CN116120689B - Acrylic acid water-absorbent resin with low reverse osmosis and low extractable content and preparation method thereof - Google Patents
Acrylic acid water-absorbent resin with low reverse osmosis and low extractable content and preparation method thereof Download PDFInfo
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- CN116120689B CN116120689B CN202310013723.4A CN202310013723A CN116120689B CN 116120689 B CN116120689 B CN 116120689B CN 202310013723 A CN202310013723 A CN 202310013723A CN 116120689 B CN116120689 B CN 116120689B
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- absorbent resin
- acrylic acid
- water
- reverse osmosis
- acid water
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- 229920005989 resin Polymers 0.000 title claims abstract description 85
- 239000011347 resin Substances 0.000 title claims abstract description 85
- 239000002250 absorbent Substances 0.000 title claims abstract description 76
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 67
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000007863 gel particle Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 230000002745 absorbent Effects 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000012632 extractable Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 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 claims description 13
- 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 claims description 13
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 11
- 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 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- MHWRYTCHHJGQFQ-UHFFFAOYSA-N prop-2-enoic acid hydrate Chemical compound O.OC(=O)C=C MHWRYTCHHJGQFQ-UHFFFAOYSA-N 0.000 claims description 6
- -1 salt inorganic compound Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910052751 metal Chemical class 0.000 claims description 5
- 239000002184 metal Chemical class 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims 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 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 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 150000002314 glycerols Chemical class 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- 238000007873 sieving Methods 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000000017 hydrogel Substances 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000499 gel Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an acrylic acid water-absorbent resin with low reverse osmosis and low extractable content and a preparation method thereof. The method of the invention comprises the following steps: neutralizing acrylic acid with sodium hydroxide solution, and mixing with a cross-linking agent and a special polyurethane prepolymer to obtain a monomer composition before polymerization; adding a thermal initiator to obtain a polymerized colloid, and granulating to obtain gel particles with the size of 1-10 mm; drying, grinding and sieving in turn, and then carrying out secondary crosslinking and sieving to obtain the 10-50 μm acrylic water-absorbent resin. The acrylic acid water-absorbing resin product prepared by the method has lower reverse osmosis and can be used in the fields of cable water resistance and the like.
Description
Technical Field
The invention belongs to the field of chemical high polymer materials, and in particular relates to an acrylic acid water-absorbent resin with low reverse osmosis and low extractable content and a preparation method thereof.
Background
The super absorbent resin (SAP) is a water-absorbing material capable of absorbing hundreds or thousands of times of pure water, has an excellent water-retaining function, and is widely applied to the sanitary industries such as paper diapers, sanitary napkins and the like, and the industrial and agricultural water-proof fields such as agriculture and forestry water retention, building construction, cable water blocking and the like. After the high water absorption resin absorbs water, the colloid expands to form gel, and a layer of water film is formed on the surface of the gel, and the water film exists in a free state to form reverse osmosis. After a large amount of water is absorbed by the high water absorption resin, the gel strength is obviously reduced, and part of water is separated out under the condition of compression, so that the water locking capacity is reduced, the reverse osmosis is increased, and the downstream application is influenced.
Taking a communication optical cable as an example, winding a water blocking tape around the optical cable, taking non-woven fabrics as a base tape for the water blocking tape, and uniformly distributing the super absorbent resin and the filler. After the water blocking tape absorbs water, if the reverse osmosis performance is poor, absorbed water can still slowly permeate into the optical cable to corrode metal and optical fibers, so that the hydrogen loss, wire breakage and insulation performance are reduced, and the signal transmission is affected. The main factor determining the reverse osmosis performance of the water-blocking tape is the reverse osmosis performance of the super absorbent resin, which is determined by the super absorbent resin added thereto. Meanwhile, the content of the extractables of the high water-absorbing resin is higher, and after the water-blocking tape absorbs moisture, the extractables can be slowly separated out along with the moisture and enter the optical cable, so that the optical cable is damaged.
Chinese patent publication No. CN113817185A relates to a preparation method of low-reverse osmosis super absorbent resin, and the purpose of low-reverse osmosis is achieved by adding a large amount of maleic acid in the polymerization process and neutralizing after polymerization. The steric hindrance effect of maleic acid is large and the reactivity is low. If the addition amount is large in the polymerization process, the free radical polymerization efficiency is seriously affected, so that a large amount of maleic acid remains in the later stage of the reaction, the molecular structure is inconsistent, the product performance is affected, and the repeatability is poor. In addition, the maleic acid has high carboxyl content and higher hydrophilicity than acrylic acid, and after the super absorbent resin is formed, the content of extractables is higher, the product is severely hydrolyzed, and the downstream application is influenced.
The method for reducing the extractables content is generally to increase the amount of crosslinking agent used in the polymerization process, and to increase the molecular weight by increasing the crosslinking density. This in turn leads to a decrease in the absorption capacity of the superabsorbent resin, further leading to a higher reverse osmosis.
Disclosure of Invention
The invention aims to provide an acrylic acid super absorbent resin with low reverse osmosis and low extractable content and a preparation method thereof by mixing polyurethane prepolymer and acrylic acid monomer.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of acrylic acid water-absorbent resin with low reverse osmosis and low extractable content, wherein polyurethane prepolymer is added in the polymerization process of the acrylic acid water-absorbent resin as a performance promoter, and the addition amount of the polyurethane prepolymer is 1.2-1.4% of the mass of acrylic acid monomers.
In a specific embodiment, the method comprises the steps of:
(1) Neutralizing acrylic acid with sodium hydroxide solution, and then mixing with a cross-linking agent and the polyurethane prepolymer to obtain a polymerized monomer composition;
(2) Adding an initiator into the polymerization monomer composition to obtain a polymerization colloid, and granulating to obtain gel particles;
(3) Drying, grinding and screening the gel particles to obtain primary acrylic acid water-absorbent resin;
(4) And (3) carrying out secondary crosslinking on the primary acrylic acid water absorbent resin by using a surface crosslinking agent, and screening to obtain the required acrylic acid water absorbent resin.
In a specific embodiment, the cross-linking agent is selected from one or more of polyethylene glycol diacrylate, pentaerythritol triallyl ether, polyethylene glycol diallyl ether, pentaerythritol triacrylate, glycerol triacrylate, ethoxylated glycerol triallyl ether, N-dimethyl bisacrylamide, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, preferably pentaerythritol triallyl ether.
In a specific embodiment, the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, di-t-butyl peroxide, azobisiso Ding Mi, or 2' 2-azo-bis (2-methyl) propylamidine dihydrochloride, preferably sodium persulfate and/or potassium persulfate; preferably, the initiator is added in an amount of 0.03 to 0.3wt% based on the mass of acrylic acid.
In a specific embodiment, the surface cross-linking agent comprises one or more of water, a polyol, an epoxy compound, or a metal salt inorganic compound.
In a specific embodiment, the polyol comprises one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, 1, 4-butanediol, pentanediol, or polyvinyl alcohol;
the epoxy compound comprises one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene carbonate or propylene carbonate;
the metal salt inorganic compound comprises one or more of kaolin, alumina, sodium sulfate, magnesium sulfate, aluminum sulfate, magnesium chloride, calcium chloride, aluminum chloride or zinc chloride;
preferably, the surface cross-linking agent is used in an amount of 2 to 8wt% based on the mass of the primary acrylic water absorbent resin.
In a specific embodiment, the polymerization monomer composition in step (2) is reacted at a temperature of 80 to 90 ℃; the reaction time is 2-10min, and the gel particle size is 1-10mm.
In a specific embodiment, the primary acrylic water absorbent resin in step (3) has a particle size of 10 to 710. Mu.m.
In a specific embodiment, the target product in step (4) has a particle size of 10-50 μm.
On the other hand, the acrylic water-absorbent resin having low reverse osmosis and low extractables content is produced by the aforementioned production method.
Compared with the prior art, the invention has the following advantages:
the preparation method has the advantages of simple route and simple process; and the resin has low reverse osmosis and extractables content, and is suitable for the industries such as cable water blocking and the like.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
A preparation method of acrylic acid water-absorbent resin with low reverse osmosis and low extractable matter content is characterized in that polyurethane prepolymer is added in the polymerization process of the acrylic acid water-absorbent resin to serve as a performance accelerator, after the polyurethane prepolymer is added, NCO at two ends of the polyurethane prepolymer is subjected to chain extension with water at high temperature to form polyurethane macromolecules and a microstructure, and the carbon-carbon macromolecule chains and the polyurethane macromolecule chains form an interpenetrating network structure in the acrylic acid/sodium polymerization process. After the high water absorption resin swells to form gel, the polyurethane macromolecular chain plays a role of framework support in the gel, so that the gel strength is improved, and reverse osmosis is prevented. If the addition amount of the polyurethane prepolymer is small, the skeleton support in the gel formed by the high water absorption resin is small, and the influence on reverse osmosis is small. If the addition amount is too large, the water absorption performance of the super absorbent resin is affected, and reverse osmosis is too large.
Meanwhile, after the interpenetrating network is formed by the molecular chains of the super absorbent resin and the polyurethane molecular chains, the low molecular weight part in the super absorbent resin is affected by the winding of the polyurethane molecular chains, so that the difficulty of free out of the gel network of the super absorbent resin is increased, and the extractable matter content of the super absorbent resin is reduced.
In the present invention, the amount of the polyurethane prepolymer to be added is 1.2 to 1.4% by mass of acrylic acid, for example, 1.2%, 1.25%, 1.3%, 1.35%, 1.4% by mass, etc.
The polyurethane prepolymer is prepared by reacting isocyanate with dihydric alcohol and then carrying out chain extension reaction by a small molecule chain extender, and the terminal group is NCO and has certain reactivity.
Specifically, the preparation method of the polyurethane prepolymer comprises the following steps:
(1) Uniformly mixing 168 parts by mass of HDI and 1000 parts by mass of PBA2000 (polybutylene adipate glycol, molecular weight 2000), and reacting for 1h at 80 ℃ to obtain NCO of 3.5-3.6%;
(2) Then adding 5 parts by mass of 1, 4-butanediol and 36 parts by mass of dimethylolpropionic acid and 100 parts by mass of acetone, reacting for 3-4 hours at 80 ℃, measuring the NCO to be 1.0-1.2%, and cooling for standby after the reaction is finished.
In the invention, the preparation method of the acrylic acid water-absorbent resin comprises the following steps:
(1) Neutralizing acrylic acid with sodium hydroxide solution, and then mixing with a cross-linking agent and the polyurethane prepolymer to obtain a polymerized monomer composition;
(2) Adding an initiator into the polymerization monomer composition to obtain a polymerization colloid, and granulating to obtain gel particles;
(3) The gel particles are dried, ground and sieved to obtain the primary acrylic acid water-absorbent resin
(4) And (3) carrying out secondary crosslinking on the primary acrylic acid water absorbent resin by using a surface crosslinking agent, and screening to obtain the required acrylic acid water absorbent resin.
In the process of the present invention, the thermal initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, di-t-butyl peroxide, 2 '2-azo [ 2-methyl-N- (2-hydroxyethyl) propionamide ], azobisiso Ding Mi, and 2' 2-azo-bis (2-methyl) propylamidine dihydrochloride, preferably sodium persulfate and/or potassium persulfate. Specifically, the thermal initiator is added in an amount of 0.03 to 0.3% by weight, for example, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3% by mass, etc., based on the mass of acrylic acid.
In the method of the invention, the cross-linking agent is selected from one or more of polyethylene glycol diacrylate, pentaerythritol triallyl ether, polyethylene glycol diallyl ether, pentaerythritol triacrylate, glycerol triacrylate, ethoxylated glycerol triallyl ether, N-dimethyl bisacrylamide, pentaerythritol tetraacrylate and trimethylolpropane triacrylate, preferably pentaerythritol triallyl ether. The amount of the crosslinking agent to be added is 0.1 to 0.8% by mass of acrylic acid, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% by mass, etc.
In the method of the present invention, the surface cross-linking agent comprises one or more of water, a polyol, an epoxy compound, and an inorganic compound.
Preferably, the polyol comprises one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentanediol, and polyvinyl alcohol.
Preferably, the epoxy compound comprises one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene carbonate, and propylene carbonate.
Preferably, the inorganic compound comprises one or more of kaolin, alumina, sodium sulfate, magnesium sulfate, aluminum sulfate, magnesium chloride, calcium chloride, aluminum chloride, and zinc chloride.
Preferably, in some specific embodiments of the present invention, the surface cross-linking agent may be formulated in a mass ratio of ethylene glycol diglycidyl ether to aluminum sulfate to ethylene glycol to water=3:8:18:50. Specifically, the surface cross-linking agent is used in an amount of 2 to 8% by weight, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8% and the like, based on the mass of the primary acrylic water absorbent resin.
In the process of the present invention, the molar ratio of sodium hydroxide to acrylic acid in step (1) is 30 to 90%, for example 30%, 40%, 50%, 60%, 70%, 80%, 90%, etc., preferably 50 to 85%.
In the process of the present invention, the polymerization reaction temperature of the polymerized monomer composition in step (2) is 80 to 100 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, etc.; the polymerization time is 2-10min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, etc.
In the process of the present invention, the granulation in the step (2) may be carried out by a method conventional in the art, and there is no particular limitation, and the size of the gel particles obtained by the granulation is 1 to 10mm, for example, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, etc.
In the method of the present invention, the gel particles in step (3) are dried at a temperature of 100 to 250℃such as 100℃110℃120℃130℃140℃150℃160℃170℃180℃190℃200℃210℃220℃230℃240℃250℃20 to 200min such as 20min 50min 100min 150min 200 min. Grinding and sieving are conventional techniques in the art, and give the primary acrylic water absorbent resin particle diameters of 10 to 710. Mu.m, for example, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, etc.
In the method of the present invention, the primary acrylic water absorbent resin in step (4) is subjected to secondary crosslinking with a surface crosslinking agent, the mass of the added surface crosslinking agent is 2 to 8% by weight, for example 2%, 3%, 4%, 5%, 6%, 7%, 8% by weight, etc., of the mass of the primary acrylic water absorbent resin, and the acrylic water absorbent resin having a target product particle diameter of 10 to 50 μm is obtained by sieving after the secondary crosslinking.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Acrylic acid: vanhua chemical group Co., ltd., industrial products;
32% by weight sodium hydroxide solution: vanhua chemical group Co., ltd., industrial products;
pentaerythritol triallyl ether: japanese DAISO Co., ltd., trade name NEOALLYL P-30;
sodium persulfate: northeast asia-tai electric company, industrial products;
ethylene glycol diglycidyl ether: japanese Renzhen Chemie, brand DENACOL EX-810;
aluminum sulfate: zibo constant environmental protection materials Co., ltd, industrial products;
the performance of the super absorbent resin product was tested according to the following analytical method:
(1) Reverse osmosis
The test method is as follows: adding 2g of super absorbent resin into 50g of normal saline, placing into a self-sealing bag, shaking uniformly, spreading gel on a surface dish with the diameter of 12cm after one hour, placing 20 pieces of qualitative filter paper with the mass of 11cm, marking as m1, pressing with 500g weight for 30 minutes, weighing the filter paper with the mass of m2, and obtaining the reverse osmosis amount of m2-m1, wherein the index range is less than or equal to 0.8 per gram
(2) Content of extractables
The testing method comprises the following steps: according to GB/T22875-2018 standard, the index range is less than or equal to 16
(2) Other performance testing criteria
Preparation example
The polyurethane prepolymer adopts the following preparation process:
168g of HDI and 1000g of PBA2000 (polybutylene adipate glycol, molecular weight 2000) were charged into a 5L four-necked flask equipped with a thermometer, reflux condenser and stirrer, and after mixing uniformly, they were reacted at 80℃for 1 hour, and NCO was found to be 3.5 to 3.6%.
Cooling to below 60 ℃, adding 5g of 1, 4-butanediol, 36g of dimethylolpropionic acid and 100g of acetone as solvents, stirring uniformly, heating to 80 ℃, continuing to react for 3-4 hours until the residual NCO is constant, measuring that the NCO is 1.0-1.2%, and cooling for later use.
Example 1
To the reaction vessel were added 1868g of acrylic acid, 1945g of a 32wt% sodium hydroxide solution, 940g of water, and 22.4g of a polyurethane prepolymer, 8g of pentaerythritol triallyl ether, to obtain a polymerized monomer composition.
The temperature of the neutralization solution (polymerized monomer composition) was controlled to 90℃while adding 65g of a 5wt% aqueous sodium persulfate solution to the reaction solution, and then the well-mixed neutralization solution was poured into the polymerization tank. The polymerization tank is put into an oven at 80 ℃ to react for 6min to obtain polymer hydrogel, the polymer hydrogel is granulated by a granulator, and the size of gel particles is between 1 and 10mm.
Drying in a 230 ℃ oven for 35min, grinding and sieving in sequence to obtain the primary acrylic acid water-absorbent resin powder with the particle size of 10-710 mu m. Taking 500g of primary acrylic acid water-absorbent resin powder, uniformly spraying 40g of surface cross-linking agent on the surface, preparing the surface cross-linking agent by mass ratio of ethylene glycol diglycidyl ether to aluminum sulfate to ethylene glycol to water=3:8:18:50, finally drying in a drying oven at 140 ℃ for 50min, grinding and screening to obtain the super absorbent resin product with the diameter of 10-50 mu m.
The properties of the super absorbent resin product are shown in Table 1.
Example 2
To the reaction vessel were added 1868g of acrylic acid, 1945g of a 32wt% sodium hydroxide solution, 940g of water, and 26.2g of a polyurethane prepolymer, 8g of pentaerythritol triallyl ether, to obtain a polymerized monomer composition.
The temperature of the neutralization solution was controlled to 90℃while adding 65g of a 5wt% aqueous sodium persulfate solution to the reaction solution, and then the well-mixed neutralization solution was poured into the polymerization tank. The polymerization tank is put into an oven at 80 ℃ to react for 6min to obtain polymer hydrogel, the polymer hydrogel is granulated by a granulator, and the size of gel particles is between 1 and 10mm.
Drying in a 230 ℃ oven for 35min, grinding and sieving in sequence to obtain the primary acrylic acid water-absorbent resin powder with the particle size of 10-710 mu m. Taking 500g of primary acrylic acid water-absorbent resin powder, uniformly spraying 40g of surface cross-linking agent on the surface, preparing the surface cross-linking agent by mass ratio of ethylene glycol diglycidyl ether to aluminum sulfate to ethylene glycol to water=3:8:18:50, finally drying in a drying oven at 140 ℃ for 50min to obtain an acrylic acid water-absorbent resin product, and grinding and screening to obtain a 10-50 mu m high water-absorbent resin product.
The properties of the super absorbent resin product are shown in Table 1.
Example 3
To the reaction vessel were added 1868g of acrylic acid, 1945g of a 32wt% sodium hydroxide solution, 940g of water, and 24.3g of a polyurethane prepolymer, 8g of pentaerythritol triallyl ether, to obtain a polymerized monomer composition.
The temperature of the neutralization solution was controlled to 90℃while 25g of a 5wt% aqueous sodium persulfate solution was added to the reaction solution, and then the well-mixed neutralization solution was poured into the polymerization tank. The polymerization tank is put into an oven at 80 ℃ to react for 6min to obtain polymer hydrogel, the polymer hydrogel is granulated by a granulator, and the size of gel particles is between 1 and 10mm.
Drying in a 230 ℃ oven for 35min, grinding and sieving in sequence to obtain the primary acrylic acid water-absorbent resin powder with the particle size of 10-710 mu m. Taking 500g of primary acrylic acid water-absorbent resin powder, uniformly spraying 12.5g of surface cross-linking agent on the surface, preparing the surface cross-linking agent by mass ratio of glycol diglycidyl ether to aluminum sulfate to glycol to water=3:8:18:50, finally drying in a 140 ℃ oven for 50min to obtain an acrylic acid water-absorbent resin product, and grinding and screening to obtain a 10-50 mu m super absorbent resin product.
The properties of the super absorbent resin product are shown in Table 1.
Comparative example 1
To the reaction vessel were added 1868g of acrylic acid, 1945g of a 32wt% sodium hydroxide solution, 940g of water, and 18.7g of a polyurethane prepolymer, 8g of pentaerythritol triallyl ether, to obtain a polymerized monomer composition.
The temperature of the neutralization solution was controlled to 90℃while adding 65g of a 5wt% aqueous sodium persulfate solution to the reaction solution, and then the well-mixed neutralization solution was poured into the polymerization tank. The polymerization tank is put into an oven at 80 ℃ to react for 6min to obtain polymer hydrogel, the polymer hydrogel is granulated by a granulator, and the size of gel particles is between 1 and 10mm.
Drying in a 230 ℃ oven for 35min, grinding and sieving in sequence to obtain the primary acrylic acid water-absorbent resin powder with the particle size of 10-710 mu m. Taking 500g of primary acrylic acid water-absorbent resin powder, uniformly spraying 40g of surface cross-linking agent on the surface, preparing the surface cross-linking agent by mass ratio of ethylene glycol diglycidyl ether to aluminum sulfate to ethylene glycol to water=3:8:18:50, finally drying in a drying oven at 140 ℃ for 50min to obtain an acrylic acid water-absorbent resin product, and grinding and screening to obtain a 10-50 mu m high water-absorbent resin product.
The properties of the super absorbent resin product are shown in Table 1.
Comparative example 2
To the reaction vessel were added 1868g of acrylic acid, 1945g of a 32wt% sodium hydroxide solution, 940g of water, and 29.9g of a polyurethane prepolymer, 8g of pentaerythritol triallyl ether, to obtain a polymerized monomer composition.
The temperature of the neutralization solution was controlled to 90℃while adding 65g of a 5wt% aqueous sodium persulfate solution to the reaction solution, and then the well-mixed neutralization solution was poured into the polymerization tank. The polymerization tank is put into an oven at 80 ℃ to react for 6min to obtain polymer hydrogel, the polymer hydrogel is granulated by a granulator, and the size of gel particles is between 1 and 10mm.
Drying in a 230 ℃ oven for 35min, grinding and sieving in sequence to obtain the primary acrylic acid water-absorbent resin powder with the particle size of 10-710 mu m. Taking 500g of primary acrylic acid water-absorbent resin powder, uniformly spraying 40g of surface cross-linking agent on the surface, preparing the surface cross-linking agent by mass ratio of ethylene glycol diglycidyl ether to aluminum sulfate to ethylene glycol to water=3:8:18:50, finally drying in a drying oven at 140 ℃ for 50min to obtain an acrylic acid water-absorbent resin product, and grinding and screening to obtain a 10-50 mu m high water-absorbent resin product.
The properties of the super absorbent resin product are shown in Table 1.
Comparative example 3
In comparison with example 1, no polyurethane prepolymer was added.
To the reaction vessel were added 1868g of acrylic acid, 1945g of a 32wt% sodium hydroxide solution, 940g of water, and 8g of pentaerythritol triallyl ether to obtain a polymerized monomer composition.
The temperature of the neutralization solution was controlled to 90℃while adding 65g of a 5wt% aqueous sodium persulfate solution to the reaction solution, and then the well-mixed neutralization solution was poured into the polymerization tank. The polymerization tank is put into an oven at 80 ℃ to react for 6min to obtain polymer hydrogel, the polymer hydrogel is granulated by a granulator, and the size of gel particles is between 1 and 10mm.
Drying in a 230 ℃ oven for 35min, grinding and sieving in sequence to obtain the primary acrylic acid water-absorbent resin powder with the particle size of 10-710 mu m. Taking 500g of primary acrylic acid water-absorbent resin powder, uniformly spraying 40g of surface cross-linking agent on the surface, preparing the surface cross-linking agent by mass ratio of ethylene glycol diglycidyl ether to aluminum sulfate to ethylene glycol to water=3:8:18:50, finally drying in a drying oven at 140 ℃ for 50min to obtain an acrylic acid water-absorbent resin product, and grinding and screening to obtain a 10-50 mu m high water-absorbent resin product.
Table 1 Properties of the super absorbent resin products in examples and comparative examples
As can be seen from Table 1, in comparative example 3, in which the technique of the present invention was not employed, the reverse osmosis amount and extractables were significantly higher than those of examples 1, 2 and 3, although the conventional absorption properties such as the liquid absorption rate, the centrifugal retention, the pressurized absorption, the liquid absorption rate and the like were not greatly different. In examples 1, 2 and 3, the polyurethane prepolymer is added as a performance promoter, the conventional absorption performance of the resin is not obviously changed, but the reverse osmosis and the extractable content are obviously improved, which shows that the polyurethane macromolecules play a role of framework support in a gel network formed by the high water absorbent resin, and the precipitation of low molecular weight polyacrylate can be prevented to a certain extent. In comparative example 1, the polyurethane prepolymer is added as a performance promoter, the addition amount is small, the skeleton supporting effect of the polyurethane macromolecule is weak, the reverse osmosis improving effect is not obvious, and meanwhile, the extractable content is reduced to a certain extent, but a certain difference is still provided compared with examples 1 and 2. In comparative example 2, the polyurethane prepolymer was added as a performance accelerator in a large amount, which had a certain influence on the conventional absorption performance and had a tendency to increase reverse osmosis. It can be seen that the improvement of the reverse osmosis effect shows a parabolic trend of influence on the extractables content and a linear trend of influence on the reverse osmosis effect by using the polyurethane prepolymer as a performance promoter. The performance improvement effect is best when the addition amount is 1.2-1.4%.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (14)
1. The preparation method of the acrylic acid water-absorbent resin with low reverse osmosis and low extractable content is characterized in that a polyurethane prepolymer is added into the acrylic acid water-absorbent resin in the polymerization process to serve as a performance promoter, and the addition amount of the polyurethane prepolymer is 1.2-1.4% of the mass of an acrylic acid monomer;
the polyurethane prepolymer is prepared by reacting isocyanate with dihydric alcohol and then carrying out chain extension reaction by a small molecule chain extender, and the end group is NCO.
2. The method of manufacturing according to claim 1, comprising the steps of:
(1) Neutralizing acrylic acid with sodium hydroxide solution, and then mixing with a cross-linking agent and the polyurethane prepolymer to obtain a polymerized monomer composition;
(2) Adding an initiator into the polymerization monomer composition to obtain a polymerization colloid, and granulating to obtain gel particles;
(3) Drying, grinding and screening the gel particles to obtain primary acrylic acid water-absorbent resin;
(4) And (3) carrying out secondary crosslinking on the primary acrylic acid water absorbent resin by using a surface crosslinking agent, and screening to obtain the required acrylic acid water absorbent resin.
3. The preparation method according to claim 2, wherein the cross-linking agent is one or more selected from polyethylene glycol diacrylate, pentaerythritol triallyl ether, polyethylene glycol diallyl ether, pentaerythritol triacrylate, glycerol triacrylate, ethoxylated glycerol triallyl ether, N-dimethyl bisacrylamide, pentaerythritol tetraacrylate, trimethylolpropane triacrylate.
4. A method of preparation according to claim 3, wherein the cross-linking agent is selected from pentaerythritol triallyl ether.
5. The method of claim 2, wherein the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, di-t-butyl peroxide, azobisis Ding Mi, or 2' 2-azo-bis (2-methyl) propylamidine dihydrochloride.
6. The process according to claim 5, wherein the initiator is selected from sodium persulfate and/or potassium persulfate.
7. The process according to claim 5, wherein the initiator is added in an amount of 0.03 to 0.3% by weight based on the mass of the acrylic acid.
8. The method of claim 2, wherein the surface cross-linking agent comprises one or more of water, a polyol, an epoxy compound, or a metal salt inorganic compound.
9. The method of claim 8, wherein the polyol comprises one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, 1, 4-butanediol, pentanediol, or polyvinyl alcohol;
the epoxy compound comprises one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
the metal salt inorganic compound comprises one or more of kaolin, sodium sulfate, magnesium sulfate, aluminum sulfate, magnesium chloride, calcium chloride, aluminum chloride or zinc chloride.
10. The method according to claim 9, wherein the surface cross-linking agent is used in an amount of 2 to 8% by weight based on the mass of the primary acrylic water absorbent resin.
11. The process according to any one of claims 2 to 10, wherein the reaction temperature of the polymerized monomer composition in step (2) is 80 to 90 ℃; the reaction time is 2-10min, and the gel particle size is 1-10mm.
12. The method according to any one of claims 2 to 10, wherein the primary acrylic water absorbent resin in step (3) has a particle size of 10 to 710 μm.
13. The process according to any one of claims 2 to 10, wherein the target product in step (4) has a particle size of 10 to 50 μm.
14. The acrylic water-absorbent resin having low reverse osmosis and low extractables content produced by the production process according to any one of claims 1 to 13.
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| JPH11347402A (en) * | 1998-04-10 | 1999-12-21 | Sanyo Chem Ind Ltd | Water absorbing agent and its production |
| CN1760225A (en) * | 2005-10-10 | 2006-04-19 | 南京师范大学 | Method for synthesizing resin with high water absorption from polyaminoester |
| CN110950993A (en) * | 2019-12-13 | 2020-04-03 | 万华化学集团股份有限公司 | Preparation method of acrylic acid water-absorbent resin with low extractable content |
| CN111333784A (en) * | 2020-03-24 | 2020-06-26 | 福建省春天生态科技股份有限公司 | Preparation method of high water absorption and water retention resin |
| CN111548464A (en) * | 2020-05-29 | 2020-08-18 | 东华大学 | Degradation-controllable super absorbent resin and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11347402A (en) * | 1998-04-10 | 1999-12-21 | Sanyo Chem Ind Ltd | Water absorbing agent and its production |
| CN1760225A (en) * | 2005-10-10 | 2006-04-19 | 南京师范大学 | Method for synthesizing resin with high water absorption from polyaminoester |
| CN110950993A (en) * | 2019-12-13 | 2020-04-03 | 万华化学集团股份有限公司 | Preparation method of acrylic acid water-absorbent resin with low extractable content |
| CN111333784A (en) * | 2020-03-24 | 2020-06-26 | 福建省春天生态科技股份有限公司 | Preparation method of high water absorption and water retention resin |
| CN111548464A (en) * | 2020-05-29 | 2020-08-18 | 东华大学 | Degradation-controllable super absorbent resin and preparation method thereof |
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