 99.3, and the two mass ratio is 1:1.
Another object of the present invention is to provide the preparation method of above-mentioned star-like netted organic-inorganic compoiste super strength water absorbent.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A preparation method for star-like netted organic-inorganic compoiste super strength water absorbent, comprises the steps:
(1) get the raw materials ready by following composition (weight part):
(2) prepare superfine silica sol: water glass is diluted water-soluble after, ultrasonic vibration 10-20min mixes, formed concentration be the water glass solution of 5wt%-40wt%; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2 ~ 1:3 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 20:1 ~ 40:1, removing impurity, obtains pretreated silicate solution; In amount of activated silicate solution, add alkaline solution, adjust ph be 9-10, normal after press control 70-85 DEG C reacting by heating 1-3 hour particle diameter be silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 10-30wt%, wherein silicon-dioxide particle diameter is between 1-100nm.
(2) under normal temperature, Vltra tears is added deionized water, be stirred under nitrogen protection and dissolve completely;
(3) add superfine silica sol solution and nano titanium oxide successively, form sol liquid;
(4) then add NIPA monomer, under nitrogen atmosphere, heating temperatures to 20-50 DEG C, stirring and dissolving, about 5-30min;
(5) when homo(io)thermism, after pH value being adjusted to 8-11 with sodium hydroxide alkaline solution, add the aqueous solution of initiator potassium persulfate and sodium sulphite anhydrous 99.3, linking agent N successively, the aqueous solution of N-methylene-bisacrylamide, accelerates to stir, makes its crosslinking polymerization, abundant reaction, after insulation reaction 3h-11h, be cooled to room temperature, obtain organic-inorganic compoiste polymer gel;
(6) gel is mixed with the aqueous solution that concentration is 2wt%-10wt%, after carrying out precipitate and separate with acetone to polymkeric substance, in vacuum drying oven, carry out drying, drying temperature is 50-80 DEG C, obtains product.
Described superfine silica sol is the parent of nano silicon, and its preparation method is: water glass is diluted water-soluble after, ultrasonic vibration 10-20min mixes, formed concentration be the water glass solution of 5wt%-40wt%; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2 ~ 1:3 be mixed to get compound exchange resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 20:1 ~ 40:1, removing impurity, obtains pretreated silicate solution; In silicate solution, add alkaline solution, adjust ph is 9-10, often obtains silicon sol mother liquor after press control 70-85 DEG C reacting by heating 1-3 hour; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 10-30wt%, wherein silicon-dioxide particle diameter is between 1-100nm.
Preferably, it is characterized in that: described superfine silica sol replaces with nano silicon.
Preferably, shared by described superfine silica sol or nano silicon, parts by weight are 35-40, more preferably 35, and thickness of silica gel is 20%.
Preferably, parts by weight shared by Vltra tears are 70-90, more preferably 75.
The performance index of the super strength water absorbent prepared are as follows:
1.00g/m
2< density <1.10g/m
2; Viscosity >800mP.S; 6<pH value <8; Maximum Water absorption: 680 times; Year degradation rate 10wt%-15wt%.Find through Electronic Speculum contrast, nano-inorganic substance has successfully entered in Mierocrystalline cellulose, forms nuclear membrane structure.
Beneficial effect:
The present invention is large according to nano particle specific surface area, and the feature that avidity is strong, prepares ultra-fine hyperpure silicasol, and nano silicon granularity is wherein little, and be uniformly dispersed, be rich in hydroxyl, water absorbing properties is superior, utilizes in-situ synthesis, adopts Nano-meter SiO_2
2clad nano titanium dioxide and Vltra tears polymer compound action mechanism, by inorganic nano-particle and Mierocrystalline cellulose compound, on the molecule being incorporated into modified-cellulose by nanoparticle, and make a nanoparticle connects multiple unmodified cellulose molecule, making it to be formed a kind of is core with nanoparticle, unmodified cellulose molecule is the star-like fibrosis reticulated structure of film, utilize crosslinking polymerization method, super absorbent resin alicyclic monomer NIPA is introduced in chain and is polymerized, crosslinked, grafting, multiple nuclear membrane star gear transmission polymkeric substance each other can through the link of multistep and combination, form nuclear membrane star-like Mierocrystalline cellulose/super-strong moisture absorbing network copolymer, water molecules is made to be easy to contact with netted chain, infiltrate through areola, form gelling material and be stored up, degree of crosslinking between polymer molecule can form reticulated structure, simultaneously intermolecular exist various ionic group, stronger water affinity can be produced, moisture can be pinned firmly, it is tightly locked within reticulated structure, formation can the gelling material of slow releasing moisture.Polymer mesh performance is more firm, and water retention property is higher.Through test, after super strength water absorbent of the present invention water suction repeatedly in the deionized water of pressurization 2KPa-dry-water suction 20 times, water absorbent rate still remains on more than 500 (g/g).
Due to the introducing of nano-inorganic substance, the hydroxyl that nano silicon and titanium dioxide contain by rich surface is by physical adsorption and chemisorption large quantity of moisture, not only increase absorb subsemimodule and repeat water absorbing properties, further improve the performance of hydroscopic high-molecular resin salt tolerance difference, the use range of water-absorbing water-retaining agent and stability.Through test, super strength water absorbent of the present invention is water absorbent rate in the salt solution of 0.9% at pressurization 1KPa massfraction, is 198 (g/g), significantly improves salt tolerance, solve the problem of High hydrophilous resin as the salt tolerance difference of polyacrylamide, can be used for the saltings of the Northwest.
Super strength water absorbent of the present invention can proportioning complete, without the need to increasing other warming-up devices under normal temperature state.It has stable excellent absorb subsemimodule, has again good salt tolerance, is mainly used in defending and controlling sand, agricultural planting crops, forestry are grown saplings, the water-absorbing-retaining on animal husbandry plantation meadow etc.Be sprayed on the top layer of sandy soil after its proportioning being completed at normal temperatures, one can be formed on surface and continue water conservation layer, provide adequate water in arid/semiarid zone, and can not environmental pollution be caused, there is huge economic benefit and the social benefit of environment protection.
Below by specific embodiment, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1-(a) and Fig. 1-(b) is respectively cellulose modified forward and backward contrast Electronic Speculum figure.
Fig. 2 is that the present invention prepares the Water absorption of super strength water absorbent and the lab diagram of water suction number of times.
Embodiment
Embodiment 1
Prepare superfine silica sol: water glass is diluted water-soluble after, ultrasonic vibration 20min mixes, formed concentration be the water glass solution of 30wt%; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 20:1, removing impurity, obtains pretreated silicate solution; In silicate solution, add alkaline solution, adjust ph be 9.5, normal press control 70 DEG C of reacting by heating after 2 hours silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 20wt%, wherein silicon-dioxide particle diameter is between 1-100nm.
Under normal temperature, 4g Vltra tears is added deionized water, be stirred under nitrogen protection and dissolve completely, adding 3g concentration is successively 20wt% superfine silica sol solution and 1g nano titanium oxide, forms sol liquid; Then 3gN-N-isopropylacrylamide monomer is added, under nitrogen atmosphere, heating temperatures to 30 DEG C, stirring and dissolving is about 25min; By NaOH solution, pH value is adjusted to 9, adds containing 0.04g Potassium Persulphate and the aqueous solution of 0.04g sodium sulphite anhydrous 99.3, the aqueous solution containing 0.03g linking agent N,N methylene bis acrylamide successively, accelerate to stir, after insulation reaction 3h, be cooled to room temperature, obtain gel; Gel is mixed with the aqueous solution that concentration is 5wt%, after carrying out precipitate and separate with acetone to polymkeric substance, in vacuum drying oven, carry out drying, drying temperature 60 DEG C, obtains super strength water absorbent of the present invention.
As shown in Figure 2, for the present embodiment prepares the Water absorption of super strength water absorbent and the lab diagram of water suction number of times.
Embodiment 2
Prepare superfine silica sol: water glass is diluted water-soluble after, ultrasonic vibration 10min mixes, formed concentration be the water glass solution of 25wt%; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:3 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 40:1, removing impurity, obtains pretreated silicate solution; In silicate solution, add alkaline solution, adjust ph be 9, normal press control 85 DEG C of reacting by heating after 1 hour silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 20wt%, wherein silicon-dioxide particle diameter is between 1-100nm.
Under normal temperature, 3g Vltra tears is added deionized water, be stirred under nitrogen protection and dissolve completely, adding 1.5g concentration is successively 20wt% superfine silica sol solution and 1g nano titanium oxide, forms sol liquid; Then 2gN-N-isopropylacrylamide monomer is added, under nitrogen atmosphere, heating temperatures to 40 DEG C, stirring and dissolving is about 25min; By NaOH solution, pH value is adjusted to 8.5, adds containing 0.05g Potassium Persulphate and the aqueous solution of 0.05g sodium sulphite anhydrous 99.3, the aqueous solution containing 0.01g linking agent N,N methylene bis acrylamide successively, accelerate to stir, after insulation reaction 3.5h, be cooled to room temperature, obtain gel; Gel is mixed with the aqueous solution that concentration is 5wt%, after carrying out precipitate and separate with acetone to polymkeric substance, in vacuum drying oven, carry out drying, drying temperature 60 DEG C, obtains super strength water absorbent of the present invention.
Embodiment 3
Prepare superfine silica sol: water glass is diluted water-soluble after, ultrasonic vibration 15min mixes, formed concentration be the water glass solution of 5wt%; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2.5 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 30:1, removing impurity, obtains pretreated silicate solution; In silicate solution, add alkaline solution, adjust ph be 10, normal press control 80 DEG C of reacting by heating after 3 hours silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 20wt%, wherein silicon-dioxide particle diameter is between 1-100nm.
Under normal temperature, 10g Vltra tears is added deionized water, be stirred under nitrogen protection and dissolve completely, adding 4g concentration is successively 20wt% superfine silica sol solution and 2g nano titanium oxide, forms sol liquid; Then 6gN-N-isopropylacrylamide monomer is added, under nitrogen atmosphere, heating temperatures to 30 DEG C, stirring and dissolving is about 30min; By NaOH solution, pH value is adjusted to 9.5, adds containing 0.05g Potassium Persulphate and the aqueous solution of 0.05g sodium sulphite anhydrous 99.3, the aqueous solution containing 1.6g linking agent N,N methylene bis acrylamide successively, accelerate to stir, after insulation reaction 3h, be cooled to room temperature, obtain gel; Gel is mixed with the aqueous solution that concentration is 5wt%, after carrying out precipitate and separate with acetone to polymkeric substance, in vacuum drying oven, carry out drying, drying temperature 60 DEG C, obtains super strength water absorbent of the present invention.
The star-like netted organic-inorganic compoiste super strength water absorbent that the present invention prepares, can proportioning complete under normal temperature state, without the need to increasing other warming-up devices, it has stable excellent absorb subsemimodule, there is again good salt tolerance, the defending and controlling sand of arid/semiarid zone can be widely used in, agricultural planting crops, forestry are grown saplings, animal husbandry plantation meadow etc.
Claims (10)
1. a star-like netted organic-inorganic compoiste super strength water absorbent, its raw material composition is as follows by weight:
Wherein, described superfine silica sol is the parent of nano silicon, and its preparation method is: water glass is diluted water-soluble after, ultrasonic vibration 10-20min mixes, formed water glass solution; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2 ~ 1:3 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 20:1 ~ 40:1, removing impurity, obtains pretreated silicate solution; In amount of activated silicate solution, add alkaline solution, adjust ph be 9-10, normal after press control 70-85 DEG C reacting by heating 1-3 hour particle diameter be silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 10-30wt%, wherein silicon-dioxide particle diameter is between 1-100nm.
2. star-like netted organic-inorganic compoiste super strength water absorbent according to claim 1, is characterized in that: described superfine silica sol replaces with nano silicon.
3. star-like netted organic-inorganic compoiste super strength water absorbent according to claim 1, it is characterized in that: parts by weight shared by described superfine silica sol are 35-40, thickness of silica gel is 20wt%.
4. the star-like netted organic-inorganic compoiste super strength water absorbent according to any one of claim 1-3, is characterized in that: parts by weight shared by Vltra tears are 70-90.
5. the star-like netted organic-inorganic compoiste super strength water absorbent according to any one of claim 1-3, it is characterized in that nano titanium oxide particle diameter is 5-50nm, shared weight fraction is 15.
6. the star-like netted organic-inorganic compoiste super strength water absorbent according to any one of claim 1-3, is characterized in that: described linking agent is N,N methylene bis acrylamide.
7. the star-like netted organic-inorganic compoiste super strength water absorbent according to any one of claim 1-3, is characterized in that: described initiator is Potassium Persulphate and sodium sulphite anhydrous 99.3, and the two mass ratio is 1:1.
8. a preparation method for star-like netted organic-inorganic compoiste super strength water absorbent as claimed in claim 1, comprises the steps:
(1) get the raw materials ready by composition described in claim 1 and proportioning;
(2) prepare superfine silica sol: water glass is diluted water-soluble after, ultrasonic vibration 10-20min mixes, formed water glass solution; By storng-acid cation exchange resin and strongly basic anion exchange resin by volume 1:2 ~ 1:3 be mixed to get compound resin; Water glass solution and compound exchange resin are fully uniformly mixed by weight 20:1 ~ 40:1, removing impurity, obtains pretreated silicate solution; In amount of activated silicate solution, add alkaline solution, adjust ph be 9-10, normal after press control 70-85 DEG C reacting by heating 1-3 hour particle diameter be silicon sol mother liquor; Silicon sol mother liquor carries out dehydration and divides, concentrates and purifying, and prepare the silicon sol that concentration is 10-30wt%, wherein silicon-dioxide particle diameter is between 1-100nm;
(3) under normal temperature, Vltra tears is added deionized water, be stirred under nitrogen protection and dissolve completely;
(4) add superfine silica sol solution and nano titanium oxide successively, form sol liquid;
(5) then add NIPA monomer, under nitrogen atmosphere, heating temperatures to 20-50 DEG C, stirring and dissolving 5-30min;
(6) when homo(io)thermism, after pH value being adjusted to 8-11 with sodium hydroxide alkaline solution, add initiator potassium persulfate and the sodium sulphite anhydrous 99.3 aqueous solution, linking agent N successively, the N-methylene-bisacrylamide aqueous solution, accelerate to stir, its crosslinking polymerization is fully reacted, after insulation reaction 3h-11h, be cooled to room temperature, obtain organic-inorganic compoiste polymer gel;
(7) gel is mixed with the aqueous solution that concentration is 2%-10%, after carrying out precipitate and separate with acetone to polymkeric substance, in vacuum drying oven, carry out drying, drying temperature 50-80 DEG C, obtains product.
9. the preparation method of star-like netted organic-inorganic compoiste super strength water absorbent according to claim 8, is characterized in that: described superfine silica sol replaces with nano silicon.
10. the preparation method of star-like netted organic-inorganic compoiste super strength water absorbent according to claim 8, it is characterized in that: parts by weight shared by described superfine silica sol are 35, thickness of silica gel is 20wt%; Parts by weight shared by described Vltra tears are 75.
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| CN105906766A (en) * | 2016-06-15 | 2016-08-31 | 武汉工程大学 | Preparation method of light/biological dual-degradation high-water-absorption resin based on natural polymer |
| CN107602932A (en) * | 2017-10-19 | 2018-01-19 | 宁波智果科技咨询服务有限公司 | A kind of preparation method of carboxyethyl cellulose benzyl acid amides/Si composite high-water-absorptivresin materials |
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| CN109970917A (en) * | 2019-04-04 | 2019-07-05 | 黑龙江大学 | A kind of super absorbent resin and preparation method thereof containing montmorillonite |
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