CN112500530A - Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof - Google Patents
Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a calcium carbonate/bagasse cellulose-based super absorbent resin and a preparation method thereof, belonging to the technical field of preparation of super absorbent resins. The invention takes bagasse and modified porous calcium carbonate as raw materials, ammonium persulfate as an initiator, N, N' -methylene bisacrylamide as a cross-linking agent, and acrylic acid and acrylamide as graft monomers, and adopts an aqueous solution polymerization grafting method to prepare the calcium carbonate/bagasse cellulose-based composite super absorbent material; under the best conditions, the water absorption multiplying power of the water absorption resin reaches more than 900 g/g, and the multiplying power of the salt (0.9wt.% NaCl) reaches more than 135 g/g, which is higher than that of the water absorption material which is industrially applied at present. And the water absorption multiplying power of the material can reach more than 300 g/g within 1 min of starting water absorption, and the salt absorption multiplying power (0.9wt.% NaCl) can reach more than 45 g/g. Due to the rapid water absorption, strong water absorption capacity and salt tolerance effect, the water-absorbing agent has wide application prospect in the fields of children and adult sanitary products, agricultural water-retaining materials and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of super absorbent resin, and particularly relates to a method for preparing calcium carbonate/bagasse cellulose-based super absorbent resin by using bagasse, a waste in sugar manufacturing, as a raw material and an inorganic porous material as an additive through aqueous solution graft polymerization.
Background
The super absorbent resin super absorbent material is a functional polymer material with a three-dimensional network structure, which can absorb and maintain hundreds to thousands of times of pure water or tens of times of normal saline by weight of the super absorbent resin super absorbent material, and is widely applied to the fields of daily use, chemical industry, light industry, medicine and health and the like, but most of the existing super absorbent materials have the related problems of high cost, poor salt tolerance, slow water absorption rate and the like. At present, the cellulose-based modified super absorbent resin which is researched more has the advantages of low cost, environmental friendliness, biocompatibility and the like. Sugarcane is a rich characteristic natural resource in Guangxi, residual bagasse after sugar pressing is rich in a large amount of cellulose, bagasse produced by sugar production from sugarcane per year exceeds 2000 million tons, a small part of the bagasse is used in the papermaking industry, and most of the bagasse is combusted, so that the resource is wasted, the environment is polluted, and therefore, the preparation of the composite super absorbent resin by utilizing the bagasse not only has economic value but also has environmental protection significance, and a new idea is improved for comprehensive utilization of the bagasse.
When the water-absorbing material components are all organic components, the gel strength, thermal stability, water retention and salt resistance after liquid absorption are poor, and the preparation cost is high. The organic-inorganic composite water-absorbing resin is obtained by modifying and compounding cheap inorganic raw materials, and various performances of the resin can be greatly improved. The modified porous calcium carbonate is added, and physical cross-linking points are introduced, so that the water-absorbing resin forms a semi-through network structure, the water-absorbing effect and salt tolerance of water absorption are increased, the gel strength after water absorption is increased, and the water-retaining property is better.
At present, most of cellulose-based super absorbent resins are produced by an aqueous solution polymerization method, wherein the aqueous solution polymerization method is a method for dissolving a monomer, an initiator and a cross-linking agent in a proper solvent under the action of light, heat, radiation and the initiator to perform polymerization reaction under a polymerization condition, and removing the solvent to obtain a polymer. The preparation of super absorbent polymers by solution polymerization is common in free radical polymerization and conforms to the general rule of free radical polymerization. The solution polymerization has the advantages of low system viscosity in the polymerization process, uniform mixing of the monomer and the polymer, easy heat transfer, controllable temperature, capability of avoiding local overheating, low cost and large-scale production. In recent years, some researches are made in China on the preparation of high water absorption materials by using an aqueous solution graft polymerization method, for example, the literature uses etherified pretreated corn straws (PTCS) as a matrix, Acrylic Acid (AA) and Acrylamide (AM) as monomers, potassium persulfate as an initiator, N, N-Methylene Bisacrylamide (MBA) as a cross-linking agent, and the aqueous solution polymerization method is adopted to prepare PTCS graft AA and AM copolymers [ PTCS-g-P (AA-co-AM) ]. The influence of synthesis conditions on the water absorption of the resin is researched, the repeated water absorption and water retention performance of the resin are examined, the maximum water absorption of the prepared super absorbent resin to distilled water and 0.9% NaCl aqueous solution is 144.04 g/g and 30.60 g/g respectively, and the repeated water absorption and water retention performance are good. (progress of the chemical industry, 2015, 1: 198-202).
Although the prior art has some researches on the water absorption and salt tolerance of the water-absorbent resin, the strength and liquid absorption rate of the resin after water absorption are not greatly improved. The inorganic calcium carbonate is added into the bagasse polymer, so that the structure of the high molecular polymer is obviously changed during polymerization, and a larger pore structure can be formed among the water-absorbent resins by changing the dosage of the calcium carbonate, so that water molecules can quickly enter the water-absorbent resins during initial water absorption; and the interpenetrating network skeleton of organic and inorganic materials improves the strength of the resin after water absorption, and has better water retention rate.
Disclosure of Invention
The invention aims to solve the problems that the water absorbing material has low water absorbing speed and poor salt resistance effect and is prepared by rich bagasse and CaCO in Guangxi3Provides a method for preparing CaCO by solution graft polymerization3The method for preparing the bagasse cellulose-based composite super absorbent resin has the advantages of simple operation, good stability, easy reaction control, low production cost and simple equipment.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention uses microwave ultrasonic to assist alkaline H2O2The cellulose-based composite super absorbent material is prepared by using cellulose extracted from bagasse as a base material, modified porous calcium carbonate as an additive, ammonium persulfate as an initiator, N, N' -methylene bisacrylamide as a cross-linking agent and acrylic acid and acrylamide as grafting monomers through an aqueous solution polymerization grafting method.
The calcium carbonate/bagasse cellulose-based super absorbent resin is prepared by the following steps:
(1) extraction of bagasse cellulose: crushing and sieving a bagasse crusher, weighing bagasse, adding 0.1 mol/L HCl, carrying out water bath at 80 ℃, carrying out suction filtration and washing until the pH is =7, adding distilled water, carrying out water bath at 80 ℃ to remove residual sugar in cane sugar, and finally drying and storing;
removing sugar, and then treating bagasse by using microwave ultrasonic-assisted alkaline hydrogen peroxide: weighing bagasse, a hydrogen peroxide solution with the mass fraction of 30%, flaky sodium hydroxide, a hydrogen peroxide stabilizer and deionized water; reacting in a computer microwave ultrasonic wave combined catalytic synthesis extraction instrument, wherein the ultrasonic power is set to 250W, the microwave power is 100-300W, the reaction is carried out at 50-80 ℃, deionized water is washed until the pH value is =7, and the cellulose extracted from bagasse is obtained after drying at 60 ℃;
(2) preparation of modified porous calcium carbonate: reacting NH4HCO3Solids and CaCl2Putting the solid into a ball milling tank, adding triethanolamine and ethanolamine, ball milling for 30-60 min, washing with deionized water, and drying at 60 ℃ to obtain porous calcium carbonate; weighing the dried porous calcium carbonate, adding a 5% methyltrimethoxysilane aqueous solution, setting the rotation speed at 500 rpm by using a magnetic device, stirring for 25 min, standing for 24 h at room temperature, finally centrifugally washing for 5 times, drying for 24 h at 100 ℃, grinding into powdery particles, and sieving with a 120-mesh sieve to obtain the modified porous calcium carbonate;
(3) polymerization reaction: weighing bagasse cellulose and modified porous calcium carbonate, adding deionized water, and introducing N with flow rate of 20 mL/min2As protective gas, gelatinizing in water bath at 65 ℃, then adding initiator ammonium persulfate, cross-linking agent N, N' -methylene bisacrylamide and acrylic acid and acrylamide partially neutralized by NaOH solution, carrying out graft polymerization reaction in water bath at 55-75 ℃ under nitrogen atmosphere to obtain CaCO3Bagasse cellulose-based super absorbent resin; the mass ratio of bagasse cellulose to acrylic acid is 1: 3-1: 5, the concentration of a NaOH solution is 1 mol/L, the molar ratio of NaOH to acrylic acid is 1:1.5, the mass ratio of bagasse cellulose to acrylamide is 1: 2-1: 4, the mass of ammonium persulfate is 1% -3% of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene bisacrylamide is 0.2% -1% of the total mass of acrylic acid and acrylamide, and the mass ratio of bagasse cellulose to modified porous calcium carbonate is 1: 0.1-1: 1.
Preferably, in the method for preparing the calcium carbonate/bagasse cellulose-based composite super absorbent resin, the raw bagasse is residue obtained by extracting sugar from a sugar mill and then mechanically dehydrating the sugar.
Preferably, in the preparation method of the calcium carbonate/bagasse cellulose-based composite super absorbent resin, the mass ratio of the bagasse cellulose to the acrylamide in the step (3) is 1: 2.
Preferably, in the method for preparing the calcium carbonate/bagasse cellulose-based composite super absorbent resin, the mass of the ammonium persulfate in the step (3) is 1.5% of the total mass of the acrylic acid and the acrylamide.
Preferably, in the method for preparing the calcium carbonate/bagasse cellulose-based composite super absorbent resin, the mass of the N, N' -methylene bisacrylamide in the step (3) is 0.5% of the total mass of the acrylic acid and the acrylamide.
Compared with the existing water-absorbing resin, the water-absorbing resin has the following beneficial effects:
(1) the invention takes the rich bagasse in Guangxi as the raw material, extracts the cellulose, opens up a channel for the utilization of the bagasse in Guangxi, and promotes the economic sustainable development of the Guangxi area; assisting alkaline H with ultrasonic microwaves2O2The bagasse is processed quickly and efficiently, lignin and hemicellulose in the bagasse can be removed in a short time, and a large number of crystallization areas in the bagasse cellulose are destroyed simultaneously, so that the bagasse cellulose is easier to modify in the subsequent process;
(2) the invention utilizes the natural activity and the cheap characteristic of rich mineral resource calcium carbonate in Guangxi, and from the perspective of molecular structure design, prepares the calcium carbonate/bagasse cellulose-based organic/inorganic interpenetrating network structure super absorbent composite material with porous structure, aims to accelerate the liquid absorption rate, improves the gel strength and the water absorption rate of the resin after absorbing water, and has important significance for promoting the sustainable development of Guangxi economy; the addition of the modified calcium carbonate enables the cross-linked resin to have more cross-linked positions, the structure of a cross-linked network can be changed by regulating the dosage of the calcium carbonate, and different from the addition of the traditional inorganic additive, the modified calcium carbonate is not formed by simply adding inorganic matters into the cross-linked resin, but is combined with acrylic acid and the like in a chemical bond mode;
(3) the aqueous solution graft polymerization is in an operation range, the viscosity of a system is low in the polymerization process, the monomers and the polymers are uniformly mixed, the heat transfer is easy, the temperature is controllable, the local overheating can be avoided, and the large-scale production can be realized;
(4) according to the calcium carbonate/bagasse cellulose-based composite super absorbent resin product produced by the invention, the water absorption capacity of the product water absorbent resin reaches over 900 g/g, the salt (0.9wt.% NaCl) absorption capacity reaches over 135 g/g, the water absorption capacity can reach over 300 g/g within 1 min of the beginning water absorption stage, the salt (0.9wt.% NaCl) absorption capacity reaches over 45 g/g, and the liquid absorption balance can be achieved within 8-12 min.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.
Example 1
(1) Extraction of bagasse cellulose: crushing and sieving a bagasse crusher, weighing bagasse, adding 0.1 mol/L HCl, carrying out water bath at 80 ℃, carrying out suction filtration and washing until the pH is =7, adding distilled water, carrying out water bath at 80 ℃ to remove residual sugar in cane sugar, and finally drying and storing;
removing sugar, and then treating bagasse by using microwave ultrasonic-assisted alkaline hydrogen peroxide: weighing 5 g of bagasse, 3 g of 30% hydrogen peroxide solution, 4.5 g of flaky sodium hydroxide, hydrogen peroxide stabilizer (0.6 g of solid EDTA powder and 0.03 g of magnesium sulfate solid powder) and 140 g of deionized water; reacting in a computer microwave ultrasonic wave combined catalytic synthesis extraction instrument, wherein the ultrasonic power is set to be 250W, the microwave power is 150W, reacting for 70 min at 60 ℃, washing with deionized water until the pH value is =7, and drying at 60 ℃ to obtain cellulose extracted from bagasse;
(2) preparation of modified porous calcium carbonate: 7.2 g of NH4HCO3Solid and 5.5 g of CaCl2Putting the solid into a 50 mL ball milling tank, adding 0.2 g of triethanolamine and 0.2 g of ethanolamine, carrying out ball milling for 50 min, washing for 3 times by deionized water, and drying at 60 ℃ to obtain the porous calcium carbonate. 2.5 g of dried porous CaCO were weighed3Adding 50 mL of 5% methyltrimethoxysilane aqueous solution, setting the rotation speed to be 500 rpm by using a magnetic device, stirring for 25 min, standing for 24 h at room temperature, finally centrifugally washing for 5 times, drying for 24 h at 100 ℃, grinding into powder particles, and sieving by using a 120-mesh sieve to obtain the modified porous calcium carbonate;
(3) polymerization reaction: 0.75 g of bagasse cellulose and a certain mass of modified porous calcium carbonate are weighed, 40 mL of deionized water is added, and N with the flow rate of 20 mL/min is introduced2As protective gas, gelatinizing for 40 min in water bath at 65 ℃, then adding initiator ammonium persulfate, cross-linking agent N, N' -methylene-bisacrylamide and using NaOH solution to partially neutralizeThe acrylic acid and the acrylamide are subjected to graft polymerization reaction for 2 hours in a water bath at 60 ℃ under nitrogen atmosphere; wherein the mass ratio of bagasse cellulose to acrylic acid is 1:3, the concentration of NaOH solution is 1 mol/L, the molar ratio of NaOH to acrylic acid is 1:1.5, the mass ratio of bagasse cellulose to acrylamide is 1:2, the mass of ammonium persulfate is 1% of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene bisacrylamide is 0.4% of the total mass of acrylic acid and acrylamide, and the mass ratio of bagasse cellulose to modified porous CaCO3The mass ratio is 1: 0.5;
the reaction can be kept stable under the operating conditions, no implosion phenomenon is generated, the product viscosity is low, and the product can be directly dried. The monomer grafting rate reaches more than 99 percent, the water absorption rate of the calcium carbonate/bagasse cellulose-based composite water-absorbent resin reaches 800 g/g, the salt absorption (0.9wt.%) rate reaches 85 g/g, the water absorption rate reaches 210 g/g in 1 min, the salt absorption (0.9wt.%) rate reaches 35 g/g, and the water absorption saturation is reached within 8 min.
Example 2
(1) Extraction of bagasse cellulose: crushing and sieving a bagasse crusher, weighing bagasse, adding 0.1 mol/L HCl, carrying out water bath at 80 ℃, carrying out suction filtration and washing until the pH is =7, adding distilled water, carrying out water bath at 80 ℃ to remove residual sugar in cane sugar, and finally drying and storing;
removing sugar, and then treating bagasse by using microwave ultrasonic-assisted alkaline hydrogen peroxide: weighing 5 g of bagasse, 3 g of 30% hydrogen peroxide solution, 4.5 g of flaky sodium hydroxide, hydrogen peroxide stabilizer (0.6 g of solid EDTA powder and 0.03 g of magnesium sulfate solid powder) and 140 g of deionized water; reacting in a computer microwave ultrasonic wave combined catalytic synthesis extraction instrument, wherein the ultrasonic power is set to be 250W, the microwave power is 200W, the reaction is carried out for 70 min at 70 ℃, deionized water is washed until the pH is =7, and the cellulose extracted from bagasse is obtained after drying at 60 ℃;
(2) preparation of modified porous calcium carbonate: 7.2 g of NH4HCO3Solid and 5.5 g of CaCl2Putting the solid into a 50 mL ball milling tank, adding 0.25 g of triethanolamine and 0.2 g of ethanolamine, ball milling for 40 min, washing for 3 times by deionized water, and drying at 60 ℃ to obtain the porous calcium carbonate. 2.5 g of dried porous CaCO were weighed3Adding 50 mL of 5% methyltrimethoxysilane aqueous solution, setting the rotation speed to be 500 rpm by using a magnetic device, stirring for 25 min, standing for 24 h at room temperature, finally centrifugally washing for 5 times, drying for 24 h at 100 ℃, grinding into powder particles, and sieving by using a 120-mesh sieve to obtain the modified porous calcium carbonate;
(3) polymerization reaction: 0.75 g of bagasse cellulose and a certain mass of modified porous calcium carbonate are weighed, 40 mL of deionized water is added, and N with the flow rate of 20 mL/min is introduced2As a protective gas, gelatinizing for 40 min in a water bath at 65 ℃, then adding an initiator ammonium persulfate, a cross-linking agent N, N' -methylene bisacrylamide and acrylic acid and acrylamide partially neutralized by using a NaOH solution, and carrying out graft polymerization reaction for 1.5 h in a nitrogen atmosphere in the water bath at 60 ℃; wherein the mass ratio of bagasse cellulose to acrylic acid is 1:4, the concentration of NaOH solution is 1 mol/L, the molar ratio of NaOH to acrylic acid is 1:1.5, the mass ratio of bagasse cellulose to acrylamide is 1:3, the mass of ammonium persulfate is 1.5 percent of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene bisacrylamide is 0.2 percent of the total mass of acrylic acid and acrylamide, and the mass ratio of bagasse cellulose to modified porous CaCO is 1:43The mass ratio is 1: 0.6;
the reaction can be kept stable under the operating conditions, no implosion phenomenon is generated, the product viscosity is low, and the product can be directly dried. The monomer grafting rate reaches more than 99 percent, the water absorption rate of the calcium carbonate/bagasse cellulose-based composite water-absorbent resin reaches 750 g/g, the salt absorption (0.9wt.%) rate reaches 95 g/g, the water absorption rate reaches 180 g/g in 1 min after the water absorption is started, and the salt absorption (0.9wt.%) rate reaches 40 g/g, so that the water absorption is saturated in 9 min.
Example 3
(1) Extraction of bagasse cellulose: crushing and sieving a bagasse crusher, weighing bagasse, adding 0.1 mol/L HCl, carrying out water bath at 80 ℃, carrying out suction filtration and washing until the pH is =7, adding distilled water, carrying out water bath at 80 ℃ to remove residual sugar in cane sugar, and finally drying and storing;
removing sugar, and then treating bagasse by using microwave ultrasonic-assisted alkaline hydrogen peroxide: weighing 5 g of bagasse, 3 g of 30% hydrogen peroxide solution, 4.5 g of flaky sodium hydroxide, hydrogen peroxide stabilizer (0.6 g of solid EDTA powder and 0.03 g of magnesium sulfate solid powder) and 140 g of deionized water; reacting in a computer microwave ultrasonic wave combined catalytic synthesis extraction instrument, wherein the ultrasonic power is set to 250W, the microwave power is 200W, the reaction is carried out for 70 min at 65 ℃, washing with deionized water until the pH value is =7, and drying at 60 ℃ to obtain cellulose extracted from bagasse;
(2) preparation of modified porous calcium carbonate: 7.2 g of NH4HCO3Solid and 5.5 g of CaCl2Putting the solid into a 50 mL ball milling tank, adding 0.2 g of triethanolamine and 0.5 g of ethanolamine, carrying out ball milling for 50 min, washing for 3 times by deionized water, and drying at 60 ℃ to obtain the porous calcium carbonate. 2.5 g of dried porous CaCO were weighed3Adding 50 mL of 5% methyltrimethoxysilane aqueous solution, setting the rotation speed to be 500 rpm by using a magnetic device, stirring for 25 min, standing for 24 h at room temperature, finally centrifugally washing for 5 times, drying for 24 h at 100 ℃, grinding into powder particles, and sieving by using a 120-mesh sieve to obtain the modified porous calcium carbonate;
(3) polymerization reaction: 0.75 g of bagasse cellulose and a certain mass of modified porous calcium carbonate are weighed, 40 mL of deionized water is added, and N with the flow rate of 20 mL/min is introduced2As a protective gas, gelatinizing for 40 min in a water bath at 65 ℃, then adding an initiator ammonium persulfate, a cross-linking agent N, N' -methylene bisacrylamide and acrylic acid and acrylamide partially neutralized by using a NaOH solution, and carrying out graft polymerization reaction for 2 h in a nitrogen atmosphere in the water bath at 65 ℃; wherein the mass ratio of bagasse cellulose to acrylic acid is 1:4, the concentration of NaOH solution is 1 mol/L, the molar ratio of NaOH to acrylic acid is 1:1.5, the mass ratio of bagasse cellulose to acrylamide is 1:2, the mass of ammonium persulfate is 1.5 percent of the total mass of acrylic acid and acrylamide, the mass of N, N' -methylene bisacrylamide is 0.5 percent of the total mass of acrylic acid and acrylamide, and the mass of bagasse cellulose and modified porous CaCO3The mass ratio is 1: 0.5;
the reaction can be kept stable under the operating conditions, no implosion phenomenon is generated, the product viscosity is low, and the product can be directly dried. The monomer grafting rate reaches more than 99 percent, the water absorption rate of the calcium carbonate/bagasse cellulose-based composite water-absorbent resin reaches 800 g/g, the salt absorption (0.9wt.%) rate reaches 135 g/g, the water absorption rate can reach 300 g/g within 1 min of the initial water absorption stage, the salt absorption (0.9wt.% NaCl) rate reaches 45 g/g, and the water absorption saturation can be reached within 11 min.
Claims (5)
1. A calcium carbonate/bagasse cellulose-based super absorbent resin is characterized by being prepared by the following steps:
(1) extraction of bagasse cellulose: crushing and sieving a bagasse crusher, weighing bagasse, adding 0.1 mol/L HCl, carrying out water bath at 80 ℃, carrying out suction filtration and washing until the pH is =7, adding distilled water, carrying out water bath at 80 ℃ to remove residual sugar in cane sugar, and finally drying and storing;
removing sugar, and then treating bagasse by using microwave ultrasonic-assisted alkaline hydrogen peroxide: weighing bagasse, a hydrogen peroxide solution with the mass fraction of 30%, flaky sodium hydroxide, a hydrogen peroxide stabilizer and deionized water; reacting in a computer microwave ultrasonic wave combined catalytic synthesis extraction instrument, wherein the ultrasonic power is set to 250W, the microwave power is 100-300W, the reaction is carried out at 50-80 ℃, deionized water is washed until the pH value is =7, and the cellulose extracted from bagasse is obtained after drying at 60 ℃;
(2) preparation of modified porous calcium carbonate: reacting NH4HCO3Solids and CaCl2Putting the solid into a ball milling tank, adding triethanolamine and ethanolamine, ball milling for 30-60 min, washing with deionized water, and drying at 60 ℃ to obtain porous calcium carbonate; weighing the dried porous calcium carbonate, adding a 5% methyltrimethoxysilane aqueous solution, setting the rotation speed at 500 rpm by using a magnetic device, stirring for 25 min, standing for 24 h at room temperature, finally centrifugally washing for 5 times, drying for 24 h at 100 ℃, grinding into powdery particles, and sieving with a 120-mesh sieve to obtain the modified porous calcium carbonate;
(3) polymerization reaction: weighing bagasse cellulose and modified porous calcium carbonate, adding deionized water, and introducing N with flow rate of 20 mL/min2As protective gas, gelatinizing in water bath at 65 ℃, then adding initiator ammonium persulfate, cross-linking agent N, N' -methylene bisacrylamide and acrylic acid and acrylamide partially neutralized by NaOH solution, carrying out graft polymerization reaction in water bath at 55-75 ℃ under nitrogen atmosphere to obtain CaCO3Bagasse cellulose-based super absorbent resin; wherein the bagasse fiberThe mass ratio of the cellulose to the acrylic acid is 1: 3-1: 5, the concentration of a NaOH solution is 1 mol/L, the molar ratio of NaOH to the acrylic acid is 1:1.5, the mass ratio of bagasse cellulose to acrylamide is 1: 2-1: 4, the mass of ammonium persulfate is 1% -3% of the total mass of the acrylic acid and the acrylamide, the mass of N, N' -methylene bisacrylamide is 0.2% -1% of the total mass of the acrylic acid and the acrylamide, and the mass ratio of the bagasse cellulose to the modified porous calcium carbonate is 1: 0.1-1: 1.
2. The calcium carbonate/bagasse cellulose-based composite super absorbent resin according to claim 1, characterized in that the raw bagasse is a residue of a sugar mill from which sugar is extracted and which is mechanically dewatered.
3. The calcium carbonate/bagasse cellulose-based composite super absorbent resin according to claim 1, characterized in that the bagasse cellulose to acrylamide mass ratio in step (3) is 1: 2.
4. The calcium carbonate/bagasse cellulose-based composite super absorbent resin according to claim 1, wherein the mass of ammonium persulfate in step (3) is 1.5% of the total mass of acrylic acid and acrylamide.
5. The calcium carbonate/bagasse cellulose-based composite super absorbent resin according to claim 1, wherein the mass of N, N' -methylene bisacrylamide in step (3) is 0.5% of the total mass of acrylic acid and acrylamide.
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| CN113462113A (en) * | 2021-06-25 | 2021-10-01 | 广西大学 | Preparation method of bagasse cellulose/polyvinyl alcohol semi-through network high water absorption material |
| CN114903804A (en) * | 2022-06-06 | 2022-08-16 | 云南白药集团健康产品有限公司 | Bagasse/calcium carbonate composite material and preparation method and application thereof |
| CN115093508A (en) * | 2022-07-14 | 2022-09-23 | 青岛蓝博环境科技有限公司 | Corn stalk cellulose sludge-based biochar-based composite super absorbent resin |
| CN115109377A (en) * | 2022-07-14 | 2022-09-27 | 青岛蓝博环境科技有限公司 | Wheat straw cellulose sludge-based biochar-based super absorbent resin |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4344224A1 (en) * | 1993-12-23 | 1995-06-29 | Stockhausen Chem Fab Gmbh | Crosslinked synthetic polymers with porous structure, high absorption rate for water, aqueous solutions and body fluids, a process for their preparation and their use for the absorption and / or retention of water and / or aqueous liquids |
| CN1760261A (en) * | 2005-10-12 | 2006-04-19 | 西南石油学院 | Nano composite water absorbing material, and preparation method |
| CN102060959A (en) * | 2010-12-03 | 2011-05-18 | 中国科学院长春应用化学研究所 | Method for preparing polyacrylic acid water-retaining agent |
| CN102633945A (en) * | 2012-05-03 | 2012-08-15 | 山东大学 | Manufacturing method of compound type super absorbent resin |
| CN103333292A (en) * | 2013-06-17 | 2013-10-02 | 海南大学 | Preparation method of bagasse high-water-absorptivity resin |
| CN104140506A (en) * | 2014-07-18 | 2014-11-12 | 武汉理工大学 | Palm fiber stem grafting ternary polymerization high-salt-resistance water-absorbent resin and preparing method thereof |
| CN104386726A (en) * | 2014-04-25 | 2015-03-04 | 广西大学 | Method for preparing vaterite type calcium carbonate microballoon through room-temperature solid-phase reaction |
| CN105399900A (en) * | 2015-12-22 | 2016-03-16 | 兰州大学 | Preparation method of superabsorbent resin |
| CN105693934A (en) * | 2016-03-10 | 2016-06-22 | 南京博星科技有限公司 | Organic-inorganic composite super absorbent polymer |
| CN106117443A (en) * | 2016-08-20 | 2016-11-16 | 蚌埠学院 | The synthetic method of the ter-polymer resin of starch graft acrylic acid acrylamide |
| CN107245127A (en) * | 2017-04-12 | 2017-10-13 | 广西民族大学 | A kind of preparation method of starch base composite high water absorption resin |
| CN107417858A (en) * | 2017-07-21 | 2017-12-01 | 南京理工大学 | A kind of preparation method of the composite high-water-absorptivresin resin comprising diatomite and cellulose |
| CN110563877A (en) * | 2019-09-29 | 2019-12-13 | 中国石油大学(华东) | preparation method of composite salt-resistant super absorbent resin |
-
2020
- 2020-10-30 CN CN202011188108.XA patent/CN112500530B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ175996A3 (en) * | 1993-12-23 | 1996-10-16 | Stockhausen Chem Fab Gmbh | Cross-linked synthetic polymers having porous structure, high speed of water, aqueous solution and body liquid absorption, process of their preparation and their application for absorption and/or water and/or aqueous liquid retention |
| DE4344224A1 (en) * | 1993-12-23 | 1995-06-29 | Stockhausen Chem Fab Gmbh | Crosslinked synthetic polymers with porous structure, high absorption rate for water, aqueous solutions and body fluids, a process for their preparation and their use for the absorption and / or retention of water and / or aqueous liquids |
| CN1760261A (en) * | 2005-10-12 | 2006-04-19 | 西南石油学院 | Nano composite water absorbing material, and preparation method |
| CN102060959A (en) * | 2010-12-03 | 2011-05-18 | 中国科学院长春应用化学研究所 | Method for preparing polyacrylic acid water-retaining agent |
| CN102633945A (en) * | 2012-05-03 | 2012-08-15 | 山东大学 | Manufacturing method of compound type super absorbent resin |
| CN103333292A (en) * | 2013-06-17 | 2013-10-02 | 海南大学 | Preparation method of bagasse high-water-absorptivity resin |
| CN104386726A (en) * | 2014-04-25 | 2015-03-04 | 广西大学 | Method for preparing vaterite type calcium carbonate microballoon through room-temperature solid-phase reaction |
| CN104140506A (en) * | 2014-07-18 | 2014-11-12 | 武汉理工大学 | Palm fiber stem grafting ternary polymerization high-salt-resistance water-absorbent resin and preparing method thereof |
| CN105399900A (en) * | 2015-12-22 | 2016-03-16 | 兰州大学 | Preparation method of superabsorbent resin |
| CN105693934A (en) * | 2016-03-10 | 2016-06-22 | 南京博星科技有限公司 | Organic-inorganic composite super absorbent polymer |
| CN106117443A (en) * | 2016-08-20 | 2016-11-16 | 蚌埠学院 | The synthetic method of the ter-polymer resin of starch graft acrylic acid acrylamide |
| CN107245127A (en) * | 2017-04-12 | 2017-10-13 | 广西民族大学 | A kind of preparation method of starch base composite high water absorption resin |
| CN107417858A (en) * | 2017-07-21 | 2017-12-01 | 南京理工大学 | A kind of preparation method of the composite high-water-absorptivresin resin comprising diatomite and cellulose |
| CN110563877A (en) * | 2019-09-29 | 2019-12-13 | 中国石油大学(华东) | preparation method of composite salt-resistant super absorbent resin |
Non-Patent Citations (6)
| Title |
|---|
| QI SHI等: "The Preparation of Calcium Carbonate Modified High Water-Absorbing", 《ADVANCED MATERIALS RESEARCH》 * |
| RUI-JIE WANG等: "Synthesis of Super Absorbent Resin from Starch/Bentonite", 《ADVANCED MATERIALS RESEARCH》 * |
| WEI LUO等: "Synthesis and Properties of Starch Grafted", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 张立颖等: "高吸水树脂介绍", 《大众科技》 * |
| 王淋靓等: "超声波辅助碱性双氧水法提取甘蔗渣纤维素最优工艺探讨", 《南方农业学报》 * |
| 马红梅等: "蔗渣纤维/高岭土/丙烯酸复合高吸水树脂的制备及性能研究", 《轻工科技》 * |
Cited By (8)
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|---|---|---|---|---|
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| CN112920332B (en) * | 2021-03-18 | 2023-03-10 | 河南工程学院 | Method for preparing green hydrogel by crosslinking of various wastes |
| CN113462113A (en) * | 2021-06-25 | 2021-10-01 | 广西大学 | Preparation method of bagasse cellulose/polyvinyl alcohol semi-through network high water absorption material |
| CN113443941A (en) * | 2021-08-13 | 2021-09-28 | 承德石油高等专科学校 | Composite water-retention slow-release fertilizer and preparation method thereof |
| CN114903804A (en) * | 2022-06-06 | 2022-08-16 | 云南白药集团健康产品有限公司 | Bagasse/calcium carbonate composite material and preparation method and application thereof |
| CN114903804B (en) * | 2022-06-06 | 2023-08-08 | 云南白药集团健康产品有限公司 | Bagasse/calcium carbonate composite material, and preparation method and application thereof |
| CN115093508A (en) * | 2022-07-14 | 2022-09-23 | 青岛蓝博环境科技有限公司 | Corn stalk cellulose sludge-based biochar-based composite super absorbent resin |
| CN115109377A (en) * | 2022-07-14 | 2022-09-27 | 青岛蓝博环境科技有限公司 | Wheat straw cellulose sludge-based biochar-based super absorbent resin |
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