CN117050350A - Preparation method and application of low-odor water-absorbent resin - Google Patents
Preparation method and application of low-odor water-absorbent resin Download PDFInfo
- Publication number
- CN117050350A CN117050350A CN202311067153.3A CN202311067153A CN117050350A CN 117050350 A CN117050350 A CN 117050350A CN 202311067153 A CN202311067153 A CN 202311067153A CN 117050350 A CN117050350 A CN 117050350A
- Authority
- CN
- China
- Prior art keywords
- absorbent resin
- solution
- acrylic acid
- crosslinked polymer
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 229920005989 resin Polymers 0.000 title claims abstract description 75
- 239000002250 absorbent Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 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 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 24
- 239000000017 hydrogel Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 238000003892 spreading Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000007872 degassing Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 40
- 230000002745 absorbent Effects 0.000 claims description 35
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229960004063 propylene glycol Drugs 0.000 claims description 16
- 239000002211 L-ascorbic acid Substances 0.000 claims description 13
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 9
- 235000013772 propylene glycol Nutrition 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 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 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 11
- 229920000247 superabsorbent polymer Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 206010021639 Incontinence Diseases 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-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
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of C08F120/06, in particular to a preparation method and application of low-odor water-absorbent resin, at least comprising the following steps: (1) Adding an internal crosslinking agent into an acrylic acid solution to prepare a monomer solution, degassing under a nitrogen atmosphere, controlling the temperature of the monomer solution, blowing nitrogen, performing nitrogen replacement when the dissolved oxygen concentration is lower than 1ppm, and adding an initiator and a reducing agent to perform polymerization reaction to generate a hydrogel crosslinked polymer; (2) Pre-breaking the hydrogel gel-like crosslinked polymer into block-like gel-like crosslinked polymer, and then breaking the block-like gel-like crosslinked polymer by a granulator, and adding a neutralizing agent in the breaking process for neutralization to obtain hydrogel particles; (3) Spreading the hydrogel particles on a metal net for drying treatment, crushing by a grinder and sieving by a sieving machine to obtain SAP basic resin particles; (4) Mixing SAP basic resin particles with a surface cross-linking agent solution, and performing secondary cross-linking treatment.
Description
Technical Field
The invention relates to the technical field of C08F120/06, in particular to a preparation method and application of a low-odor water-absorbent resin.
Background
In the field of sanitary articles such as diapers, incontinence pads and sanitary napkins, an absorber is widely used which absorbs body fluid and comprises a water absorbing agent as a constituent material, and the absorber comprises hydrophilic fibers such as pulp and a Super Absorbent Polymer (SAP) as main materials, and the water absorbing resin is known to be a crosslinked product of partially neutralized polyacrylic acid, a hydrolysate of a starch-acrylic acid graft polymer, a saponified product of a vinyl acetate-acrylic ester copolymer, a crosslinked product of an acrylonitrile copolymer, a crosslinked product of an acrylamide copolymer, a crosslinked product of a cationic monomer, or the like, and is a crosslinked polymer which contains a strongly hydrophilic group, is insoluble in water, and can absorb several tens, hundreds, or even thousands of times the weight of water.
Based on the specificity of the application field of the high water-absorbing resin, in practical application, besides the high requirements on the centrifugal water-holding rate and the pressurized water-absorbing rate of the water-absorbing resin, the odor of the water-absorbing resin is required to be strict, because the sanitary article prepared by taking the water-absorbing resin as the raw material is worn on a human body, and the thickness of the related sanitary article is gradually reduced in recent years, the content of the water-absorbing resin is higher, and the odor of the water-absorbing resin seriously influences the use experience. However, the current preparation process of the super absorbent resin cannot effectively reduce the odor of the water absorbent resin, and various deodorants and antibacterial agents are added to endow the water absorbent resin with the deodorizing function, for example, the Chinese patent application (the authorized publication number is CN 112011006B) discloses a super absorbent resin for removing the odor of adult urine and a preparation method thereof, and particularly, an adsorption material containing the deodorants and a plant type deodorants are added in the preparation process of the super absorbent resin, but the characteristic odor of the water absorbent resin cannot be eliminated.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a low-odor water absorbent resin, which obtains a water absorbent resin having reduced bad odor while securing water absorption properties of the water absorbent resin by optimizing drying conditions of hydrogel particles and conditions of secondary crosslinking treatment.
In one aspect, the present invention provides a method for preparing a low odor water absorbent resin, comprising at least the steps of:
(1) Adding an internal crosslinking agent into an acrylic acid solution to prepare a monomer solution, degassing under a nitrogen atmosphere, controlling the temperature of the monomer solution, blowing nitrogen, performing nitrogen replacement when the dissolved oxygen concentration is lower than 1ppm, and adding an initiator and a reducing agent to perform polymerization reaction to generate a hydrogel crosslinked polymer;
(2) Pre-breaking the hydrogel gel-like crosslinked polymer into block-like gel-like crosslinked polymer, and then breaking the block-like gel-like crosslinked polymer by a granulator, and adding a neutralizing agent in the breaking process for neutralization to obtain hydrogel particles;
(3) Spreading the hydrogel particles on a metal net for drying treatment, crushing by a grinder and sieving by a sieving machine to obtain SAP basic resin particles;
(4) Mixing SAP basic resin particles with a surface cross-linking agent solution, and performing secondary cross-linking treatment.
As a preferable technical scheme, the acrylic acid solution in the step (1) is an acrylic acid aqueous solution with the acrylic acid monomer concentration of 20-30wt%, preferably an acrylic acid aqueous solution with the acrylic acid monomer concentration of 26 wt%.
As a preferable technical scheme, the internal crosslinking agent in the step (1) is at least one of polyethylene glycol diacrylate, glycerol triacrylate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate; polyethylene glycol diacrylate is preferred.
Preferably, the amount of the internal crosslinking agent added in the step (1) is 0.08 to 0.12% by mass, preferably 0.1% by mass of the acrylic acid solution.
As a preferable technical scheme, the temperature of the monomer solution in the step (1) is controlled to be 8-12 ℃.
As a preferred technical scheme, the initiator in the step (1) is a peroxy initiator, preferably sodium persulfate, and the reducing agent is at least one of sodium sulfite, sodium bisulfite, ferrous sulfate and L-ascorbic acid, preferably L-ascorbic acid.
Preferably, the sodium persulfate is specifically sodium persulfate aqueous solution with the concentration of 8-12wt%, and the addition amount of the sodium persulfate aqueous solution is 0.4-0.6% of the mass of the acrylic acid solution. Preferably, the sodium persulfate is specifically a 10wt% sodium persulfate aqueous solution, and the addition amount of the sodium persulfate aqueous solution is 0.51% of the mass of the acrylic acid solution.
Preferably, the L-ascorbic acid is an L-ascorbic acid aqueous solution with the concentration of 3-6wt%, and the addition amount of the L-ascorbic acid aqueous solution is 0.03-0.05% of the mass of the acrylic acid solution. Preferably, the L-ascorbic acid is specifically an L-ascorbic acid aqueous solution with a concentration of 5wt%, and the addition amount of the L-ascorbic acid aqueous solution is 0.04% of the mass of the acrylic acid solution.
According to the preparation method provided by the invention, the acrylic acid solution, the internal crosslinking agent, the initiator and the reducing agent are controlled to carry out polymerization reaction according to the addition amount and the reaction condition, so that the reaction time and the reaction rate are effectively balanced, and the residual monomers in the hydrogel crosslinked polymer are reduced. The analysis of the reasons by the inventors is probably that under the above reaction conditions and the addition amounts, the acrylic acid monomer in the system is polymerized by the free radical generated by the initiator and the free radical active center formed by the reducing agent, so that the residual monomer in the hydrogel crosslinked polymer is reduced, the temperature of the monomer solution is too high, the polymerization reaction is severe, and the residual monomer amount is increased.
As a preferable technical scheme, the specification of the block gel-like crosslinked polymer in the step (2) is 4cm multiplied by 4cm, the neutralizing agent is sodium carbonate or sodium bicarbonate, and the addition amount of the neutralizing agent is 10-15% of the mass of the acrylic acid solution, preferably 13.11%.
According to the preparation method provided by the invention, sodium carbonate or sodium bicarbonate is added into the pre-disintegrated 4cm multiplied by 4cm block gel-like crosslinked polymer in the disintegrating process for neutralization, the addition amount of the neutralizing agent is controlled, and about 70mol% of acid groups in acrylic acid are neutralized, so that the water absorption capacity and the safety of the subsequent water absorbent resin are ensured.
As a preferable technical scheme, the temperature of the drying treatment in the step (3) is 90-180 ℃ and the time is 40-100min; preferably, the temperature of the drying treatment in the step (3) is 90-110 ℃ and the time is 80-100min.
In order to reduce the water content in the hydrogel particles, the current preparation method generally controls the drying temperature to be in the range of 120-200 ℃ in the shortest time, however, the inventor finds that the water-absorbent resin produced at the drying temperature has unpleasant characteristic smell in the actual production process, and the inventor reduces the water content in the hydrogel particles to below 3% by controlling the drying temperature to be 90-110 ℃ for 80-100min, and simultaneously effectively controls the generation of the smell of the product to obtain the water-absorbent resin with excellent smell performance, and the prolonging of the drying time can also cause the deterioration of the smell of the water-absorbent resin.
As a preferred embodiment, the particle size of the SAP base resin particles is 150-850. Mu.m.
As a preferable technical scheme, the surface cross-linking agent solution in the step (4) is composed of a surface cross-linking agent, an organic solvent and water, wherein the mass ratio of the surface cross-linking agent to the organic solvent to the water is (1-3): (10-15): 30, preferably 2:12:30.
Preferably, the surface cross-linking agent is at least one of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, and 1, 6-hexanediol diglycidyl ether, and preferably ethylene glycol diglycidyl ether. The organic solvent is at least one of ethylene glycol, 1, 2-propylene glycol and 1, 4-butanediol, and preferably 1, 2-propylene glycol. Further preferably, the 1, 2-propanediol is pharmaceutical grade 1, 2-propanediol or chromatographic grade 1, 2-propanediol.
As a preferable technical scheme, the adding amount of the surface cross-linking agent solution in the step (4) is SAP
The mass of the base resin particles is 3 to 4%, preferably 3.6%.
As a preferable technical scheme, the temperature of the secondary crosslinking treatment in the step (4) is 80-130 ℃ and the time is 40-80min; preferably, the temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 40-60min.
The preparation method provided by the invention adopts the surface cross-linking agent solution consisting of ethylene glycol diglycidyl ether, 1, 2-propanediol and water according to the mass ratio to carry out secondary cross-linking, so that the cross-linking depth and the severe caking phenomenon in the surface cross-linking process are effectively controlled, monomer residues in the water-absorbent resin product are effectively reduced, especially, the temperature of the secondary cross-linking treatment is controlled to be 80 ℃ by adopting medical grade 1, 2-propanediol or chromatographic grade 1, 2-propanediol, the time is 40-60min, the centrifugal water retention rate and the pressurized water absorption rate of the product are ensured, meanwhile, unpleasant odor generated in the water-absorbent resin finished product is effectively improved, the provided low-odor water-absorbent resin meets the actual application requirements of thin sanitary products, and the use experience of the product is improved.
Advantageous effects
1. The invention provides a preparation method of low-odor water-absorbent resin, which is characterized in that the water-absorbent resin with reduced bad odor is obtained by optimizing the drying condition of hydrogel particles and the secondary crosslinking treatment condition, and the water-absorbent property of the water-absorbent resin is ensured.
2. According to the method provided by the invention, the water content in the hydrogel particles is reduced to below 3% by controlling the temperature of the drying treatment to be 90-110 ℃ and the time to be 80-100min, and meanwhile, the odor of the product is effectively controlled, so that the water-absorbent resin with excellent odor performance is obtained.
3. The medical grade 1, 2-propylene glycol or chromatographic grade 1, 2-propylene glycol is adopted, the temperature of the secondary crosslinking treatment is controlled to be 80 ℃, the time is 40-60min, the centrifugal water retention multiplying power and the pressurized water absorption multiplying power of the product are ensured, meanwhile, unpleasant odor generated in the water absorbent resin finished product is effectively improved, the provided low-odor water absorbent resin meets the actual application requirements of thin sanitary products, and the use experience of the product is improved.
4. According to the preparation method provided by the invention, sodium carbonate or sodium bicarbonate is added into the pre-disintegrated 4cm multiplied by 4cm block gel-like crosslinked polymer in the disintegrating process for neutralization, the addition amount of the neutralizing agent is controlled, and about 70mol% of acid groups in acrylic acid are neutralized, so that the water absorption capacity and the safety of the subsequent water absorbent resin are ensured.
5. According to the preparation method provided by the invention, the acrylic acid solution, the internal crosslinking agent, the initiator and the reducing agent are controlled to carry out polymerization reaction according to the addition amount and the reaction condition, so that the reaction time and the reaction rate are effectively balanced, and the residual monomers in the hydrogel crosslinked polymer are reduced.
Detailed Description
Example 1
Example 1 of the present invention provides a method for producing a low-odor water absorbent resin, comprising the steps of:
(1) Adding an internal crosslinking agent into 4088g of acrylic acid solution to prepare monomer solution, degassing under nitrogen atmosphere, controlling the temperature of the monomer solution, blowing nitrogen, performing nitrogen substitution when the dissolved oxygen concentration is lower than 1ppm, adding an initiator and a reducing agent, and performing polymerization reaction to generate a hydrogel crosslinked polymer;
(2) Pre-breaking the hydrogel gel-like crosslinked polymer into block-like gel-like crosslinked polymer, and then breaking the block-like gel-like crosslinked polymer by a granulator, and adding a neutralizing agent in the breaking process for neutralization to obtain hydrogel particles;
(3) Spreading the hydrogel particles on a metal net for drying treatment, crushing by a grinder and sieving by a sieving machine to obtain SAP basic resin particles;
(4) 100g of SAP basic resin particles and the surface cross-linking agent solution are mixed and subjected to secondary cross-linking treatment, thus obtaining the SAP.
The acrylic acid solution in the step (1) is an acrylic acid aqueous solution with an acrylic acid monomer concentration of 26 wt%.
The internal cross-linking agent in the step (1) is polyethylene glycol diacrylate.
The addition amount of the internal crosslinking agent in the step (1) is 0.1% of the mass of the acrylic acid solution.
The temperature of the monomer solution in the step (1) is controlled to be 10 ℃.
The initiator in the step (1) is sodium persulfate, and the reducing agent is L-ascorbic acid.
The sodium persulfate is specifically sodium persulfate aqueous solution with the concentration of 10 weight percent, the addition amount of the sodium persulfate aqueous solution is 0.51 percent of the mass of the acrylic acid solution,
the L-ascorbic acid is specifically an L-ascorbic acid aqueous solution with the concentration of 5 weight percent, and the addition amount of the L-ascorbic acid aqueous solution is 0.04 percent of the mass of the acrylic acid solution.
The specification of the block gel-like crosslinked polymer in the step (2) is 4cm multiplied by 4cm, the neutralizer is sodium bicarbonate, and the addition amount of the neutralizer is 13.11% of the mass of the acrylic acid solution.
The temperature of the drying treatment in the step (3) is 90 ℃ and the time is 100min.
The particle size of the SAP base resin particles is 150-850 mu m.
The surface cross-linking agent solution in the step (4) consists of a surface cross-linking agent, an organic solvent and water, wherein the mass ratio of the surface cross-linking agent to the organic solvent to the water is 2:12:30.
The surface cross-linking agent is ethylene glycol diglycidyl ether. The organic solvent is 1, 2-propylene glycol. The 1, 2-propylene glycol is medical grade 1, 2-propylene glycol.
The addition amount of the surface cross-linking agent solution in the step (4) is 3.6% of the mass of the SAP base resin particles.
The temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 40min.
Example 2
Example 2 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the drying treatment in the step (3) is 110 ℃ and the time is 80min.
Example 3
Example 3 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 60min.
Comparative example 1
Comparative example 1 of the present invention provides a method for preparing a low odor water absorbent resin, which is different from example 1 in specific embodiments thereof in that: the temperature of the drying treatment in the step (3) is 140 ℃ and the time is 40min.
Comparative example 2
Comparative example 2 of the present invention provides a method for preparing a low odor water absorbent resin, which is different from example 1 in specific embodiments thereof in that: the temperature of the drying treatment in the step (3) is 160 ℃ and the time is 40min.
Comparative example 3
Comparative example 3 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the drying treatment in the step (3) is 90 ℃ and the time is 120min.
Comparative example 4
Comparative example 4 of the present invention provides a method for preparing a low odor water absorbent resin, which is different from example 1 in specific embodiment in that: the temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 20min.
Comparative example 5
Comparative example 5 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 80min.
Comparative example 6
Comparative example 6 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 100min.
Comparative example 7
Comparative example 7 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the secondary crosslinking treatment in the step (4) is 80 ℃ and the time is 120min.
Comparative example 8
Comparative example 8 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: the temperature of the secondary crosslinking treatment in the step (4) is 130 ℃ and the time is 40min.
Comparative example 9
Comparative example 9 of the present invention provides a method for producing a low-odor water absorbent resin, which differs from example 1 in that: there is no step (4).
Comparative example 10
Comparative example 10 of the present invention provides a method for preparing a low odor water absorbent resin, which is different from example 1 in the specific embodiment thereof in that: the 1, 2-propanediol is technical grade 1, 2-propanediol.
Performance test method
1. Centrifugal water retention ratio (CRC): 0.20g of a water-absorbent resin was weighed and the recording weight was W 0 (g) Placing the above materials into cloth bag made of nonwoven fabric, sealing, and soaking in physiological saline solution at 25+ -2deg.C. After 30 minutes, the bag containing the water-absorbent resin was taken out of the saline solution. Dewatering at 250G for 3 min with a centrifuge, and weighing to obtain weight W 2 (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite Measuring the weight W of the bag after a similar operation without using any water-absorbing agent 1 (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite The centrifuge retention capacity (g/g) was calculated according to the following formula, and the results are shown in Table 1.
Centrifugal water retention multiplying power (g/g) = ((W) 2 (g)-W 1 (g))/W 0 (g))-1。
2. Pressurized water absorption capacity (AUP): the weighed sample was spread on a filter screen, covering the bottom of a special cylinder, starting with a uniform pressure (0.7 kPa) applied to the test sample, and the cylinder was placed in a petri dish filled with aqueous sodium chloride. After 1 hour of sample absorption, the cylinder was removed and the amount of absorbed liquid was measured as follows:
0.900g of a water-absorbent resin was weighed and the recording weight was W 3 (g) Spreading on a dry plexiglas cylindrical filter screen to make it uniformly distributed. The piston was placed on the cylinder and the whole set of cylinders was weighed and recorded as W 4 (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite Placing a filter plate on120 ml of 0.9% strength by mass aqueous sodium chloride solution was added to the dish to submerge the surface of the aluminum plate. The round filter paper is put on a filter plate and is completely wetted by sodium chloride aqueous solution, so that bubbles on the surface are avoided. The whole set of cylinder equipment was placed on the soaked filter paper and after 1 hour of placement, the sample was allowed to fully absorb the aqueous sodium chloride solution. Lifting the whole set and removing its piston, reweighing the cylinder device, recorded as W 5 (g) A. The invention relates to a method for producing a fibre-reinforced plastic composite The Absorbency Under Pressure (AUP) was calculated according to the following formula, and the results are shown in Table 1.
Pressurized water absorption capacity (g/g) = (W) 5 (g)-W 4 (g))/W 3 (g)-1。
3. Odor test, weighing 5g of low odor water-absorbing resin in a glass vial at 25 ℃, adding 25mL of sodium chloride aqueous solution with mass concentration of 0.9%, sealing for 10min, opening a bottle cap, fanning the odor in the bottle, scoring according to the following scoring standard, taking the average value of scoring results of 4 panelists, and recording and table 1.
The scoring criteria were:
0: no smell
1: smell only audible
2: audible but tolerable smell
3: strong smell easy to smell
4: stronger odor
5: intense smell
TABLE 1,
Claims (10)
1. A method for preparing a low-odor water-absorbent resin, which is characterized by comprising at least the following steps:
(1) Adding an internal crosslinking agent into an acrylic acid solution to prepare a monomer solution, degassing under a nitrogen atmosphere, controlling the temperature of the monomer solution, blowing nitrogen, performing nitrogen replacement when the dissolved oxygen concentration is lower than 1ppm, and adding an initiator and a reducing agent to perform polymerization reaction to generate a hydrogel crosslinked polymer;
(2) Pre-breaking the hydrogel gel-like crosslinked polymer into block-like gel-like crosslinked polymer, and then breaking the block-like gel-like crosslinked polymer by a granulator, and adding a neutralizing agent in the breaking process for neutralization to obtain hydrogel particles;
(3) Spreading the hydrogel particles on a metal net for drying treatment, crushing by a grinder and sieving by a sieving machine to obtain SAP basic resin particles;
(4) Mixing SAP basic resin particles with a surface cross-linking agent solution, and performing secondary cross-linking treatment.
2. The method for producing a low odor water absorbent resin according to claim 1, wherein the acrylic acid solution in the step (1) is an acrylic acid aqueous solution having an acrylic acid monomer concentration of 20 to 30% by weight.
3. The method for producing a low odor water absorbent resin according to claim 2, wherein the amount of the internal crosslinking agent added in the step (1) is 0.08 to 0.12% by mass of the acrylic acid solution.
4. The method for preparing a low odor water absorbent resin according to claim 3, wherein the initiator in the step (1) is a peroxy initiator, and the reducing agent is at least one of sodium sulfite, sodium bisulphite, ferrous sulfate and L-ascorbic acid.
5. The method for producing a low odor water absorbent resin according to claim 4, wherein the neutralizing agent in the step (2) is sodium carbonate or sodium bicarbonate, and the amount of the neutralizing agent added is 10 to 15% of the mass of the acrylic acid solution.
6. The method for producing a low odor water absorbent resin according to claim 5, wherein the drying treatment in the step (3) is carried out at a temperature of 90 to 180℃for a time of 40 to 100 minutes.
7. The method for producing a low odor water absorbent resin according to claim 6, wherein the surface cross-linking agent solution in the step (4) is composed of a surface cross-linking agent, an organic solvent and water in a mass ratio of (1-3): (10-15): 30.
8. the method for preparing a low odor water absorbent resin according to claim 7, wherein the surface cross-linking agent is at least one of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, and the organic solvent is at least one of ethylene glycol, 1, 2-propanediol, and 1, 4-butanediol.
9. The method for producing a low odor water absorbent resin according to claim 8, wherein the secondary crosslinking treatment in the step (4) is carried out at a temperature of 80 to 130 ℃ for 40 to 80 minutes.
10. Use of a method for producing a low-odor water-absorbent resin according to any one of claims 1 to 9, characterized by being applied to the production of a low-odor water-absorbent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311067153.3A CN117050350A (en) | 2023-08-23 | 2023-08-23 | Preparation method and application of low-odor water-absorbent resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311067153.3A CN117050350A (en) | 2023-08-23 | 2023-08-23 | Preparation method and application of low-odor water-absorbent resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117050350A true CN117050350A (en) | 2023-11-14 |
Family
ID=88666024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311067153.3A Pending CN117050350A (en) | 2023-08-23 | 2023-08-23 | Preparation method and application of low-odor water-absorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117050350A (en) |
-
2023
- 2023-08-23 CN CN202311067153.3A patent/CN117050350A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100340631B1 (en) | Water-absorbing agent and production process therefor | |
| JP4380873B2 (en) | Water absorbent resin powder and use thereof | |
| US7816301B2 (en) | Aqueous-liquid-absorbing agent and its production process | |
| FI105564B (en) | Superabsorbent polymer with improved absorption properties | |
| CA2166779C (en) | Powder-form cross-linked polymers capable of absorbing aqueous liquids and body fluids, method of preparing them and their use | |
| EP1029886B1 (en) | Water-absorbent resin powder and its production process and use | |
| US6372852B2 (en) | Water-absorbing composition and production process for water-absorbing agent | |
| KR100441472B1 (en) | Absorbing agents for water and aqueous liquids and process for their prodn. and use | |
| TWI406883B (en) | Water absorbing agent, water absorbing article and method for production of water absorbing agent | |
| TWI654236B (en) | Particulate superabsorbent polymer composition having improved stability | |
| JP4162746B2 (en) | Water-absorbing agent composition and absorbent article using the same | |
| TW201504314A (en) | Particulate superabsorbent polymer composition having improved stability | |
| CN1291203A (en) | Cross-linked polymers capable of swelling | |
| JP3913867B2 (en) | Water absorbing agent and method for producing the same | |
| JP7064614B2 (en) | Method for manufacturing a water-absorbent resin containing a chelating agent | |
| JP4308382B2 (en) | Water absorbing agent and method for producing the same | |
| JP4256484B2 (en) | Water-absorbing agent, water-absorbing article, and method for producing water-absorbing agent | |
| JP3810899B2 (en) | Method for producing water-absorbing agent | |
| KR20200132929A (en) | Super absorbent polymer and method of making and using the same | |
| CN117050350A (en) | Preparation method and application of low-odor water-absorbent resin | |
| JP5008790B2 (en) | Surface-crosslinked water-absorbing resin and surface-crosslinking method of water-absorbing resin | |
| CN112574450B (en) | Preparation method of high-absorptivity resin for sanitary towels | |
| CN114044921B (en) | Water-absorbent resin and preparation method and application thereof | |
| CN112011007B (en) | High water absorption resin capable of multiple absorption and preparation method thereof | |
| CN113943433B (en) | High-performance acrylic acid water-absorbent resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |