CN114478926B - Salt-resistant super absorbent resin of water hyacinth carboxymethyl cellulose and preparation method thereof - Google Patents
Salt-resistant super absorbent resin of water hyacinth carboxymethyl cellulose and preparation method thereof Download PDFInfo
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- CN114478926B CN114478926B CN202210263339.5A CN202210263339A CN114478926B CN 114478926 B CN114478926 B CN 114478926B CN 202210263339 A CN202210263339 A CN 202210263339A CN 114478926 B CN114478926 B CN 114478926B
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- 239000011347 resin Substances 0.000 title claims abstract description 76
- 229920005989 resin Polymers 0.000 title claims abstract description 76
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 40
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 40
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 40
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 40
- 239000002250 absorbent Substances 0.000 title claims abstract description 38
- 230000002745 absorbent Effects 0.000 title claims abstract description 28
- 150000003839 salts Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 240000003826 Eichhornia crassipes Species 0.000 title 1
- 241000169203 Eichhornia Species 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 13
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 12
- 230000006378 damage Effects 0.000 abstract description 3
- 239000003337 fertilizer Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 51
- 238000010008 shearing Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 22
- 229920002678 cellulose Polymers 0.000 description 20
- 239000001913 cellulose Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 9
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 240000003183 Manihot esculenta Species 0.000 description 4
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 230000015784 hyperosmotic salinity response Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 230000004103 aerobic respiration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin and a preparation method thereof. The preparation method of the invention comprises the following steps: firstly, respectively preparing a mixed monomer solution and a water hyacinth carboxymethyl cellulose solution; then introducing nitrogen into the prepared water hyacinth carboxymethyl cellulose solution, simultaneously adding an initiator and a crosslinking agent for reaction, then adding a mixed monomer solution, stirring, sealing and standing to obtain a resin sample; finally, cutting and soaking the resin sample, drying, crushing and sieving to obtain the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin. The polymer water-absorbing resin prepared by the invention improves the degradability of the resin, solves the problem of harm caused by water hyacinth, can be hydrolyzed and fermented after being abandoned, and can be used as fertilizer, and the degraded liquid can be further treated as solid.
Description
Technical Field
The invention belongs to the technical field of water-absorbent resin preparation, and particularly relates to a salt-resistant and super-absorbent resin of water hyacinth carboxymethyl cellulose and a preparation method thereof.
Background
The super absorbent resin is a functional polymer material with a three-dimensional network structure, has extremely high water absorption performance, can absorb hundreds to thousands times of liquid exceeding the self weight, and has been widely applied to agriculture and forestry, medical and health industries, environmental protection industries and intelligent component industries due to the excellent water absorption and retention performance. The acrylic water-absorbent resin has low cost and high water absorption rate, and is widely applied. However, when a small amount of small molecular electrolyte exists in water, the water absorption rate of the resin is seriously reduced, and a large amount of electrolyte of ions or ion groups is often dissolved in a real environment solution. In addition, the traditional water-absorbent resin is not degradable, and is often treated in a landfill mode after being abandoned, so that the transportation cost is increased, and the landfill site is occupied. Therefore, development of a water absorbent resin having good salt resistance and good degradability has been desired.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin and a preparation method thereof. According to the invention, the water hyacinth carboxymethyl cellulose is used as a raw material to prepare the high molecular water-absorbing resin, and compared with the common resin, the degradability, the salt tolerance and the water-absorbing capacity of the prepared resin are obviously improved, the water hyacinth carboxymethyl cellulose can be hydrolyzed and fermented after being abandoned, the degraded liquid is used as a fertilizer, and the solid is further treated.
The technical scheme of the invention is as follows:
a preparation method of water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
(1) Adding sodium hydroxide into acrylic acid for neutralization, adding dimethylaminopropyl acrylamide, and stirring to obtain a mixed monomer solution;
(2) Mixing water hyacinth carboxymethyl cellulose with water, heating, stirring, condensing, refluxing, cooling and preserving heat to obtain water hyacinth carboxymethyl cellulose solution;
(3) Introducing nitrogen into the water hyacinth carboxymethyl cellulose solution prepared in the step (2), simultaneously adding an initiator and a crosslinking agent for reaction, adding the mixed monomer solution prepared in the step (1), stirring, sealing and standing until the system has no fluidity, and obtaining a resin sample;
(4) Cutting and soaking the resin sample prepared in the step (3), and then drying, crushing and sieving to obtain the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin.
Further, in the step (1), the neutralization degree of the neutralization is 65-75%; the concentration of the sodium hydroxide is 25-30wt%; the mass ratio of the acrylic acid to the dimethylaminopropyl acrylamide is 1: (1.5-2); the stirring speed is 200-400 r/min, and the stirring time is 0.5-1 h.
Further, in the step (2), the mass ratio of the water hyacinth carboxymethyl cellulose to the water is (1-4): (20-40); the temperature of the stirring is 80-90 ℃, the speed is 200-400 r/min, and the time is 0.5-1 h; the time of condensation reflux is 1-2 h; the cooling refers to cooling to 50-60 ℃.
Further, in the step (3), the nitrogen gas is introduced at a rate of 10 to 15mL/min.
Further, in the step (3), the initiator consists of potassium persulfate and sodium bisulfite, and the mass ratio of the potassium persulfate to the sodium bisulfite is (4-8): (1.5-3); the cross-linking agent is N, N' -methylene bisacrylamide; the mass ratio of the initiator to the crosslinking agent to the water hyacinth carboxymethyl cellulose is 0.2: (0.02-0.1) and (1-4).
Further, in the step (3), the reaction time is 1-2 h; the volume mass ratio of the mixed monomer solution to the water hyacinth carboxymethyl cellulose is (20-40 ml): 1g.
Further, in the step (3), the stirring speed is 200-400 r/min, the stirring time is 3-5 h, and the stirring temperature is 50-60 ℃; the standing time is 3 hours, and the temperature is 60 ℃.
Further, in the step (4), the shearing refers to shearing the resin sample to a length of 0.5-1 cm.
The soaking is performed by using acetone; the temperature of the drying is 50-60 ℃ and the time is 8-12 h; the sieving refers to sieving by a 50-100 mesh sieve.
The water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin prepared by the preparation method.
The water hyacinth has extremely strong reproduction capability and environmental adaptability, becomes a main external invasive species in the fresh water body, causes river blockage, causes floods, prevents underwater organisms from carrying out aerobic respiration and photosynthesis, and breaks ecological balance to cause green pollution. However, the water hyacinth is taken as a natural and easily obtained biomass material, the main body of the water hyacinth is mainly cellulose, the content of the water hyacinth is about 18 percent, and the water hyacinth is a cheap and environment-friendly renewable resource. Cellulose also contains a large amount of hydroxyl groups with polymerization capacity, has high chemical reaction activity, and can be used as a raw material for developing the super absorbent resin, so that the biodegradability of the resin can be improved, and the problem of damage of water hyacinth can be solved.
The beneficial technical effects of the invention are as follows:
(1) The invention utilizes the water hyacinth carboxymethylation cellulose to prepare the high molecular water absorbent resin, thereby solving the problem of harm caused by the water hyacinth.
(2) The invention adopts acrylic acid and dimethylaminopropyl acrylamide as monomers, utilizes the inverse polyelectrolyte effect of the zwitterionic polymer, improves the salt tolerance of the resin, has high repeated water absorption capacity of the prepared resin, and saves the use cost.
(3) Compared with the common resin, the water-absorbent resin prepared by the invention has obviously improved degradability, can be subjected to hydrolytic fermentation after being abandoned, can be used as fertilizer after being degraded, can be further treated as solid, and can realize the pollution minimization and resource maximization of the whole process by using the resin.
Detailed Description
The present invention will be specifically described with reference to examples.
Example 1:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to the neutralization degree of 65%, 20g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 0.5h at 400r/min, and mixed evenly to obtain mixed monomer solution.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 20g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature of the oil bath is raised to 90 ℃, the mixture is magnetically stirred for 0.5h at 400r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃, and the temperature is kept.
15mL/min nitrogen is introduced into the water hyacinth carboxymethylated cellulose, 0.15g of potassium persulfate and 0.05g of sodium bisulphite are added as an initiator, 0.02g of N, N' -methylene bisacrylamide are added after 10min, 20mL of mixed monomer solution is added after 10min, the mixture is stirred at 60 ℃ for 3h at 400r/min, and the mixture is sealed and placed in an oil bath at 60 ℃ for 3h until the system has no fluidity after even sealing.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 50 ℃ oven for 12 hours, crushing the dried sample, and sieving the crushed sample with a 50-mesh sieve to obtain a white powdery solid sample, namely the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin.
Example 2:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to the neutralization degree of 75%, 20g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 0.8h at 200r/min, and mixed evenly to obtain a mixed monomer solution.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 20g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature is raised to 90 ℃ by an oil bath, the mixture is magnetically stirred for 1h at 300r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃ and the temperature is kept.
Introducing nitrogen into the water hyacinth carboxymethylated cellulose at a speed of 10mL/min, adding 0.15g of potassium persulfate and 0.05g of sodium bisulphite as an initiator, adding 0.02g of N, N' -methylenebisacrylamide, adding 20mL of monomer solution after 10min, stirring at a speed of 200r/min for 4h at a temperature of 55 ℃, sealing and standing in an oil bath at a temperature of 60 ℃ until the system has no fluidity.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 50 ℃ oven for 8 hours, crushing the dried sample, and sieving the crushed sample with a 50-mesh sieve to obtain a white powdery solid sample, namely the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin.
Example 3:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to the neutralization degree of 65%, 20g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 1h at 300r/min, and mixed monomer solution is obtained after uniform mixing.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 20g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature of the oil bath is raised to 90 ℃, the mixture is continuously stirred for 0.8h at 200r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃, and the temperature is kept at the same time.
Introducing nitrogen into the water hyacinth carboxymethylated cellulose at 12mL/min, adding 0.15g of potassium persulfate and 0.05g of sodium bisulphite as an initiator, adding 0.04g of N, N' -methylenebisacrylamide, adding 20mL of monomer solution after 10min, stirring at 50 ℃ at 300r/min for 5h, sealing and standing in an oil bath at 60 ℃ until the system has no fluidity.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 50 ℃ oven for 10 hours, crushing the dried sample, and sieving the crushed sample with a 50-mesh sieve to obtain a white powdery solid sample, namely the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin.
Example 4:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with the mass fraction of 30% is added to neutralize the acrylic acid to 70%, 15g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 1h at 300r/min, and mixed monomer solution is obtained after uniform mixing.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 40g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature is raised to 80 ℃ by an oil bath, the mixture is magnetically stirred for 1h at 400r/min, the mixture is condensed and refluxed for about 2h, the temperature is reduced to 50 ℃, and the temperature is kept at the same time.
15mL/min nitrogen is introduced into the water hyacinth carboxymethylated cellulose, 0.16g of potassium persulfate and 0.04g of sodium bisulphite are added as an initiator, 0.1g of N, N' -methylene bisacrylamide is added after 10min, a single 30mL solution is added, the mixture is stirred at 60 ℃ for 3h at 400r/min, and the mixture is sealed and placed in an oil bath at 60 ℃ until the system has no fluidity after being uniformly stirred.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 55 ℃ oven for 12 hours, crushing the dried sample, and sieving the crushed sample with a 100-mesh sieve to obtain a white powdery solid sample, namely the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin.
Example 5:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
40g of acrylic acid is taken, sodium hydroxide with the mass fraction of 28% is added to neutralize the acrylic acid to 70%, 72g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 1h at 300r/min, and mixed monomer solution is obtained after uniform mixing.
The sample is prepared by using an aqueous solution polymerization method, 4g of water hyacinth carboxymethylated cellulose is mixed with 30g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature of the oil bath is raised to 85 ℃, the mixture is magnetically stirred for 0.8h at 400r/min, the mixture is condensed and refluxed for about 1.5h, the temperature is reduced to 55 ℃, and the mixture is kept at the temperature.
11mL/min nitrogen is introduced into the water hyacinth carboxymethylated cellulose, 0.15g of potassium persulfate and 0.05g of sodium bisulphite are added as an initiator, 0.04g of N, N' -methylene bisacrylamide are added after 10min, 80mL of monomer solution is added, the mixture is stirred at 60 ℃ for 3h at 400r/min, and the mixture is sealed and placed in an oil bath at 60 ℃ until the system has no fluidity after being even.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 60 ℃ oven for 12 hours, crushing the dried sample, and sieving the crushed sample with a 80-mesh sieve to obtain a white powdery solid sample, namely the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin.
Comparative example 1:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
30g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to the neutralization degree of 65%, and the mixture is continuously stirred and uniformly mixed to obtain a monomer solution.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 20g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature of the oil bath is raised to 90 ℃, the mixture is magnetically stirred for 0.5h at 400r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃, and the temperature is kept.
15mL/min nitrogen is introduced into the water hyacinth carboxymethylated cellulose, 0.15g of potassium persulfate and 0.05g of sodium bisulphite are added as an initiator, 0.02g of N, N' -methylene bisacrylamide are added after 10min, 20mL of mixed monomer solution is added after 10min, the mixture is stirred at 60 ℃ for 3h at 400r/min, and the mixture is sealed and placed in an oil bath at 60 ℃ for 3h until the system has no fluidity after even sealing.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 50 ℃ oven for 12 hours, crushing the dried sample, and sieving the crushed sample with a 50-mesh sieve to obtain a white powdery solid sample, namely the water-absorbent resin. (monomer only acrylic acid).
Comparative example 2
The preparation method of the water hyacinth carboxymethylated cellulose salt-resistant super absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to the neutralization degree of 65%, 20g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 0.5h at 400r/min, and mixed evenly to obtain mixed monomer solution.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 20g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature of the oil bath is raised to 90 ℃, the mixture is magnetically stirred for 0.5h at 400r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃, and the temperature is kept.
15mL/min nitrogen is introduced into the water hyacinth carboxymethylated cellulose, 0.15g of potassium persulfate and 0.05g of sodium bisulphite are added as an initiator, 0.01g of N, N' -methylene bisacrylamide are added after 10min, 20mL of mixed monomer solution is added after 10min, the mixture is stirred at 60 ℃ for 3h at 400r/min, and the mixture is sealed and placed in an oil bath at 60 ℃ for 3h until the system has no fluidity after even sealing.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 50 ℃ oven for 12 hours, crushing the dried sample, and sieving the crushed sample with a 50-mesh sieve to obtain a white powdery solid sample, namely the water-absorbent resin.
Comparative example 3:
the preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to 80% of neutralization degree, 20g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred for 0.5h at 400r/min, and mixed evenly to obtain mixed monomer solution.
The sample is prepared by using an aqueous solution polymerization method, 1g of water hyacinth carboxymethylated cellulose is mixed with 20g of pure water, then the mixture is put into a three-neck round bottom flask, the temperature of the oil bath is raised to 90 ℃, the mixture is magnetically stirred for 0.5h at 400r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃, and the temperature is kept.
15mL/min nitrogen is introduced into the water hyacinth carboxymethylated cellulose, 0.15g of potassium persulfate and 0.05g of sodium bisulphite are added as an initiator, 0.02g of N, N' -methylene bisacrylamide are added after 10min, 20mL of mixed monomer solution is added after 10min, the mixture is stirred at 60 ℃ for 3h at 400r/min, and the mixture is sealed and placed in an oil bath at 60 ℃ for 3h until the system has no fluidity after even sealing.
Taking out the sample, shearing the sample (shearing means shearing the resin sample until the length is 0.5-1 cm.) and washing and soaking the sample with 100mL of acetone overnight, drying the sample in a 50 ℃ oven for 12 hours, crushing the dried sample, and sieving the crushed sample with a 50-mesh sieve to obtain a white powdery solid sample, namely the water-absorbent resin.
Comparative example 4:
the preparation method of the cassava water-absorbent resin comprises the following steps:
10g of acrylic acid is taken, sodium hydroxide with mass fraction of 25% is added to neutralize the acrylic acid to the neutralization degree of 65%, 20g of dimethylaminopropyl acrylamide is added to the neutralized acrylic acid, and the mixture is continuously stirred and uniformly mixed to obtain a mixed monomer solution.
The sample is prepared by using an aqueous solution polymerization method, 1g of tapioca starch and 20g of pure water are mixed, then the mixture is put into a three-neck round bottom flask, the temperature is raised to 90 ℃ by an oil bath, the mixture is magnetically stirred for 0.5h at 400r/min, the mixture is condensed and refluxed for about 1h, the temperature is reduced to 60 ℃ and the temperature is kept.
15mL/min nitrogen is introduced into the cassava starch, 0.15g of potassium persulfate and 0.05g of sodium bisulphite are added as an initiator, 0.02g of N, N' -methylene bisacrylamide are added after 10min, 20mL of mixed monomer solution is added, the mixture is stirred for 4h at 55 ℃ at 200r/min, and the mixture is sealed and is kept in an oil bath at 60 ℃ until the system has no fluidity after being even.
Taking out the sample, shearing, washing with 100mL of acetone, soaking overnight, drying in a 50 ℃ oven, crushing, and sieving with a 50-mesh sieve to obtain a white powdery solid sample, namely the water-absorbent resin.
Test example:
comparative examples 1 to 3 and comparative example 1 to4, carrying out water absorption performance test on the resin prepared in the step 4, wherein the water absorption performance test method comprises the following steps: accurately weighing a certain amount of sample (the mass is recorded as m 1 ) In a 1L beaker, a sufficient amount of 5wt.% sodium chloride solution was added, and after standing for 24 hours, filtration was performed with a standard sieve (100 mesh), and weighing was performed again after dropping without water to obtain the resin mass after water absorption (denoted as m) 2 ). The water absorption rate Q is calculated as follows:
the water absorption rate calculation formula is shown as follows:
wherein: q is water absorption rate (g/g), m 1 M is the mass of the resin before water absorption 2 For the quality of the resin after water absorption, the resin was reused 2 times to obtain water absorption ratio 1 and water absorption ratio 2, respectively, and the record is shown in table 1 below.
TABLE 1
From table 1, it can be presumed that the resin prepared by using only acrylic acid as a monomer has a low water absorption capacity, and the resin prepared by using acrylic acid and dimethylaminopropyl acrylamide as monomers has a high water absorption capacity, which indicates that the zwitterionic polymer has an inverse polyelectrolyte effect, resulting in an improvement in salt tolerance. It is presumed from examples 1 and 2 that when the amount of the crosslinking agent is too large, the pores between the system network structures are reduced due to the too large crosslinking degree of the resin, so that molecules and ions are not likely to penetrate into the resin, and the swelling degree of the resin is limited, thereby reducing the water absorbing capacity of the resin. Comparative example 3, example 2 and example 1 are different in neutralization degree, and when the neutralization degree is low, the molecular chains among the crosslinking points are short, the three-dimensional network structure is dense, the electrostatic repulsive force between the crosslinking points and-COO-is small, and the water absorption rate is low; when the neutralization degree is 65%, the chain length of molecules among crosslinking points is moderate, the number of formed effective three-dimensional network structures is the largest, generated-COO-is increased, electrostatic repulsive force with the molecules is moderate, and the water absorption multiplying power is large; when the neutralization degree is high, the generated-COO-is more and more, the electrostatic repulsive force is gradually increased, the three-dimensional net structure becomes loose, and the water absorption rate is low. It is presumed from example 1 and comparative example 3 that the three-dimensional network structure becomes loose and the water absorption capacity is low when the degree of neutralization is high. From example 1 and comparative example 4, it can be presumed that the resin prepared from tapioca starch has a low repeated water absorption capacity.
The foregoing results illustrate the principles and principal features of the invention and the advantages of the invention. The present invention is not limited to the embodiments described above, which are merely illustrative of the principles and advantages of the present invention. The present invention is capable of numerous modifications and variations without departing from the spirit of the invention and is intended to be included within the scope of the present invention.
Claims (8)
1. The preparation method of the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin is characterized by comprising the following steps of:
(1) Adding sodium hydroxide into acrylic acid for neutralization, adding dimethylaminopropyl acrylamide, and stirring to obtain a mixed monomer solution;
(2) Mixing water hyacinth carboxymethyl cellulose with water, heating, stirring, condensing, refluxing, cooling and preserving heat to obtain water hyacinth carboxymethyl cellulose solution;
(3) Introducing nitrogen into the water hyacinth carboxymethyl cellulose solution prepared in the step (2), simultaneously adding an initiator and a crosslinking agent for reaction, adding the mixed monomer solution prepared in the step (1), stirring, sealing and standing until the system has no fluidity, and obtaining a resin sample;
(4) Cutting and soaking the resin sample prepared in the step (3), and then drying, crushing and sieving to obtain the water hyacinth carboxymethyl cellulose salt-resistant super absorbent resin;
in the step (1), the neutralization degree of the neutralization is 65-75%; the concentration of the sodium hydroxide is 25-30wt%; the mass ratio of the acrylic acid to the dimethylaminopropyl acrylamide is 1: (1.5-2); the stirring speed is 200-400 r/min, and the stirring time is 0.5-1 h;
in the step (3), the mass ratio of the initiator, the cross-linking agent and the water hyacinth carboxymethyl cellulose is 0.2: (0.02-0.1): (1-4) 。
2. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the water hyacinth carboxymethyl cellulose to the water is (1-4): (20-40); the temperature of the stirring is 80-90 ℃, the speed is 200-400 r/min, and the time is 0.5-1 h; the time of condensation reflux is 1-2 h; the cooling refers to cooling to 50-60 ℃.
3. The method according to claim 1, wherein in the step (3), the nitrogen gas is introduced at a rate of 10 to 15mL/min.
4. The preparation method according to claim 1, wherein in the step (3), the initiator consists of potassium persulfate and sodium bisulfite, and the mass ratio of the potassium persulfate to the sodium bisulfite is (4-8): (1.5-3); the cross-linking agent is N, N' -methylene bisacrylamide.
5. The method according to claim 1, wherein in the step (3), the reaction time is 1 to 2 hours; the volume mass ratio of the mixed monomer solution to the water hyacinth carboxymethyl cellulose is (20-30 ml): 1g.
6. The method according to claim 1, wherein in the step (3), the stirring speed is 200 to 400r/min, the time is 3 to 5 hours, and the temperature is 50 to 60 ℃.
7. The method of claim 1, wherein in step (4), the soaking is with acetone; the temperature of the drying is 50-60 ℃ and the time is 8-12 h; the sieving refers to sieving by a 50-100 mesh sieve.
8. A water hyacinth carboxymethyl cellulose salt-tolerant super absorbent resin prepared by the preparation method of any one of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647617A (en) * | 1985-01-19 | 1987-03-03 | Hayashikane Shipbuilding & Engineering Co., Ltd. | Water absorbent crosslinked polymer and a method of producing the same containing cellulosis fibers |
| CN1772780A (en) * | 2005-10-28 | 2006-05-17 | 中国林业科学研究院林产化学工业研究所 | Amphoteric ion high water absorption resin and its prepn |
| CN102702425A (en) * | 2012-05-22 | 2012-10-03 | 中国农业大学 | Salt-tolerant cationic super-absorbent resin and preparation method and application of salt-tolerant cationic super-absorbent resin |
| CN104693361A (en) * | 2014-12-19 | 2015-06-10 | 广东工业大学 | Method for preparing binary copolymerized water hyacinth carboxymethyl cellulose super absorbent resin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647617A (en) * | 1985-01-19 | 1987-03-03 | Hayashikane Shipbuilding & Engineering Co., Ltd. | Water absorbent crosslinked polymer and a method of producing the same containing cellulosis fibers |
| CN1772780A (en) * | 2005-10-28 | 2006-05-17 | 中国林业科学研究院林产化学工业研究所 | Amphoteric ion high water absorption resin and its prepn |
| CN102702425A (en) * | 2012-05-22 | 2012-10-03 | 中国农业大学 | Salt-tolerant cationic super-absorbent resin and preparation method and application of salt-tolerant cationic super-absorbent resin |
| CN104693361A (en) * | 2014-12-19 | 2015-06-10 | 广东工业大学 | Method for preparing binary copolymerized water hyacinth carboxymethyl cellulose super absorbent resin |
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