CN116178614A - High-hydroscopicity resin and preparation method thereof - Google Patents
High-hydroscopicity resin and preparation method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 151
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002245 particle Substances 0.000 claims abstract description 111
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 230000018044 dehydration Effects 0.000 claims abstract description 40
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 40
- 239000000725 suspension Substances 0.000 claims abstract description 37
- 238000004132 cross linking Methods 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000002612 dispersion medium Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002250 absorbent Substances 0.000 claims abstract description 17
- 230000002745 absorbent Effects 0.000 claims abstract description 16
- 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 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
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- 239000007863 gel particle Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005054 agglomeration Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- -1 sucrose fatty acid esters Chemical class 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
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- 238000010992 reflux Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 125000004386 diacrylate group Chemical group 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000003204 osmotic effect Effects 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- UZHLIYLFVKXHST-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide;dihydrochloride Chemical compound Cl.Cl.NC(=O)C(C)(C)N=NC(C)(C)C(N)=O UZHLIYLFVKXHST-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MXFQRSUWYYSPOC-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical class C=CC(=O)OCC(C)(C)COC(=O)C=C MXFQRSUWYYSPOC-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- PQSQBXGSIRXRFL-UHFFFAOYSA-N 2-methylpropanamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=O PQSQBXGSIRXRFL-UHFFFAOYSA-N 0.000 description 1
- BPAZNZINLQSFMN-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole;dihydrochloride Chemical compound Cl.Cl.CC(C)C1=NCCN1 BPAZNZINLQSFMN-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Images
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts 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)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a high water absorption resin and a preparation method thereof, comprising the following steps: uniformly mixing an acrylic acid monomer, sodium hydroxide and desalted water, adding an initiator and a cross-linking agent, and uniformly stirring to obtain a polymerization solution; stirring a surfactant, a dispersion medium and a first-stage polymerization solution to form a first suspension, carrying out first-stage polymerization, and simultaneously carrying out azeotropic dehydration to ensure that the dehydration amount reaches a first preset content; changing the high-temperature water bath into a normal-temperature water bath, adding the pre-cooling second-stage polymerization liquid, stirring to form a second suspension, performing second-stage polymerization, performing azeotropic dehydration to reach a second preset content, and performing solid-liquid separation on the second suspension to obtain agglomerated basic particles; and spraying coating liquid on the surfaces of the basic particles to carry out surface cross-linking to obtain finished particles of the super absorbent resin. The preparation method of the super absorbent resin provided by the invention effectively reduces the water content of the finished product particles and increases the particle size of the finished product particles.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a high water absorption resin and a preparation method thereof.
Background
The polymerization process of the super absorbent resin is mainly divided into an aqueous solution polymerization method and a suspension polymerization method. The super absorbent resin prepared by the method has larger specific surface area due to the characteristics of the reverse suspension polymerization process, and the liquid absorption speed is obvious compared with other process advantages. However, the inverse suspension polymerization process is more complex, the control requirement on the process condition is higher, and the production efficiency is relatively low, so that how to more efficiently prepare the super absorbent resin by adopting the inverse suspension polymerization process is a problem to be solved.
In the publication No. CN103003313A, a multistage polymerization mode is adopted, and the process route sequentially carried out by azeotropic drying, surface crosslinking and continuous phase distillation removal is finished, so that the product is finally obtained, the whole process route is complex and takes longer time, and meanwhile, the frequent adjustment of the temperature of the oil bath in the reaction kettle is involved, so that the energy utilization rate is low, and the equipment input cost is high.
In the publication No. CN101410419A, a preparation method is adopted, wherein primary particles are aggregated into large-particle-diameter water-absorbent resin particles by utilizing a water-soluble solvent after primary polymerization, and a mode of filtering and recycling aqueous gel produced by polymerization for vacuum drying is adopted in the drying process, and the filtered aqueous gel has a certain viscosity due to high water content, so that the aggregated aqueous gel particles are adhered again in the vacuum drying process, the drying effect and the particle forming effect are affected, and meanwhile, the removal of residual organic solvent is not facilitated.
Disclosure of Invention
The invention provides a high water absorption resin and a preparation method thereof, which improve the dehydration efficiency and reduce the water content in finished particles. The cross-linking strength among the agglomerated basic particles is improved, and a better agglomeration forming effect is realized, so that the particle size of the finished product particles is effectively increased.
The invention is realized by the following technical scheme.
The invention provides a preparation method of a super absorbent resin, which at least comprises the following steps:
preparing a polymerization solution: uniformly stirring and mixing an acrylic acid monomer, sodium hydroxide and desalted water, adding an initiator and a cross-linking agent, and uniformly stirring to obtain a polymerization solution, wherein the polymerization solution comprises a first-stage polymerization solution and a second-stage polymerization solution;
and (3) one-stage polymerization dehydration: stirring a surfactant, a dispersion medium and the first-stage polymerization liquid to form a first suspension, performing high-temperature water bath treatment to enable the first suspension to perform first-stage polymerization, and simultaneously performing azeotropic dehydration to enable the dehydration amount to reach a first preset content, and stopping the high-temperature water bath;
two-stage polymerization dehydration: changing a high-temperature water bath into a normal-temperature water bath, adding the pre-cooled second-stage polymerization liquid into the first suspension, stirring to form a second suspension, performing high-temperature water bath again to enable the second suspension to perform second-stage polymerization, performing azeotropic dehydration at the same time to enable the dehydration amount to reach a second preset content, stopping the high-temperature water bath, and performing solid-liquid separation on the second suspension to obtain agglomerated basic particles; and
surface cross-linking: and spraying coating liquid on the surfaces of the base particles, and heating, wherein the base particles and the coating liquid are subjected to surface cross-linking to obtain finished particles of the super absorbent resin.
In one embodiment of the invention, the addition amount of the acrylic acid monomer accounts for 25-40 wt% of the total mass of the polymerization solution, and the neutralization degree of the polymerization solution is 60-80%.
In one embodiment of the present invention, the initiator is added in an amount of 0.02wt% to 0.30wt% of the acrylic monomer.
In one embodiment of the present invention, the amount of the crosslinking agent is 0.02wt% to 0.50wt% of the amount of the acrylic monomer.
In one embodiment of the present invention, the mass ratio of the first polymerization liquid to the dispersion medium is (0.2-1.0): 1.
in an embodiment of the present invention, the period of polymerization is 20min to 60min, and the first preset content is 10wt% to 50wt%.
In one embodiment of the present invention, the mass ratio of the two-stage polymerization liquid to the dispersion medium is (0.05-0.5): 1.
in an embodiment of the present invention, the time of the two-stage polymerization is 60min to 180min, and the second preset content is 50wt% to 95wt%.
In one embodiment of the present invention, the water content of the finished particles is less than 5wt%, and the yield of particles with a particle diameter of more than 150 μm in the finished particles is more than 97.5%.
The invention also provides the super absorbent resin which is prepared by the preparation method.
The high water-absorbing resin and the preparation method thereof provided by the invention simplify the process flow and improve the heat utilization rate, thereby improving the dehydration efficiency and ensuring that the water content in finished particles is below 5wt%. The cross-linking strength among agglomerated basic particles is improved, a better agglomeration forming effect is realized, the particle agglomeration rate is effectively improved, the particle size of finished particles is improved, and the particle yield of particles larger than 150 mu m in the finished particles is more than 97.5%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a superabsorbent resin according to the present invention.
FIG. 2 is a microstructure of finished particles of the superabsorbent resin of example 1.
FIG. 3 is a microstructure of finished particles of the superabsorbent resin of example 2.
FIG. 4 is a microstructure of finished particles of the superabsorbent resin of example 3.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the present invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Referring to fig. 1, the present invention provides a method for preparing a superabsorbent resin, including but not limited to steps S10-S40.
Step S10, preparing a polymerization solution: and uniformly stirring and mixing the acrylic acid monomer, sodium hydroxide and desalted water, adding an initiator and a crosslinking agent, and uniformly stirring to obtain a polymerization solution, wherein the polymerization solution comprises a first-stage polymerization solution and a second-stage polymerization solution.
Step S20, one-stage polymerization dehydration: stirring the surfactant, the dispersion medium and the first-stage polymerization liquid to form a first suspension, carrying out high-temperature water bath treatment to enable the first suspension to carry out first-stage polymerization, and simultaneously carrying out azeotropic dehydration to enable the dehydration amount to reach a first preset content, and stopping the high-temperature water bath.
Step S30, two-stage polymerization dehydration: changing the high-temperature water bath into a normal-temperature water bath, adding the pre-cooling second-stage polymerization liquid into the first suspension, stirring to form a second suspension, carrying out high-temperature water bath again to enable the second suspension to carry out second-stage polymerization, carrying out azeotropic dehydration at the same time to enable the dehydration amount to reach a second preset content, stopping the high-temperature water bath, and carrying out solid-liquid separation on the second suspension to obtain agglomerated basic particles.
Step S40, surface crosslinking: and spraying coating liquid on the surfaces of the base particles, heating, and carrying out surface cross-linking on the base particles and the coating liquid to obtain agglomerated finished particles.
Referring to fig. 1, in step S10, in an embodiment of the present invention, the acrylic monomer is added in an amount of, for example, 25wt% to 40wt% of the total mass of the polymerization solution. After acrylic acid, sodium hydroxide and desalted water are stirred and mixed, the acrylic acid and the sodium hydroxide are subjected to acid-base neutralization reaction, and the neutralization degree of the final polymerization solution is 60% -80%, for example.
Referring to fig. 1, in step S10, in an embodiment of the present invention, the polymerization solution includes a first-stage polymerization solution and a second-stage polymerization solution, and the preparation ratio of the first-stage polymerization solution to the second-stage polymerization solution may be the same or different. In one embodiment of the invention, the concentration of the acrylic acid monomer in the first-stage polymerization solution is higher than or equal to that in the second-stage polymerization solution, and the agglomeration effect of the polymerized particles is better.
Referring to FIG. 1, in step S10, in one embodiment of the present invention, the initiator is selected from persulfate thermal initiator or azo thermal initiator, wherein the azo thermal initiator comprises one or more of 2,2 '-azobis (2-amidinopropane) dihydrochloride, 2' -azobis (2-methylpropionamide) dihydrochloride, 4 '-azobis (4-cyanovaleric acid), 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2 '-azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride or 2,2' -azobis (2-methylpropionamide) dihydrochloride, etc. In one embodiment of the present invention, the initiator is added in an amount of, for example, 0.02wt% to 0.30wt% of the acrylic monomer.
Referring to fig. 1, in step S10, in an embodiment of the present invention, the cross-linking agent is selected from one or more of polyethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol triallyl ether, dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, triethoxylated glycerol triacrylate, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylolethane triglycidyl ether, 1, 4-butanediol diglycidyl ether, N-methylene bisacrylamide, and the like. In one embodiment of the present invention, the crosslinking agent is added in an amount of, for example, 0.02wt% to 0.50wt% of the acrylic monomer.
Referring to fig. 1, in step S20, in an embodiment of the present invention, for example, a surfactant, a dispersion medium and a polymerization solution are added to a reaction kettle and stirred. Specifically, after negative pressure is pumped in the reaction kettle, a dispersing medium, a mixed solution dissolved with a surfactant and a section of polymerization solution are sequentially sucked in, stirred to form a first suspension, then the negative pressure is continuously pumped, and nitrogen is filled in the reaction kettle. After the nitrogen is filled into the reaction kettle, the oxygen content in the first suspension is greatly reduced, so that the conversion rate of the polymerized monomers can be improved. In one embodiment of the invention, the mass ratio of the first stage polymerization liquid to the dispersion medium is, for example, (0.2 to 1.0): 1, further, the mass ratio of the first stage polymerization liquid to the dispersion medium is, for example, (0.4 to 0.8): 1.
referring to fig. 1, in step S20, in an embodiment of the present invention, the dispersion medium is selected from linear alkanes such as n-hexane and n-heptane, or cycloalkanes such as cyclohexane and cyclopentane. The surfactant is, for example, one or more selected from sucrose fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, etc. having a hydrophilic-lipophilic balance (HLB value) of 1 to 6. In one embodiment of the present invention, a small amount of dispersion medium is heated to dissolve, a surfactant is added to the dissolved dispersion medium, and the addition amount of the surfactant is, for example, 0.01wt% to 2.00wt% of the mass of the dispersion medium, to form a mixed solution in which the surfactant is dissolved.
Referring to fig. 1, in step S20, in an embodiment of the present invention, after forming a first suspension, a high-temperature water bath treatment is performed to make the first suspension undergo a one-stage polymerization and simultaneously undergo azeotropic dehydration. And stopping the high-temperature water bath when the dehydration amount of the first suspension reaches a first preset content. The proportion of the mass of water evaporated at this stage to the initial mass of water in the first suspension is defined as a first preset content, which is, for example, 10% to 50% by weight. The temperature of the high-temperature water bath treatment in the whole process of the first stage polymerization is 92-97 ℃ for example, and the time of the high-temperature water bath treatment is 20-60 min for example. The first stage polymerization reaction and azeotropic dehydration are synchronously carried out, after the polymerization reaction is initiated, the stable release of polymerization heat is started, the temperature of the polymerization system gradually reaches the azeotropic temperature of water and a dispersion medium in the system, and azeotropic steam is formed. Through cyclic condensation operation, the water in the azeotropic system is separated, so that the polymerization reaction heat is effectively utilized, and the effect of removing the water in the system is achieved. In the subsequent steps, separate material drying and dewatering operations are not needed, so that extra energy consumption and time consumption are avoided, the process flow is simplified, and the production efficiency of the resin is improved.
Referring to FIG. 1, in step S30, in one embodiment of the present invention, after the first stage polymerization is completed, the high temperature water is changed to the normal temperature water, and a normal temperature circulating water bath is performed, and the temperature of the normal temperature water is, for example, less than 30 ℃, so that the temperature of the first suspension is reduced to less than 30 ℃. And adding the pre-cooling second-stage polymerization solution into the reaction kettle, and stirring to form a second suspension. Wherein the mass ratio of the added two-stage polymerization liquid to the dispersion medium is, for example, (0.05-0.5): 1, further, the mass ratio of the two-stage polymerization liquid to the dispersion medium is, for example, (0.1 to 0.4): 1. in one embodiment of the invention, the second-stage polymerization liquid is subjected to pre-cooling treatment at the temperature of-5 ℃ to 20 ℃, and the temperature of the pre-cooling treatment is 0 ℃ to 15 ℃ for example, so that the agglomeration effect of the first-stage polymerization particles and the second-stage polymerization liquid is effectively improved. After the formation of the second suspension, the second suspension was subjected to a second polymerization stage by again carrying out a high-temperature water bath while carrying out azeotropic dehydration. And stopping the high-temperature water bath when the dehydration amount reaches the second preset content. The ratio of the total mass of azeotropic distilled water in the first and second polymerization stages to the total mass of water contained in the first and second polymerization stages is defined as a second preset content, and the second preset content is, for example, 50wt% to 95wt%. The temperature of the high-temperature water bath treatment in the whole process of the second stage polymerization is 92-97 ℃ for example, and the time of the high-temperature water bath treatment is 60-180 minutes for example. And after the second-stage polymerization is finished, carrying out solid-liquid separation on the materials to obtain agglomerated basic particles.
Referring to fig. 1, in step S30, in an embodiment of the present invention, the two-stage polymerization reaction and azeotropic dehydration are performed simultaneously, and after the polymerization reaction is initiated, the polymerization heat is released steadily, and the temperature of the polymerization system gradually reaches the azeotropic temperature of the water and the dispersion medium to form azeotropic steam. Through cyclic condensation operation, the water in the azeotropic system is separated, so that the polymerization reaction heat is effectively utilized, and the effect of removing the water in the system is achieved. And the total reaction time of the first-stage polymerization and the second-stage polymerization is 2-4 h, the total dehydration amount can reach more than 90wt% of the water content in the initial system, no separate material drying and dehydration operation is needed in the subsequent steps, and after the reaction is finished, the solid-liquid separation is carried out to obtain the agglomerated base particles with the water content less than 10 wt%. And the water content of the first-stage polymerized gel particles is reduced by adopting a two-stage polymerization mode and through the pre-dehydration operation of the first-stage polymerization process, after the first-stage polymerized gel particles are contacted with the second-stage polymerized liquid, the surface layer of the first-stage polymerized gel particles can absorb part of the second-stage polymerized liquid to reach osmotic pressure balance under the action of osmotic pressure difference, so that deep cross-linking interpenetrating can be realized between molecular chains of the first-stage polymerized gel particles and the second-stage polymerized gel particles in the second-stage polymerization process, the cross-linking strength between agglomerated basic particles is higher, better agglomeration forming effect is realized, and the agglomerated particles can still keep original form without breaking even under a certain pressure state. The water bath heating is adopted to meet the temperature requirements of polymerization and azeotropic dehydration, the water bath temperature is constant in the whole polymerization process, frequent adjustment and switching of the temperature are not needed, and compared with the heating modes such as oil bath or water-oil bath alternation, the reaction process is safer and more environment-friendly, the energy utilization rate is higher, and the equipment cost of the reaction system is lower.
Referring to fig. 1, in step S40, before surface cross-linking, the base particles separated in step S30 are subjected to vacuum devolatilization treatment to remove trace dispersion medium components remained on the surfaces and inside of the base particles. On the one hand, the peculiar smell of particles caused by the residue of the dispersion medium can be removed, and on the other hand, the problem of poor surface crosslinking effect caused by the residue of the dispersion medium can be avoided. After the vacuum devolatilization treatment, coating liquid is sprayed on the surfaces of the base particles and heated, so that the base particles and the coating liquid are subjected to surface cross-linking, and the finished product particles of the agglomerated super absorbent resin are obtained. The water content in the granules is further reduced, the water content of the final finished granules can reach below 5wt%, and the granule yield of the finished granules with the particle diameter of more than 150 mu m is above 97.5%. The higher the particle content of the super absorbent resin with the particle diameter smaller than 150 mu m, the more easily dust phenomenon is formed in the use process, and the material loss is caused to a certain extent while the use environment is influenced. The super absorbent resin particles prepared by the preparation method disclosed by the invention are subjected to primary polymerization and secondary polymerization, so that deeper and efficient cross-linking interpenetrating of the particles is realized, the particle agglomeration rate is effectively improved, and the particle yield of more than 150 mu m in finished particles can reach more than 97.5%, thereby obviously reducing the generation rate of powder particles less than 150 mu m. And the surface crosslinking is performed outside the reaction kettle, so that continuous operation of surface crosslinking can be realized, the water content of finished product particles is further reduced in the heating crosslinking reaction process, the utilization rate of the polymerization reaction kettle and the energy utilization rate of the surface crosslinking are effectively improved, and the process flow is simpler and more efficient.
The technical solution of the present invention will be described in further detail below with reference to several embodiments and the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Step S10, preparing a polymerization solution: 93.1g of acrylic acid is diluted with 134.6g of desalted water, 72.0g of 50% sodium hydroxide is added dropwise in an ice-water bath under stirring to perform neutralization reaction, after the reaction is completed, 0.14g of sodium persulfate and 0.28g of polyethylene glycol 200 diacrylate are added, and a section of polymer solution 300.12g is obtained after uniform stirring.
52.0g of acrylic acid is diluted by 84.7g of desalted water, 40.3g of 50% sodium hydroxide is added dropwise in an ice-water bath under stirring to perform neutralization reaction, after the reaction is completed, 0.08g of sodium persulfate and 0.15g of polyethylene glycol 200 diacrylate are added, and after the reaction is completed, 177.23g of second-stage polymerization solution is obtained after uniform stirring.
Step S20, one-stage polymerization dehydration: 0.3g of sorbitan fatty acid ester having an HLB of 4.7 was weighed into 50g of cyclohexane, and dissolved by stirring and heating. The stirred reactor equipped with the reflux condenser was evacuated to a negative pressure, and 450g of cyclohexane, 50.3g of a cyclohexane mixed solution in which sorbitan fatty acid ester was dissolved, and 300.12g of a first-stage polymerization solution after nitrogen treatment were sequentially sucked in, followed by stirring to form a first suspension.
Sequentially carrying out negative pressure pumping and nitrogen filling operation in the reaction kettle, repeating the operation for 2 times, then starting a water bath at 95 ℃, gradually raising the temperature of a polymerization system in the kettle and initiating polymerization reaction, forming azeotropic steam in a gas phase space in the kettle, separating condensate water after reflux condensation, carrying out one-stage polymerization water bath for 35min, separating 83.3g of condensate water altogether, stopping a high-temperature water bath, switching a normal-temperature circulating water bath, and cooling the temperature in the kettle to the room temperature.
Step S30, two-stage polymerization dehydration: 177.23g of the two-stage polymerization solution was cooled to 15℃and then treated with nitrogen, followed by addition to the reaction vessel and stirring to form a second suspension. Starting a water bath at 95 ℃ again to initiate two-stage polymerization, wherein the water bath lasts for 110min, 197.2g of condensed water is separated, 280.5g of condensed water is separated after the first-stage polymerization and the second-stage polymerization, the total water content of the system is 93.3wt%, then stopping the water bath, carrying out solid-liquid separation on materials in a kettle, and carrying out vacuum devolatilization on the separated basic particles to obtain 194.8g of agglomerated basic particles, wherein the water content is 9.0wt%.
Step S40, surface crosslinking: and (3) spraying coating liquid on the surfaces of the obtained basic particles by using a coating machine, heating in an oven for 10min to finish surface crosslinking reaction, and finally obtaining 185.0g of agglomerated finished particles with the water content of 4.5wt%. The particle size distribution, measured by sieving, was 16.7%, 65.8%, 15.1%, 1.2% and 1.2% for particles > 710 μm, 710-500 μm, 500-300 μm, 300-150 μm and < 150 μm, respectively, with a particle size > 150 μm of 98.8%.
FIG. 2 is a microscopic morphology of the finished particles of the superabsorbent resin of example 1. As can be seen from FIG. 2, the finished particles of the superabsorbent resin are sparkling and transparent spherical particles, and a plurality of small particles are agglomerated to form large particles.
Example 2
Step S10, preparing a polymerization solution: 90.6g of acrylic acid is diluted by 121.6g of desalted water, 68.1g of 50% sodium hydroxide is dropwise added in an ice-water bath under stirring to perform neutralization reaction, after the reaction is completed, 0.05g of 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride and 0.23g of polyethylene glycol 400 diacrylate are added, and a first-stage polymerization solution 280.58g is obtained after uniform stirring.
49.5g of acrylic acid is diluted with 70.6g of desalted water, 37.2g of sodium hydroxide with the concentration of 50% is dropwise added in an ice-water bath while stirring for neutralization reaction, after the reaction is completed, 0.03g of 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride and 0.12g of polyethylene glycol 400 diacrylate are added, and 157.45g of two-stage polymerization solution is obtained after uniform stirring.
Step S20, one-stage polymerization dehydration: 0.4g of polyglycerin fatty acid ester with HLB of 4 is weighed into 50g of n-heptane, stirred and heated for dissolving for standby. The stirred reactor equipped with the reflux condenser was evacuated to a negative pressure, and 450g of n-heptane, 50.4g of a mixed solution of n-heptane in which polyglycerin fatty acid ester was dissolved, and 280.58g of a first-stage polymerization solution treated with nitrogen were sequentially sucked in, followed by stirring to form a first suspension.
Sequentially carrying out negative pressure pumping and nitrogen filling operation in the reaction kettle, repeating the operation for 2 times, then starting a water bath at 97 ℃, gradually raising the temperature of a polymerization system in the kettle and initiating polymerization reaction, forming azeotropic steam in a gas phase space in the kettle, separating condensate water after reflux condensation, carrying out one-stage polymerization water bath for 30min, separating 48.9g of condensate water altogether, stopping a high-temperature water bath, switching a normal-temperature circulating water bath, and cooling the temperature in the kettle to the room temperature.
Step S30, two-stage polymerization dehydration: 157.45g of the two-stage polymerization solution was cooled to 12℃and then treated with nitrogen, followed by addition to the reaction vessel and stirring to form a second suspension. Starting a water bath at 97 ℃ again to initiate two-stage polymerization, wherein the water bath lasts for 120min, 204.2g of condensed water is separated, 253.1g of condensed water is separated after the two-stage polymerization and the one-stage polymerization, the total water content of the system is 94.3wt%, then stopping the water bath, carrying out solid-liquid separation on materials in a kettle, and carrying out vacuum devolatilization on the separated basic particles to obtain 184.0g of agglomerated basic particles, wherein the water content is 7.9wt%.
Step S40, surface crosslinking: and (3) spraying coating liquid on the surfaces of the obtained basic particles by using a coating machine, heating in an oven for 10min, and finishing surface crosslinking reaction to finally obtain 176.7g of agglomerated finished particles with the water content of 4.0wt%. The particle size distribution, measured by sieving, was 11.7%, 55.3%, 27.7%, 3.2%, 2.1% for particles > 710 μm, 710-500 μm, 500-300 μm, 300-150 μm, < 150 μm, respectively, with a particle size > 150 μm of 97.9%.
FIG. 3 is a microscopic morphology of the finished particles of the superabsorbent resin of example 2. As can be seen from FIG. 3, the finished particles of the superabsorbent resin are sparkling and transparent spherical particles, and a plurality of small particles are agglomerated to form large particles.
Example 3
Step S10, preparing a polymerization solution: 200.1g of acrylic acid is diluted by 323.7g of desalted water, 165.9g of 50% sodium hydroxide is added dropwise in an ice-water bath under stirring to perform neutralization reaction, after the reaction is completed, 0.16g of potassium persulfate, 0.03g of 2,2' -azobis (2-methylpropionamide) dihydrochloride and 0.10g of ethylene glycol diglycidyl ether are added, and after uniform stirring, 689.9g of polymerization solution is obtained, and the polymerization solution is divided into two parts for use, wherein one part of polymerization solution is 400.0g, and the other part of polymerization solution is 289.9g.
Step S20, one-stage polymerization dehydration: 0.7g of sucrose fatty acid ester with HLB of 3 is weighed into 50g of cyclohexane, stirred and heated for dissolving. The stirred reactor equipped with reflux condenser was evacuated to a negative pressure, and 650g of cyclohexane, 50.7g of a cyclohexane mixed solution in which sucrose fatty acid ester was dissolved, and 400.0g of a first-stage polymerization solution after nitrogen treatment were sequentially sucked in, and stirred to form a first suspension.
Sequentially carrying out negative pressure pumping and nitrogen filling operation in the reaction kettle, repeating the operation for 2 times, then starting a water bath at 92 ℃, gradually raising the temperature of a polymerization system in the kettle and initiating polymerization reaction, forming azeotropic steam in a gas phase space in the kettle, separating condensate water after reflux condensation, carrying out one-stage polymerization water bath for 25min, separating 84.6g of condensate water altogether, stopping a high-temperature water bath, switching a normal-temperature circulating water bath, and cooling the temperature in the kettle to the room temperature.
Step S30, two-stage polymerization dehydration: 289.9g of the two-stage polymerization solution was cooled to 8℃and then treated with nitrogen, followed by addition to the reaction vessel and stirring to form a second suspension. Starting a water bath at 92 ℃ again to initiate two-stage polymerization, wherein the water bath lasts 140min, 332.3g of condensed water is separated, 416.9g of condensed water is separated after the first-stage polymerization and the second-stage polymerization, the total water content of the system is 93.9wt%, then stopping the water bath, carrying out solid-liquid separation on materials in a kettle, and carrying out vacuum devolatilization on the separated basic particles to obtain 270.3g of agglomerated basic particles, wherein the water content of the agglomerated basic particles is 9.0wt%.
Step S40, surface crosslinking: coating liquid is sprayed on the surfaces of the obtained basic particles by using a coating machine, and the surface crosslinking reaction is completed after heating for 10min in an oven, so that 272.7g of agglomerated finished particles with water content of 5.0wt% are finally obtained. The particle size distribution, measured by sieving, was 31.3%, 48.7%, 17.7%, 1.2% and 1.1% for particles > 710 μm, 710-500 μm, 500-300 μm, 300-150 μm and < 150 μm, respectively, with a particle size > 150 μm of 98.9%.
FIG. 4 is a microscopic morphology of the finished particles of the superabsorbent resin of example 3. As can be seen from FIG. 4, the finished particles of the superabsorbent resin are sparkling and transparent spherical particles, and a plurality of small particles are agglomerated to form large particles.
In summary, the invention provides a superabsorbent resin and a preparation method thereof, wherein the heat provided by a water bath and the heat of polymerization reaction are used for azeotropic dehydration while maintaining the reaction rate by synchronously carrying out polymerization and drying processes, the materials in a kettle are dried, the moisture removal proportion in a reaction system after the polymerization process is over 90wt%, the water content in finished product particles is below 5wt% after subsequent surface crosslinking, and the particle yield of > 150 μm in the finished product particles can reach over 97.5%. On the premise of ensuring the stability of the polymerization reaction, the heat of the polymerization reaction is fully utilized, the heat utilization rate is effectively improved, and a separate azeotropic drying process is not needed, so that the extra energy consumption and time consumption are avoided. After the reaction is finished, the materials are loose agglomerated particles, so that solid-liquid separation of the particles and a dispersion medium is easier, and the problem of particle adhesion in a mode of polymerizing before separating and drying is effectively avoided.
The water content of the first-stage polymerized gel particles is reduced by carrying out segmented polymerization and pre-dewatering operation in the first-stage polymerization process, after the first-stage polymerized gel particles are contacted with the second-stage polymerized liquid, the surface layer of the first-stage polymerized gel particles can absorb part of the second-stage polymerized liquid to reach osmotic pressure balance under the action of osmotic pressure difference, so that deep cross-linking interpenetrating can be realized between molecular chains of the first-stage polymerized gel particles and the second-stage polymerized gel particles in the second-stage polymerization reaction process, the cross-linking strength between agglomerated basic particles is higher, better agglomeration forming effect is realized, the particle agglomeration rate is effectively improved, the particle yield of more than 150 mu m in finished particles can reach more than 97.5%, and the agglomerated particles can still keep the original form without breaking even under a certain pressure state.
The water bath heat tracing method meets the temperature requirements of polymerization and drying, the water bath temperature is constant in the whole process, frequent adjustment and switching of the temperature are not needed, and compared with an oil bath or water-oil bath alternate heat tracing mode, the reaction process is safer and more environment-friendly, the energy utilization rate is higher, and the equipment cost of a reaction system is lower. Through carrying out the vacuum devolatilization to basic granule, can effectively get rid of the interior remaining continuous phase of granule, on the one hand can dispel the peculiar smell that leads to because of the oil phase remains, on the other hand can guarantee the effect of surface cross-linking. The continuous operation of surface crosslinking can be realized by carrying out the surface crosslinking reaction outside the reactor, the water content of the finished product particles is further reduced in the heating crosslinking reaction process, the utilization rate of the polymerization reactor and the energy utilization rate of the surface crosslinking are effectively improved, and the process flow is more concise and efficient.
The foregoing description is only illustrative of the preferred embodiments of the present application and the technical principles employed, and it should be understood by those skilled in the art that the scope of the invention in question is not limited to the specific combination of features described above, but encompasses other technical solutions which may be formed by any combination of features described above or their equivalents without departing from the inventive concept, such as the features described above and the features disclosed in the present application (but not limited to) having similar functions being interchanged.
Other technical features besides those described in the specification are known to those skilled in the art, and are not described herein in detail to highlight the innovative features of the present invention.
Claims (10)
1. The preparation method of the super absorbent resin is characterized by at least comprising the following steps:
preparing a polymerization solution: uniformly stirring and mixing an acrylic acid monomer, sodium hydroxide and desalted water, adding an initiator and a cross-linking agent, and uniformly stirring to obtain a polymerization solution, wherein the polymerization solution comprises a first-stage polymerization solution and a second-stage polymerization solution;
and (3) one-stage polymerization dehydration: stirring a surfactant, a dispersion medium and the first-stage polymerization liquid to form a first suspension, performing high-temperature water bath treatment to enable the first suspension to perform first-stage polymerization, and simultaneously performing azeotropic dehydration to enable the dehydration amount to reach a first preset content, and stopping the high-temperature water bath;
two-stage polymerization dehydration: changing a high-temperature water bath into a normal-temperature water bath, adding the pre-cooled second-stage polymerization liquid into the first suspension, stirring to form a second suspension, performing high-temperature water bath again to enable the second suspension to perform second-stage polymerization, performing azeotropic dehydration at the same time to enable the dehydration amount to reach a second preset content, stopping the high-temperature water bath, and performing solid-liquid separation on the second suspension to obtain agglomerated basic particles; and
surface cross-linking: and spraying coating liquid on the surfaces of the base particles, and heating, wherein the base particles and the coating liquid are subjected to surface cross-linking to obtain finished particles of the super absorbent resin.
2. The method for preparing a superabsorbent resin of claim 1 wherein the amount of acrylic acid monomer added is 25 to 40wt% of the total mass of the polymerization solution, and the degree of neutralization of the polymerization solution is 60 to 80%.
3. The method for producing a superabsorbent resin of claim 2 wherein the initiator is added in an amount of from 0.02% to 0.30% by weight of the acrylic monomer.
4. The method for producing a superabsorbent resin of claim 2 wherein the amount of the crosslinking agent added is 0.02 to 0.50% by weight of the amount of the acrylic acid monomer added.
5. The method for producing a superabsorbent resin according to claim 1, wherein the mass ratio of the first-stage polymerization liquid to the dispersion medium is (0.2 to 1.0): 1.
6. the method for preparing a super absorbent resin according to claim 1, wherein the period of polymerization is 20min to 60min, and the first preset content is 10wt% to 50wt%.
7. The method for producing a superabsorbent resin according to claim 1, wherein the mass ratio of the two-stage polymerization liquid to the dispersion medium is (0.05-0.5): 1.
8. the method for preparing a super absorbent resin according to claim 1, wherein the time of the two-stage polymerization is 60min to 180min, and the second preset content is 50wt% to 95wt%.
9. The method for producing a super absorbent resin according to claim 1, wherein the water content of the final particles is 5wt% or less, and the yield of particles having a particle diameter of more than 150 μm in the final particles is 97.5% or more.
10. A superabsorbent resin prepared by the method of any one of claims 1-9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210159A (en) * | 1990-04-03 | 1993-05-11 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing porous and water-absorbent resin |
| US5508381A (en) * | 1991-09-20 | 1996-04-16 | Lucky Limited | Process for preparing highly water absorbent resin |
| CN113912779A (en) * | 2021-11-01 | 2022-01-11 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Super absorbent resin and preparation method thereof |
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- 2023-03-20 CN CN202310271321.4A patent/CN116178614A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210159A (en) * | 1990-04-03 | 1993-05-11 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing porous and water-absorbent resin |
| US5508381A (en) * | 1991-09-20 | 1996-04-16 | Lucky Limited | Process for preparing highly water absorbent resin |
| CN113912779A (en) * | 2021-11-01 | 2022-01-11 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Super absorbent resin and preparation method thereof |
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