CN102167768A - Super absorbent degradable colorful crystal soil containing nano-clay and preparation method thereof - Google Patents
Super absorbent degradable colorful crystal soil containing nano-clay and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a super absorbent degradable colorful crystal soil containing nano-clay and a preparation method thereof. The polymerization of acrylamide monomer M1, sodium acrylate M2, N, N'-methylene-bisacrylamide M3, inorganic nano-clay M4, water soluble biomacromolecule M5 and water soluble pigment M6 are dissolved in water and are synthesized to prepare the crystal soil in redox initiator system. The crystal soil not only processes high water absorption and color absorption, but also has certain mechanical property and biodegradability. The preparation method is simple and has controllable condition without polluting the environment. The water-absorbing capacity and the biodegradation time of the prepared crystal soil can be adjusted by parameters of temperature, PH value, degree of cross linking, dosage and type of water soluble biomacromolecule and nano-clay and reactant proportion, and the appearance color can be adjusted by the pigment type. The crystal soil of the invention is used for environment decoration of household, flower market and gardening, etc, and engineering field of nursery stock breeding, garden greening, agricultural producing, environment improving, revegetating, etc.
Description
Technical field
The invention belongs to super absorbent resin and preparation method thereof technical field, be particularly related to high-hydroscopicity degradable multiple-colour crystal mud that contains nanoclay and preparation method thereof, prepared quartzy mud can be used for family, flowers market, the environmental decoration of gardening etc. and beautify etc.
Background technology
Quartzy mud is a kind of water-loss reducer of soil that is similar to quartzy transparent cake material, can absorb and store moisture, nutrient and trace element repeatedly and the slow release that can keep easing up is put branch in a suitable place to breed, make plant vigorous, yield positive results.China is production of flowers and plants big country, and quartzy mud is the ideal material of soilless culture as flower cultivation matrix, has changed traditional earth cultivation, has improved appreciation effect and economic benefit.As novel cultivation matrix, quartzy mud mainly is that raw material develops with the water-absorbing material, is gel, have following advantage: (1) gross weight is light, and total porosity is big, the water-intake rate height, retention ability is strong, has certain elasticity and extensibility, and thermal capacity is big, heat insulating ability good.(2) nontoxic, tasteless, do not touch with one's hand, easy cleaning, clean hygiene, can be made into distinct colors, have sight preferably.(3) with low cost, be easy to make, convenient management, saved the trouble of often watering, and be not subjected to the provincialism resource limit, can large-scale production.
Chinese patent CN1626575A discloses and a kind ofly has been used to arrange flowers, grow flower and bottle is decorated educates the quartzy mud of colored illusion-colour, mainly adopts resins such as polyacrylate or polyacrylamide that high-hydroscopicity is provided, and organic solvent mill base dyestuff provides color.Chinese patent CN101747688A discloses a kind of water-based pigment preparation matter for crystal soil coloring, it is characterized in that adding in crystal soil coloring pigment powder such as carbon black, Pigment Yellow 73 188.Chinese patent CN101525458A discloses a kind of have good drawing effect and tack-free quartzy mud, mainly is to add material at high temperature such as xanthan gum and shimmering powder to be polymerized in polyvinyl alcohol solution.Chinese patent CN11772776B discloses a kind of have higher gel-strength and water-retentivity, quartzy mud that production cost is lower and preparation method thereof, prominent feature is by in the sodium hydroxide part and vinylformic acid, acrylamide, linking agent N, the mixed solution of N '-methylene-bisacrylamide and water low temperature or normal temperature under redox initiation make, and the complete drying state can absorb sole mass 24-200 water doubly down.By last analysis as can be seen, the quartzy mud of existing report does not all relate to its degradation property and mechanical property.Can be decomposed into water and carbonic acid gas after the degradation property of quartzy mud is meant degraded, can not have remnants, avoid secondary pollution fully by plant absorbing.The mechanical property of quartzy mud is meant to have certain mechanical strength after swelling, is convenient to operation, prevents cracked.
Biodegradable material is meant suitably and can show under the natural environmental condition in time limit, can be decomposed the material that becomes low molecular compound fully by microorganism (as bacterium, fungi and algae etc.).As Xylo-Mucine, polycaprolactone, polyvinyl alcohol, poly(lactic acid), chitosan, semi-lactosi, silk gum, sodium alginate and starch etc.Nano material mechanics, optics and chemically reactive with and the peculiar performance that has of special aspects such as interfacial effect, inorganic nano-particle is added the mechanical property that can improve quartzy mud in the quartzy mud.Chinese patent CN101319019A discloses a kind of preparation method with Nanometer composite hydrogel of excellent mechanical performances, has promptly adopted the inorganic nanometer powder lithium to cover soil.Its reason is that there is very strong interaction in the ion of initiator and inorganic clay sheet surfaces, cause initiator molecule closely attached to its sheet surfaces, the trigger monomer polymerization, the polymer macromolecule chain that generates is attached on the clay layer, form stable physical crosslinking gel network, this thought is equally applicable to the preparation of quartzy mud.
To sum up analyze, the quartzy mud that development has over-all propertieies such as favorable biological degradability, mechanical property and water-absorbent simultaneously is the emphasis of present quartzy mud development, and in traditional quartzy mud, introduce the hydrophilic high mol and the inorganic nanometer powder clay mineral of biological degradability, advantages such as the high-specific surface area of the biocompatibility of comprehensive utilization water-soluble polymer and high-hydrophilic, inorganic nano clay and mechanics enhancement then can realize having complementary advantages, and promote the suitability for industrialized production and the widespread use of quartzy mud.
Summary of the invention
Two key technical problems that quartzy mud quasi-solution of the present invention is determined are: design a kind of quartzy mud with good wetting ability and biological degradability, the quartzy mud of gained can absorb self 100～300 times moisture, but self degradation in the given time limit simultaneously.Next is a kind of quartzy mud with certain mechanical property and high rate of dyeing of design, and the quartzy mud of gained still can keep definite shape after absorbing moisture, do not fall apart or cracked, appearance transparent, and be easy to dyestuff in conjunction with and colour-fast.
The preparation method of quartzy mud of the present invention is that described quartzy mud can prepare under normal temperature or heating condition, and operation is few, and is easy and simple to handle, and condition is controlled, is easy to popularize.
The high-hydroscopicity degradable multiple-colour crystal mud that contains nanoclay that the present invention is prepared, by suc as formula the acrylamide monomers shown in the M1, suc as formula the sodium acrylate shown in the M2, suc as formula the linking agent N shown in the M3, N '-methylene-bisacrylamide, suc as formula the inorganic nano clay shown in the M4 (concrete) as hectorite and lithium magnesium silicate, water-soluble biological polymer M5 is (concrete as starch, Xylo-Mucine, sodium alginate, L-glutamic acid, guar gum, collagen protein, agar, semi-lactosi, Sodium salts humic acids and silk silk gum etc.) and water colo(u)r M6 (concrete as famille rose, lemon yellow, Sunset yellow, amaranth, light blue, lure red, apple green, brilliant black pigment or chocolate brown pigments) water-solublely under redox initiation system, be polymerized, described M1, M2, M3, M4, the mass percent of M5 and M6 is M1:10-25%, M2:70-86%, M3:0-2%, M4:1-10%, M5:2-5%, M6:0-1%;
Hectorite (Hectorite): [Mg
5.34Li
0.66Si
8O
20(OH)
4] Na
0.66M4
Lithium magnesium silicate (Magnesium lithium silicate): [Mg, Li]
3Si
8O
20(OH)
24H
2O
Wherein, R1, R2 are hydrogen atom, or R1 is hydrogen atom, and R2 is a sec.-propyl, or R1 is ethyl, and R2 is an ethyl;
Suc as formula the acrylamide monomers shown in the M1 is the main ingredient of the quartzy mud of preparation, is acrylamide or N-isopropylacrylamide or N, a kind of in N '-two ethyl acrylamides.
Suc as formula the sodium acrylate shown in the M2 is to be formed than neutralization in 4: 3 according to molar mass by vinylformic acid and sodium hydroxide.
Suc as formula the N shown in the M3, N '-methylene-bisacrylamide is the linking agent of the quartzy mud of preparation, is a kind of white crystalline powder, and tasteless, water absorbability is minimum, meets high temperature or high light self-crosslinkable.
Suc as formula the inorganic nano clay shown in the M4, crystal belongs to monoclinic trioctahedron type layer silicate mineral, can be dispersed in preferably in the water, hydration swelling forms translucent-transparent thixotropy gel, have very strong absorption property and ion-exchange capacity, can reach with reactions such as aliphatic amide, quaternary amines and organise, have the essence of absorption, pigment, pigment or zymin, tart up, reduce functions such as bitter taste of drug.
Has degradability suc as formula the water-soluble biological polymer shown in the M5, a kind of in starch or Xylo-Mucine or sodium alginate or L-glutamic acid or guar gum or collagen protein or agar or semi-lactosi or Sodium salts humic acids or the silk silk gum, all can obtain the homogeneous mixing solutions in the deionized water of adding certain pH value, under the natural environmental condition in certain time limit (as temperature, pH value, oxygen level and soil property etc.), can be decomposed fully by microorganism and become low molecular compound.
Suc as formula the water colo(u)r shown in the M6, for carmine or lemon yellow or Sunset yellow or amaranth or light blue or lure a kind of in red or apple green or brilliant black pigment or the chocolate brown pigments, can be used for industries such as food, medicine, makeup.
The present invention contains high-hydroscopicity degradable multiple-colour crystal mud of nanoclay and preparation method thereof, comprises the steps:
1) be M1:10-25% with inorganic nano clay M4, acrylamide monomers M1, sodium acrylate M2, water-soluble biological polymer M5, linking agent M3, water colo(u)r M6 according to mass percent, M2:70-86%, M3:0-2%, M4:1-10%, M5:2-5%, M6:0-1% successively add in the deionized water, are mixed with the aqueous solution that mass concentration is 25-45%, continue to stir 60-120min, until the mixing solutions that disperses to form homogeneous fully;
2) under the room temperature be that initiator and the catalyzer of the 0.1-5% of reaction monomers total mass joins in the mixing solutions in (1) successively, continue to stir 5-20min quality;
3) reaction mixture in (2) is poured in the aggregation container, placed 30-45 ℃ thermostat container to react 5-10h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity;
4), or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor with the direct pelletizing packing of reacted product.
According to the present invention, the preparation method of described quartzy mud is characterized in that polymerization temperature is 35～45 ℃, and aggregation container can be bar-shaped, tubulose, hollow form, bulk and spherical, and polymerization process need not nitrogen protection for opening wide system.
According to the present invention, the preparation method of described quartzy mud is characterized in that initiator is ammonium persulphate (APS) or Potassium Persulphate (KPS), and catalyzer is N, N, N ' N '-Tetramethyl Ethylene Diamine or sodium bisulfite.
Adopt the quartzy mud of method for preparing to can be used for the environmental decoration of family, flowers market and gardening etc., and seedling-wood breeding, planting trees and grass, agriculture production, ecological environment treatment, Revegetation, soil engineering field such as reclaim.
Compared with prior art, the present invention has following beneficial effect:
(1) introducing of inorganic nano clay can increase water regain on the one hand, keep certain intensity after can improving quartzy mud swelling on the other hand, and the high molecular introducing of water-soluble biological can make the degraded automatically after certain time limit of quartzy mud, avoid permanent pollution to environment, not only water-intake rate and dye uptake height of Zhi Bei quartzy mud also has certain mechanical property and biological degradability thus.
(2) preparation method is simple, easy and simple to handle, condition is controlled, it is convenient, free from environmental pollution to be easy to popularize, to manage, and has high ornamental value and industrialization promotion prospect.
(3) water regain of prepared quartzy mud and biological degradation time can be by pH value, degree of crosslinking, water-soluble biological polymer and nanoclay consumption and kinds, and reactant feeds intake and recently regulate, and appearance color can be regulated by kind of pigment.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.Should understand; these embodiment only are used to the present invention is described and are not used in and limit the scope of the invention; other any do not run counter to change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
0.5 kilogram hectorite, 3.75 kilograms of acrylamides, 18.9 kilograms of sodium acrylates, 1 kilogram of sodium alginate, 25 gram methylene-bisacrylamides, 0.2 kilogram of carmine priority are added in the deionized water, be mixed with mass concentration and be 35% the aqueous solution, continue to stir 70min, until the mixing solutions that disperses to form homogeneous fully; With 100 gram ammonium persulphate and 100mL N, N, N ' N '-Tetramethyl Ethylene Diamine join in the above-mentioned mixing solutions successively under the room temperature, continue to stir 10min; Above-mentioned reaction mixture is poured in the aggregation container, placed 40 ℃ thermostat container to react 7h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity; With the direct pelletizing packing of reacted product, or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor; Product is red after absorbing distilled water, and water absorbent rate is that 230%, 35 ℃ of dry weight uses after 10 months and can degrade down.
Embodiment 2
Successively add 0.6 kilogram lithium magnesium silicate, 4 kilograms of N-isopropylacrylamide, 20 kilograms of sodium acrylates, 1.5 kilograms of Xylo-Mucines, 30 gram methylene-bisacrylamides, 0.25 kilogram of chocolate brown pigments in the deionized water, be mixed with mass concentration and be 30% the aqueous solution, continue to stir 100min, until the mixing solutions that disperses to form homogeneous fully; With 120 gram Potassium Persulphate and 150mL N, N, N ' N '-Tetramethyl Ethylene Diamine join in the above-mentioned mixing solutions successively under the room temperature, continue to stir 15min; Above-mentioned reaction mixture is poured in the aggregation container, placed 30 ℃ thermostat container to react 10h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity; With the direct pelletizing packing of reacted product, or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor; Product is brown after absorbing distilled water, and water absorbent rate is that 168%, 35 ℃ of dry weight uses after 12 months and can degrade down.
Embodiment 3
0.8 kilogram hectorite, 3 kilograms of acrylamides, 16 kilograms of sodium acrylates, 1 kilogram of sericin, 30 gram methylene-bisacrylamides, 0.2 kilogram of lemon yellow priority are added in the deionized water, be mixed with mass concentration and be 40% the aqueous solution, continue to stir 120min, until the mixing solutions that disperses to form homogeneous fully; Under the room temperature 100 gram Potassium Persulphates and sodium bisulfite are joined in the above-mentioned mixing solutions successively, continue to stir 10min; Above-mentioned reaction mixture is poured in the aggregation container, placed 40 ℃ thermostat container to react 7h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity; With the direct pelletizing packing of reacted product, or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor; Product is yellow after absorbing distilled water, and water absorbent rate is 271% of a dry weight, and soda acid uses after 5 months and can degrade down.
Embodiment 4
0.6 kilogram lithium magnesium silicate, 3.7 kilograms of acrylamides, 16.3 kilograms of sodium acrylates, 0.4 kilogram of Sodium salts humic acids, 30 gram methylene-bisacrylamides, 0.1 kilogram of apple green priority are added in the deionized water, be mixed with mass concentration and be 30% the aqueous solution, continue to stir 80min, until the mixing solutions that disperses to form homogeneous fully; With 120 gram ammonium persulphate and 100mL N, N, N ' N '-Tetramethyl Ethylene Diamine join in the above-mentioned mixing solutions successively under the room temperature, continue to stir 10min; Above-mentioned reaction mixture is poured in the aggregation container, placed 45 ℃ thermostat container to react 5h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity; With the direct pelletizing packing of reacted product, or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor; Product is green after absorbing distilled water, and water absorbent rate is that 213%, 35 ℃ of dry weight uses after 9 months and can degrade down.
Embodiment 5
Successively add 0.8 kilogram lithium magnesium silicate, 4.5 kilograms of two ethyl acrylamides, 14.5 kilograms of sodium acrylates, 0.2 kilogram of semi-lactosi, 40 gram methylene-bisacrylamides, 0.3 kilogram of light blue in the deionized water, be mixed with mass concentration and be 30% the aqueous solution, continue to stir 70min, until the mixing solutions that disperses to form homogeneous fully; Under the room temperature 150 gram Potassium Persulphates and 100mL sodium bisulfite are joined in the above-mentioned mixing solutions successively, continue to stir 20min; Above-mentioned reaction mixture is poured in the aggregation container, placed 35 ℃ thermostat container to react 10h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity; With the direct pelletizing packing of reacted product, or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor; Product is blue after absorbing distilled water, and water absorbent rate is 286% of a dry weight, and soda acid uses after 5 months and can degrade down.
Claims (10)
1. the high-hydroscopicity degradable multiple-colour crystal mud that contains nanoclay, it is characterized in that by acrylamide monomers M1, sodium acrylate M2, linking agent N, N '-methylene-bisacrylamide M3, inorganic nano clay M4, water-soluble biological polymer M5 and water colo(u)r M6 is water-soluble is polymerized under redox initiation system, the quartzy mud of gained not only has high water absorbing capacity and dye uptake, also has certain mechanical property and biological degradability.
2. quartzy mud according to claim 1 is characterized in that described M1 is acrylamide or N-isopropylacrylamide or N, a kind of in N '-two ethyl acrylamides.
3. quartzy mud according to claim 1 is characterized in that described sodium acrylate M2 is formed than neutralization in 4: 3 according to molar mass by vinylformic acid and sodium hydroxide.
4. quartzy mud according to claim 1 is characterized in that described N, and N '-methylene-bisacrylamide M3 is the linking agent of the quartzy mud of preparation, is a kind of white crystalline powder, and tasteless, water absorbability is minimum, meets high temperature or high light self-crosslinkable.
5. quartzy mud according to claim 1, it is characterized in that described inorganic nano clay M4, crystal belongs to monoclinic trioctahedron type layer silicate mineral, can be dispersed in preferably in the water, hydration swelling forms translucent-transparent thixotropy gel has very strong absorption property and ion-exchange capacity, can reach with reactions such as aliphatic amide, quaternary amines to organise, have the essence of absorption, pigment, pigment or zymin, tart up, reduce functions such as bitter taste of drug.
6. quartzy mud according to claim 1, it is characterized in that described water-soluble biological polymer M5 has degradability, a kind of in starch or Xylo-Mucine or sodium alginate or L-glutamic acid or guar gum or collagen protein or agar or semi-lactosi or Sodium salts humic acids or the silk silk gum, all can obtain the homogeneous mixing solutions in the deionized water of adding certain pH value, under the natural environmental condition in certain time limit (as temperature, pH value, oxygen level and soil property etc.), can be decomposed fully by microorganism and become low molecular compound.
7. quartzy mud according to claim 1 is characterized in that described water colo(u)r M6, for carmine or lemon yellow or Sunset yellow or amaranth or light blue or lure a kind of in red or apple green or brilliant black pigment or the chocolate brown pigments.
8. a preparation method who contains the high-hydroscopicity degradable multiple-colour crystal mud of nanoclay as claimed in claim 1 comprises the following steps:
1) be M1:10-25% with inorganic nano clay M4, acrylamide monomers M1, sodium acrylate M2, water-soluble biological polymer M5, linking agent M3, water colo(u)r M6 according to mass percent, M2:70-86%, M3:0-2%, M4:1-10%, M5:2-5%, M6:0-1% successively add in the deionized water, are mixed with the aqueous solution that mass concentration is 25-45%, continue to stir 60-120min, until the mixing solutions that disperses to form homogeneous fully;
2) under the room temperature be that initiator and the catalyzer of the 0.1-5% of reaction monomers total mass joins in the mixing solutions in (1) successively, continue to stir 5-20min quality;
3) reaction mixture in (2) is poured in the aggregation container, placed 30-45 ℃ thermostat container to react 5-10h, promptly obtain the degradable multiple-colour crystal mud of described high-hydroscopicity;
4), or, obtain the finished product through water absorption and swelling, pelletizing, drying and packing supervisor with the direct pelletizing packing of reacted product.
9. the preparation method who contains the high-hydroscopicity degradable multiple-colour crystal mud of nanoclay according to claim 7; it is characterized in that polymerization temperature is 35～45 ℃; aggregation container can be bar-shaped, tubulose, hollow form, bulk and spherical, and polymerization process need not nitrogen protection for opening wide system.
10. the preparation method who contains the high-hydroscopicity degradable multiple-colour crystal mud of nanoclay according to claim 7, it is characterized in that described initiator is ammonium persulphate or Potassium Persulphate, catalyzer is N, N, N ' N '-Tetramethyl Ethylene Diamine or sodium bisulfite, the water regain of quartzy mud and biological degradation time can be by temperature, pH value, degree of crosslinking, water-soluble biological polymer and nanoclay consumption and kinds, and reactant feeds intake and recently regulate, and appearance color can be regulated by kind of pigment.
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| CN111548441B (en) * | 2020-06-17 | 2022-04-29 | 自然资源部第三海洋研究所 | Ink melanin nanoparticle composite gel and preparation method thereof |
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