CN111793169A - High-salt-tolerance super absorbent resin and preparation process thereof - Google Patents
High-salt-tolerance super absorbent resin and preparation process thereof Download PDFInfo
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- CN111793169A CN111793169A CN202010799937.5A CN202010799937A CN111793169A CN 111793169 A CN111793169 A CN 111793169A CN 202010799937 A CN202010799937 A CN 202010799937A CN 111793169 A CN111793169 A CN 111793169A
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- 229920005989 resin Polymers 0.000 title claims abstract description 102
- 239000011347 resin Substances 0.000 title claims abstract description 102
- 239000002250 absorbent Substances 0.000 title claims abstract description 57
- 230000002745 absorbent Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000661 sodium alginate Substances 0.000 claims abstract description 46
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 46
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 46
- 238000010521 absorption reaction Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004021 humic acid Substances 0.000 claims abstract description 32
- 229920001661 Chitosan Polymers 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- -1 azobisisobutyronitrile peroxide Chemical class 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- OVARTXYXUGDZHU-UHFFFAOYSA-N 4-hydroxy-n-phenyldodecanamide Chemical compound CCCCCCCCC(O)CCC(=O)NC1=CC=CC=C1 OVARTXYXUGDZHU-UHFFFAOYSA-N 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 9
- BVVRPVFKRUVCJX-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)CO BVVRPVFKRUVCJX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 9
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 9
- 125000004386 diacrylate group Chemical group 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000005189 flocculation Methods 0.000 abstract description 4
- 230000016615 flocculation Effects 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 19
- 238000004132 cross linking Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 229920006026 co-polymeric resin Polymers 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000002700 urine Anatomy 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
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of resin, and particularly relates to a high-salt-tolerance super absorbent resin and a preparation process thereof, wherein the high-salt-tolerance super absorbent resin comprises the following raw materials in parts by mass: 5-10 parts of sodium alginate, 80-100 parts of acrylic acid, 50-60 parts of acrylamide, 20-30 parts of chitosan, 10-20 parts of diatomite, 10-20 parts of humic acid, 0.05-2.5 parts of an initiator, 0.3-5 parts of a cross-linking agent and 0.05-3 parts of an antioxidant. The preparation process of the invention directly dissolves the chitosan in the acrylic acid solution for reaction, and plays a role in neutralizing the acrylic acid, so that the acrylic acid does not need to be neutralized before the reaction, the process steps are reduced, and the production cost is reduced. The sodium alginate is utilized to improve the degradability of the resin, and the function of protecting the environment is played. The porous structure of the diatomite plays a bearing role for other raw materials, the water absorption rate of the resin is improved, and the flocculation performance of the diatomite is improved through the reaction of the diatomite and the sodium alginate.
Description
Technical Field
The invention belongs to the technical field of resin, and particularly relates to high-salt-tolerance super absorbent resin and a preparation process thereof.
Background
The super absorbent resin is a cross-linked network polymer containing a large number of strong polar groups, and is firstly prepared by adopting starch grafted polyacrylonitrile by Fanta and the like and then saponifying. From the last 60 s to date, super absorbent resins have been developed globally and can be divided into two main categories according to raw materials, wherein the first category is natural polymers such as starch and cellulose; the second type is a synthetic polymer, such as polyacrylic acid, polyoxyethylene, polyvinyl alcohol, wherein at present more than 80% of the super absorbent resin is polymerized from acrylic acid monomers.
The super absorbent resin is used as a novel functional polymer material, and has wide application in the aspects of medicine and health, agriculture, forestry, gardening, desert control and the like due to the unique water absorption and water retention performance. The reason for the water absorption of the super absorbent resin is that a large number of hydrophilic functional groups exist on the molecular chain of the super absorbent resin. These hydrophilic groups are most likely carboxyl groups, and furthermore, hydroxyl groups, amide groups, amino groups, sulfonic acid groups, phosphoric acid groups, sulfinic acid groups, and the like can be used. From the beginning of the 80 s, superabsorbent resins were used in sanitary materials as carriers for absorption of artificial body fluids. Thereafter, the demand for superabsorbent resins has risen dramatically, with 80% to 85% of the production being applied to sanitary articles as the most predominant absorbent material for human body fluids, particularly urine. The application environment of the super absorbent resin mostly contains K+、Ca2+、Na+When inorganic salt ions are used, the water absorption capacity of the resin is easily reduced by metal ions, and is generally reduced from hundreds of times to dozens of times.
At present, the super absorbent resin generally has the problems of higher synthesis industrial cost and poorer salt resistance, and the traditional super absorbent resin cannot be naturally degraded, thereby causing the problem of environmental pollution.
Disclosure of Invention
The invention aims to: the high salt-resistant super absorbent resin and the preparation process thereof have good biodegradability, high water absorption and simple preparation process.
The technical scheme of the invention is as follows: the high salt-resistant super absorbent resin comprises the following raw materials: sodium alginate, acrylic acid, acrylamide, chitosan, diatomite, humic acid, an initiator, a cross-linking agent and an antioxidant.
Preferably, the raw materials comprise the following components in mass percentage: 5-10 parts of sodium alginate, 80-100 parts of acrylic acid, 50-60 parts of acrylamide, 20-30 parts of chitosan, 10-20 parts of diatomite, 10-20 parts of humic acid, 0.05-2.5 parts of an initiator, 0.3-5 parts of a cross-linking agent and 0.05-3 parts of an antioxidant.
Preferably, the cross-linking agent is one or a mixture of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylolmethane triacrylate and sodium citrate.
Preferably, the initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
Preferably, the antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The invention also provides a preparation process of the high salt-resistant super absorbent resin, which comprises the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 60-80%, and the reaction temperature is 25-30 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B;
step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 60-90 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistance high-water-absorption resin particles;
and 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 20-30 min, taking out and drying.
Preferably, the concentration of the sodium alginate solution is 15 g/L-40 g/L.
Preferably, the drying temperature in the step 4 and the step 5 is 60-70 ℃.
Preferably, the particle size of the high salt-resistant super absorbent resin particles sieved in the step 4 is 20-100 meshes.
Preferably, the cross-linking agent is one or a mixture of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylolmethane triacrylate and sodium citrate; the initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide; the antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The invention has the beneficial effects that:
1. the chitosan is directly dissolved in the acrylic acid solution for reaction, the acrylic acid solution replaces the common solvent acetic acid solution of the common chitosan, except that the solvent acetic acid can be subtracted, the chitosan has amino groups and plays a role in neutralizing the acrylic acid, so that the acrylic acid does not need to be neutralized before the reaction, the process steps are reduced, and the production cost is reduced.
2. Acrylamide is added into acrylic acid, is a non-ionic substance and cannot be ionized in a solution, and the salt resistance of the resin is improved by utilizing the acrylamide.
3. The sodium alginate has wide source and low cost, has good degradability and biocompatibility, improves the degradability of the resin, and plays a role in protecting the environment.
4. The porous structure of the diatomite plays a bearing role for other raw materials, the water absorption rate of the resin is improved, and the flocculation performance of the diatomite is improved through the reaction of the diatomite and the sodium alginate.
5. The chitosan not only plays a role in neutralizing acrylic acid, can enhance the bridging and net capturing effects of the sodium alginate in the reaction process with the sodium alginate, improves the flocculation effect, further promotes aggregation and growth of flocs on the basis of the adsorption bridging of the chitosan by the sodium alginate, is more favorable for forming a molecular chain net structure, promotes the net capturing effect, has a certain chelating effect on metal, also has a certain adsorption effect on copper ions by the sodium alginate, and can achieve a good turbidity removal effect.
6. The cross-linking agent mainly plays a cross-linking role in a polymerization system, so that the system can form a three-dimensional network structure, when the cross-linking agent is used in an excessive amount, pores among the network structure of the system are reduced due to the excessive cross-linking degree of the resin, molecules and ions are not easy to permeate into the resin, and meanwhile, the swelling degree of the resin is limited, so that the water absorption capacity of the resin is reduced; when the dosage of the cross-linking agent is too small, the solubility of the copolymer resin is larger due to too low cross-linking degree, and the copolymer resin is not beneficial to absorbing and maintaining water, the cross-linking agent is selected in a proper amount, the mass component value is between 0.3 and 5 parts, the proportion of the cross-linking agent and other raw materials is moderate, and the water absorption rate of the resin is further improved.
7. The degree of monomer neutralization directly influences the types of hydrophilic groups on resin molecular chains and the number of charges, and further influences the water absorption capacity of the polymer. When the neutralization degree is lower, the system is acidic, which is beneficial to initiating reaction, so that the monomer conversion rate is higher, the ion concentration in the resin is reduced, the electrostatic repulsion and osmotic pressure of a network structure are reduced, the water absorption of the copolymer resin is reduced, the metal ion concentration in the copolymer resin is increased due to the excessively high neutralization degree, the water solubility of the resin is enhanced, and the stability of the resin and the improvement of the water absorption rate are also not beneficial. The neutralization degree of the chitosan and the acrylic acid is 60-80%, and the neutralization degree is proper, so that the resin stability is facilitated, and the water absorption rate is improved. When the neutralization degree of the acrylic acid is continuously increased, the water absorption performance of the resin is gradually reduced, mainly because the reaction time is too long due to the excessively high neutralization degree, the acrylic acid cannot form a high molecular polymer, meanwhile, a large amount of cations have a shielding effect on anions on molecular chains, the expansion among the molecular chains is hindered, and the water absorption performance of the product is reduced, so the optimal neutralization degree in the invention is 70%.
8. Humic acid is added into the formula, the source of the humic acid is wide, the humic acid has good biological activity and chemical activity, and the humic acidThe acid contains a large amount of-OH, -NH2And hydrophilic groups such as-O' -CO-and the like are favorable for improving the hydrophilic performance of the resin, increasing the space network structure of the resin and improving the water absorption performance of the resin.
9. After the sodium alginate and the humic acid are mixed, free hydroxyl can appear in the solution, the binding capacity to heavy metal ions is increased, the sodium alginate and the humic acid both contain carboxyl and hydroxyl, formaldehyde is added in the preparation process, the sodium alginate and the humic acid are crosslinked, and the adsorption surface area is increased, so that the water absorption effect generated by mixing the sodium alginate and the humic acid is better than the treatment effect generated by singly using the sodium alginate.
Detailed Description
The technical solution of the present invention will be described in detail with reference to specific examples.
Example 1
The high-salt-tolerance super absorbent resin comprises the following raw materials in parts by mass: 5 parts of sodium alginate, 80 parts of acrylic acid, 50 parts of acrylamide, 20 parts of chitosan, 10 parts of diatomite, 10 parts of humic acid, 0.05 part of initiator, 0.3 part of cross-linking agent and 0.05 part of antioxidant.
The cross-linking agent is one or a plurality of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate.
The initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
The antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The high-salt-resistance super absorbent resin is prepared by the following preparation process, and comprises the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 60 percent, and the reaction temperature is 25 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B; the concentration of the sodium alginate solution is 15 g/L.
Step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 60 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistant super-absorbent resin particles, wherein the drying temperature is 60 ℃; the particle size of the screened high salt-resistant high water-absorbent resin particles is 100 meshes.
And 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 20min, taking out and drying at the drying temperature of 60 ℃.
Example 2
The high-salt-tolerance super absorbent resin comprises the following raw materials in parts by mass: 10 parts of sodium alginate, 100 parts of acrylic acid, 60 parts of acrylamide, 30 parts of chitosan, 20 parts of diatomite, 15 parts of humic acid, 2.5 parts of an initiator, 5 parts of a cross-linking agent and 3 parts of an antioxidant.
The cross-linking agent is one or a plurality of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate.
The initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
The antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The high-salt-resistance super absorbent resin is prepared by the following preparation process, and comprises the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 80%, and the reaction temperature is 30 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B;
step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 90 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistance super-absorbent resin particles;
and 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 30min, taking out and drying.
The concentration of the sodium alginate solution is 15 g/L-40 g/L.
The drying temperature in the step 4 and the step 5 is 60-70 ℃.
The granularity of the high-salt-tolerance super absorbent resin particles screened in the step 4 is 90 meshes.
Example 3
The high-salt-tolerance super absorbent resin comprises the following raw materials in parts by mass: 8 parts of sodium alginate, 90 parts of acrylic acid, 55 parts of acrylamide, 25 parts of chitosan, 15 parts of diatomite, 20 parts of humic acid, 0.1 part of initiator, 0.6 part of cross-linking agent and 0.5 part of antioxidant.
The cross-linking agent is one or a plurality of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate.
The initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
The antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The high-salt-resistance super absorbent resin is prepared by the following preparation process, and comprises the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 70%, and the reaction temperature is 28 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B;
step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 70 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistance super-absorbent resin particles;
and 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 25min, taking out and drying.
The concentration of the sodium alginate solution is 20 g/L.
The drying temperature in the step 4 and the step 5 is 65 ℃.
The particle size of the high-salt-tolerance super absorbent resin sieved in the step 4 is 80 meshes.
Example 4
The high-salt-tolerance super absorbent resin comprises the following raw materials in parts by mass: 9 parts of sodium alginate, 95 parts of acrylic acid, 55 parts of acrylamide, 23 parts of chitosan, 16 parts of diatomite, 20 parts of humic acid, 2 parts of an initiator, 0.6 part of a cross-linking agent and 1 part of an antioxidant.
The cross-linking agent is one or a plurality of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate.
The initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
The antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The high-salt-resistance super absorbent resin is prepared by the following preparation process, and comprises the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 70%, and the reaction temperature is 30 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B;
step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 90 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistance super-absorbent resin particles;
and 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 30min, taking out and drying.
The concentration of the sodium alginate solution is 40 g/L.
The drying temperature in the step 4 and the step 5 is 65 ℃.
The particle size of the high-salt-tolerance super absorbent resin sieved in the step 4 is 80 meshes.
Example 5
The high-salt-tolerance super absorbent resin comprises the following raw materials in parts by mass: 6 parts of sodium alginate, 95 parts of acrylic acid, 58 parts of acrylamide, 26 parts of chitosan, 10 parts of diatomite, 15 parts of humic acid, 2 parts of an initiator, 3 parts of a cross-linking agent and 0.08 part of an antioxidant.
The cross-linking agent is one or a plurality of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate.
The initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
The antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
The high-salt-resistance super absorbent resin is prepared by the following preparation process, and comprises the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 75%, and the reaction temperature is 26 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B;
step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 75 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistance super-absorbent resin particles;
and 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 28min, taking out and drying.
The concentration of the sodium alginate solution is 30 g/L.
The drying temperature in the step 4 and the step 5 is 66 ℃.
The particle size of the high-salt-tolerance super absorbent resin screened in the step 4 is 50 meshes.
The preparation processes in embodiments 1 to 5 all add chitosan directly into the acrylic acid solution, chitosan not only plays a role in neutralizing acrylic acid, in the reaction process with sodium alginate, the bridging and net capturing effects of sodium alginate can be enhanced, the flocculation effect is improved, sodium alginate further promotes aggregation and growth of flocs on the basis of the adsorption bridging of chitosan, formation of a molecular chain network structure is facilitated, the net capturing effect is promoted, chitosan has a certain chelating effect on metal, and sodium alginate also has a certain adsorption effect on copper ions, so that a good turbidity removal effect can be achieved.
And (3) carrying out water absorption performance test on the resin in the embodiment 1-5, 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) Adding sufficient distilled water into a 1L beaker, standing for 24 hr, filtering with a standard sieve (100 mesh), weighing again when no water is dropped to obtain water-absorbed treeMass of fat (denoted m)2). The water absorption capacity Q is calculated as follows:
as shown in Table 1, Table 1 is a table of the water absorption performance data of the highly salt-resistant super absorbent resin in examples 1 to 5.
TABLE 1
| Number of times of water absorption | 1 | 2 | 3 | 4 | 5 |
| Example 1 | 89％ | 80％ | 75％ | 70％ | 60％ |
| Example 2 | 95％ | 85％ | 80％ | 75％ | 65％ |
| Example 3 | 85％ | 75％ | 70％ | 65％ | 58％ |
| Example 4 | 90％ | 85％ | 80％ | 75％ | 68％ |
| Example 5 | 92％ | 85％ | 80％ | 75％ | 65％ |
According to the data in table 1, it can be preliminarily speculated that the crosslinking agent mainly plays a crosslinking role in the polymerization system, so that the system can form a three-dimensional network structure, when the dosage of the crosslinking agent is too large, the pores among the network structure of the system are reduced due to too large crosslinking degree of the resin, molecules and ions are not easy to permeate into the resin, and meanwhile, the swelling degree of the resin is limited, so that the water absorption capacity of the resin is reduced; when the dosage of the cross-linking agent is too small, the solubility of the copolymer resin is larger due to too low cross-linking degree, which is not beneficial to the absorption and the retention of the copolymer resin on moisture.
The water absorption rate of the resin tends to increase first and then decrease with the increase of the reaction temperature. This is probably because when the reaction temperature is low, the decomposition rate of the initiator is slow, resulting in a decrease in the reaction rate, a decrease in the degree of polymerization, and further a low water absorption of the resin; however, when the reaction temperature is too high, the copolymerization rate is reduced due to the excessively fast reaction rate and the increase of chain termination and chain transfer, and a macromolecular network structure is not easily formed, so that the relative molecular mass of the polymerization product is reduced, the water solubility is increased, and the water absorption is reduced. The reaction temperatures of examples 1 to 5 were all suitable, and no significant negative effect of reducing the water absorption of the resin occurred. The water absorption rates of examples 1 to 5 were all maintained at high levels.
The degree of monomer neutralization directly influences the types of hydrophilic groups on resin molecular chains and the number of charges, and further influences the water absorption capacity of the polymer. When the neutralization degree is lower, the system is acidic, which is beneficial to initiating reaction, so that the monomer conversion rate is higher, the ion concentration in the resin is reduced, the electrostatic repulsion and osmotic pressure of a network structure are reduced, the water absorption of the copolymer resin is reduced, the metal ion concentration in the copolymer resin is increased due to the excessively high neutralization degree, the water solubility of the resin is enhanced, and the stability of the resin and the improvement of the water absorption rate are also not beneficial.
The water absorption rate of the resins in examples 1 to 5 was gradually reduced during the repeated use, but the water absorption rates of the resins in examples 1 to 5 were all 60% or more at the time of 5 th use, which indicates that the water absorption performance of the resin of the present invention was stable and the resin could be repeatedly used for many times.
A set of comparative experiments are carried out, and by taking example 5 as a reference, the high-salt-resistance high-water-absorption resin is prepared, which is different from example 5 in that the raw materials of the high-salt-resistance high-water-absorption resin do not contain humic acid, formaldehyde is not introduced into the turbid solution B in the preparation process, only nitrogen is introduced, oxygen is removed, and the other steps are the same. Table 2 is a table of water absorption performance data of the comparative experiment and the highly salt-resistant super absorbent resin in example 5.
| Example 5 | 92％ | 85％ | 80％ | 75％ | 65％ |
| Comparative experiment | 80％ | 62％ | 55％ | 48％ | 35％ |
The alginic acid molecular chain contains carboxyl and hydroxyl, is a polyanionic electrolyte, can form a chelating ligand with various metal ions, is different from a hydrophobic organic gel formed by organic molecule crosslinking of the traditional ion exchange resin, is a hydrophilic ion crosslinking gel formed by ionic bond crosslinking, can adsorb Cu2+, Co2+, Cd2+ and Zn2+ ions, and the metal ions replace Na + to form a new ion crosslinking structure.
The humic acid is an organic high-molecular polymer with more carboxyl groups, phenolic hydroxyl groups and N-and S-binding sites, so that the humic acid has acidic cation exchange performance and complexing and chelating properties as same as alginic acid, and the adsorption of the humic acid on heavy metal ions is not only cation exchange but also forms a chelating relation, so that a plurality of metal ions can be adsorbed.
After the sodium alginate and the humic acid are mixed, free hydroxyl groups can appear in the solution, the binding capacity to heavy metal ions is increased, the sodium alginate and the humic acid both contain carboxyl groups and hydroxyl groups, formaldehyde is added in the preparation process, the sodium alginate and the humic acid are crosslinked, the adsorption surface area is increased, and as can be seen from table 2, the water absorption effect generated by mixing the sodium alginate and the humic acid is better than the treatment effect generated by independently using the sodium alginate.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (10)
1. The high-salt-tolerance super absorbent resin is characterized by comprising the following raw materials: sodium alginate, acrylic acid, acrylamide, chitosan, diatomite, humic acid, an initiator, a cross-linking agent and an antioxidant.
2. The high salt-resistant super absorbent resin as claimed in claim 1, which comprises the following raw materials by mass: 5-10 parts of sodium alginate, 80-100 parts of acrylic acid, 50-60 parts of acrylamide, 20-30 parts of chitosan, 10-20 parts of diatomite, 10-20 parts of humic acid, 0.05-2.5 parts of an initiator, 0.3-5 parts of a cross-linking agent and 0.05-3 parts of an antioxidant.
3. The high-salt-resistance high-water-absorption resin as claimed in claim 1, wherein the cross-linking agent is one or more of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate.
4. The high salt resistant super absorbent resin according to claim 1, wherein said initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide.
5. The high salt-tolerant high water absorbent resin according to claim 1, wherein the antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076, and antioxidant 264.
6. A preparation process of a high salt-resistant super absorbent resin is characterized by comprising the following steps:
step 1, directly dissolving chitosan in acrylic acid to neutralize the acrylic acid, wherein the neutralization degree is 60-80%, and the reaction temperature is 25-30 ℃;
step 2, adding acrylamide and humic acid solution, stirring for 20min, and uniformly mixing to obtain a mixed solution A; slowly adding the sodium alginate solution and the diatomite, stirring for 15min at room temperature, and uniformly mixing to obtain a turbid solution B;
step 4, introducing nitrogen and formaldehyde into the turbid liquid B, removing oxygen, adding an initiator under a stirring state for polymerization reaction at the reaction temperature of 60-90 ℃, adding a cross-linking agent, uniformly mixing, and after the reaction is finished, granulating, drying, crushing and screening to obtain high-salt-resistance high-water-absorption resin particles;
and 5, soaking the high-salt-tolerance super absorbent resin particles in an antioxidant solution for 20-30 min, taking out and drying.
7. The process for preparing the high salt-resistant high water-absorbent resin according to claim 6, wherein the concentration of the sodium alginate solution is 15 g/L-40 g/L.
8. The process for preparing the high salt-resistant high water-absorbent resin according to claim 6, wherein the drying temperature in the step 4 and the step 5 is 60 ℃ to 70 ℃.
9. The process for preparing the high-salt-tolerance super absorbent resin according to claim 6, wherein the particle size of the high-salt-tolerance super absorbent resin sieved in the step 4 is 20-100 meshes.
10. The process for preparing the high-salt-tolerance high-water-absorption resin according to claim 6, wherein the cross-linking agent is one or more of N, N-methylene bisacrylamide, polyethylene glycol diacrylate, glycerol, pentaerythritol, trimethylol methane triacrylate and sodium citrate; the initiator is benzoyl peroxide or azobisisobutyronitrile peroxide or dilauroyl peroxide or di-tert-butyl peroxide; the antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, 4-hydroxydodecanoic acid anilide, antioxidant 1076 and antioxidant 264.
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| CN114409967A (en) * | 2022-01-28 | 2022-04-29 | 长江水利委员会长江科学院 | Composite water-absorbing material and preparation method and application thereof |
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| CN111793169B (en) | 2021-09-17 |
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