CN102408505B - Method for preparing super absorbent resin by inverse suspension polymerization - Google Patents
Method for preparing super absorbent resin by inverse suspension polymerization Download PDFInfo
- Publication number
- CN102408505B CN102408505B CN201110307721.3A CN201110307721A CN102408505B CN 102408505 B CN102408505 B CN 102408505B CN 201110307721 A CN201110307721 A CN 201110307721A CN 102408505 B CN102408505 B CN 102408505B
- Authority
- CN
- China
- Prior art keywords
- suspension polymerization
- super absorbent
- absorbent resin
- inverse suspension
- acrylic acid
- 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.)
- Active
Links
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002250 absorbent Substances 0.000 title claims abstract description 23
- 230000002745 absorbent Effects 0.000 title claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- -1 polyoxyethylene Polymers 0.000 claims description 14
- 230000008719 thickening Effects 0.000 claims description 13
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000001589 sorbitan tristearate Substances 0.000 claims description 11
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 11
- 229960004129 sorbitan tristearate Drugs 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 239000004159 Potassium persulphate Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 235000019394 potassium persulphate Nutrition 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- OPPFIPBEHRZBOT-UHFFFAOYSA-N 1,1-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(O)(CC)OCC1CO1 OPPFIPBEHRZBOT-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical compound CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 0.000 claims description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000005213 imbibition Methods 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 6
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002504 physiological saline solution Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000003556 assay Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- ARIWANIATODDMH-UHFFFAOYSA-N rac-1-monolauroylglycerol Chemical compound CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- 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 1
- PWVUXRBUUYZMKM-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOCCO PWVUXRBUUYZMKM-UHFFFAOYSA-N 0.000 description 1
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- YKDMBTQVKVEMSA-UHFFFAOYSA-N diethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOCCOC(=O)CCCCCCCCCCCCCCCCC YKDMBTQVKVEMSA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229940068939 glyceryl monolaurate Drugs 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for preparing super absorbent resin by inverse suspension polymerization. With a hydrophobic and lipophilic organic substance as the solvent and a proper compound as the dispersant, the method subjects part of a neutralized acrylic acid solution to an inverse suspension polymerization reaction in the presence of a thickening agent, a cross-linking agent as well as a water-soluble initiator, and then employs a surface cross-linking agent for surface cross-linking treatment. The super absorbent resin prepared by the method of the invention has an average particle size of 100-200 micrometers, a saline water adsorption rate of over 45g/g in 1min, and an imbibition speed of less than 20s.
Description
Technical field
The present invention relates to via Inverse-Phase Suspension Polymerization and prepare the method for High hydrophilous resin, say further, relate to the preparation method with the fast High hydrophilous resin of rate of liquid aspiration.
Background technology
High hydrophilous resin is a kind of hydrophilic radicals such as carboxyl that have, and has the water-swellable superpolymer of certain degree of crosslinking, can absorb the extremely water of thousands of times of own wt hundred times.In the last few years, High hydrophilous resin was widely used in the various fields such as agricultural horticultural soil improved materials, cable material water-proof material, anti-condensation material, medical material such as sanitary product material, the water-holding agents such as paper diaper.
The preparation method of High hydrophilous resin mainly contains solution polymerization process and via Inverse-Phase Suspension Polymerization.Solution polymerization process manufacturing process is simple, but product yield is lower, aftertreatment difficulty, and product rate of liquid aspiration is slower.The relative solution polymerization process of via Inverse-Phase Suspension Polymerization has the following advantages: can direct production go out to specify the product of particle diameter, aftertreatment is easy, excellent product performance.
As the example of preparing super absorbent resin by inverse suspension polymerization, disclosed to have the vinylformic acid of take, acrylamide, cationic vinyl monomer be raw material, adopts via Inverse-Phase Suspension Polymerization to synthesize a kind of zwitterionic High hydrophilous resin (CN101012290); Take vinylformic acid, acrylamide is raw material, and hexadecanol phosphatide or stearyl alcohol phosphatide are that dispersion agent is prepared High hydrophilous resin (CN101215354); Take the vinylformic acid of part neutralization and heterogeneous ring compound that methylene radical replaces prepares the super absorbent resin (CN101134793) of fully biodegradable as raw material; Take vinylformic acid as monomer, and hexanaphthene is solvent.Tegin 55G, Arlacel-60 and stearyl alcohol phosphatide are that dispersion agent is prepared polypropylene (salt) High hydrophilous resin (CN1834122) etc.Although people have done a lot of research to inverse suspension polymerization, because inverse suspension polymerization system is unstable, when polymerization, be still easy to occur the phenomenon of implode and caking.Although can prevent by adjusting dispersion agent the generation of implode, but conventionally also can only obtain fine powder or bulk product, being difficult to directly obtain median size is the super absorbent resin fat prod of 100～200 μ m, and the performance of High hydrophilous resin will be affected like this, and then also can be restricted in application.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing super absorbent resin by inverse suspension polymerization, the stability of selecting suitable dispersion agent and thickening material to increase reaction system, strictly controlling polymerization process condition, to control size distribution and the absorptive character of particle be the key of inverse suspension polymerization synthesizing super absorbent resin.
The method of preparing super absorbent resin by inverse suspension polymerization of the present invention, the hydrophobic lipophilicity organism of take is solvent, selecting hydrophile-lipophile balance value (HLB) to be less than 8 compound is dispersion agent, makes the acrylic acid solution generation inverse suspension polymerization reaction of part neutralization at thickening material, linking agent and water soluble starter under the condition existing; Component distillation is sloughed unnecessary moisture afterwards; Then using surface crosslinking agent to carry out surface-crosslinked processing obtains.
The present invention adopts following technical scheme to realize:
A method for preparing super absorbent resin by inverse suspension polymerization, concrete steps are as follows:
1) dispersion agent is added in solvent, in 40～60 ℃ of heating for dissolving;
2) add quantitative vinylformic acid, in ice-water bath, with sodium hydroxide solution neutralization, after neutralization, add thickening material, linking agent and water soluble starter, obtain Acrylic Acid Monomer solution;
3) Acrylic Acid Monomer solution is added in solvent, pass into while stirring nitrogen 30～60 minutes, temperature is increased to 60～80 ℃, react 2～5 hours;
4) after reaction finishes, temperature is increased to 85～95 ℃, carries out azeotropic dehydration;
5) after dehydration finishes, be cooled to 40～60 ℃ and filter, use absolute ethanol washing, at 60～80 ℃, be dried 30～60 minutes;
6) use surface crosslinking agent to carry out surface-crosslinked processing, finally obtain super absorbent resin.
Solvent, should have hydrophobic lipophilicity.From making the stable angle of polymerization system consider, preferred petroleum hydrocarbon compound, Skellysolve A for example, normal hexane, normal heptane, octane, hexanaphthene, cyclooctane and methylcyclohexane one or more.These solvents are preferably used separately.Wherein normal heptane and hexanaphthene are because stable performance is the preferred solvent of the present invention.
The consumption of solvent is generally the 50%-600% of Acrylic Acid Monomer quality, preferably 200%-400%.The amount of solvent is less than 50% of Acrylic Acid Monomer quality, difficult control of temperature, and reaction heat has little time to remove, and the phenomenon of implode and caking easily occurs; Solvent load is more than 600% of Acrylic Acid Monomer quality, and polyreaction is slow, generally can only obtain having the gel of stickiness.
As the dispersion agent of inverse suspension polymerization, from arriving the angle of desirable dispersion effect and protective colloid, the compound that should select hydrophile-lipophile balance value (HLB) to be less than 8.If HLB value is greater than 8, dispersion agent is difficult to play the effect of protective colloid, and implode phenomenon easily occurs during polymerization.Can list as octadecyl phosphoric acid ester, sucrose fatty ester, mono-glycerides, sorbitan fatty acid ester, sorbitan monooleate, anhydrous sorbitol tristearate, ethylene glycol monostearate, Ethylene Glycol Distearate, diethylene glycol monostearate, diethylene glycol bis-stearate, the two stearates of poly(oxyethylene glycol) 400, Macrogol 200 bilaurate, poly(oxyethylene glycol) 400 dioleic acid ester, polyoxyethylene carboxylate, Viscotrol C/hydrogenated castor oil and ethylene oxide condensate, three Polyglycerine list hard fatty acid esters, propylene glycol monostearate, molecular distillation glyceryl monolaurate, one or more of molecule distillating monoglyceride and olein.For this patent, in order to have reached good dispersion effect and to have synthesized the High hydrophilous resin that median size is 100～200 μ m, the mixture of our preferred Tripolyglycerol monostearates and sorbitan tristearate is as dispersion agent.
The consumption of dispersion agent is generally the 0.1%-10% of Acrylic Acid Monomer quality, preferably 0.5%-10%.The ratio of Tripolyglycerol monostearates and sorbitan tristearate is that 1:2～2:1 is advisable.In order to access the narrow product of size distribution, the proportioning of dispersion agent should be strict controlled in aforementioned proportion.
As thickening material, can list Natvosol, hydroxypropylcellulose, methylcellulose gum, carboxymethyl cellulose, polyoxyethylene glycol, polyacrylamide, polyethylene, the polyacrylic acid of part neutralization, partial cross-linked polyacrylic acid etc.Thickening material can regulation system viscosity, can make High hydrophilous resin particle reach required particle size range.In order to achieve the above object, the preferred Natvosol of the present invention, carboxymethyl cellulose, a kind of as thickening material in polyoxyethylene glycol.
The consumption of thickening material is generally 0.01%～5% of Acrylic Acid Monomer quality, and preferably 0.05～1%.The consumption of thickening material, lower than 0.01% of Acrylic Acid Monomer quality, is difficult to play the effect of thickening, and the particle diameter of product is very thin; The consumption of thickening material is higher than 5% of Acrylic Acid Monomer quality, and the viscosity of system is too high, reacts unstable, and the phenomenon of caking easily occurs.
As water soluble starter, can list Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, 2,2'-azo diisobutyl amidine dihydrochloride etc.Due to the restriction of polymerizing condition, do not advise using redox class initiator.From efficiency of initiation, consider the preferred Potassium Persulphate of the present invention.
The consumption of water soluble starter is generally 0.05～3% of Acrylic Acid Monomer quality, is preferable over 0.1～1%.The amount of initiator surpasses 3%, and velocity of initiation is too fast, and the heat of system is not easy to remove, and implode easily occurs; The amount of initiator is lower than 0.05%, and velocity of initiation is excessively slow, and polymerization time can be very long, and product performance can decline to a great extent.
As linking agent, can list ethylene glycol, propylene glycol, glycerol, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propanetriol-diglycidyl-ether, one contracting two propanetriol-diglycidyl-ethers, sorbyl alcohol glycidyl ether, N, N'-methylene-bisacrylamide, N-n-methylolacrylamide, EDIA, polyethylene glycol acrylate, propylene glycol acrylate, triallylamine etc.The preferred propylene glycol diglycidylether of the present invention is as linking agent.
The consumption of linking agent is generally 0.01～3% of Acrylic Acid Monomer quality, is preferable over 0.05～1%.The consumption of linking agent is lower than 0.01%, and cross-linkage of resin is very low, has water-soluble; The consumption of linking agent surpasses 3%, and cross-linkage of resin is too high, and water absorbing properties declines.
In the present invention, owing to using Potassium Persulphate, be water soluble starter, polymerization temperature should be controlled at 60～80 ℃ and be advisable.Temperature is lower than 60 ℃, and trigger rate is slow, long reaction time; Temperature is higher than 80 ℃, and trigger rate is too fast, and reaction is difficult to control, and implode easily occurs.Polymerization time is controlled at 2-5 hour, and synthetic like this resin has good performance.
After polyreaction finishes, need carry out component distillation and slough unnecessary moisture, solvent refluxing is to reactor.The object of doing is like this to prevent that gel particle from sticking together in dry process.In the process of azeotropic dehydration, generally to slough more than 90% water of theoretical water content, if water content higher than 10%, particle easily bonds, and affects the effect of surface-crosslinked processing, makes the degradation of product.
From adding dispersion agent to start to finish to azeotropic dehydration, whole process all needs to stir.Stirring velocity is generally at 200～500rpm.
After azeotropic dehydration finishes, be cooled to 40～60 ℃ and filter, use absolute ethanol washing, remove the dispersion agent that sticks to resin surface.At 60～80 ℃, be dried 30～60 minutes.
Surface-crosslinked processing generally can be carried out after dry.As surface crosslinking agent, can list as ethanol, ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, glycerol, polyglycerol, Virahol, 1,4-butyleneglycol, diethanolamine, trolamine, polyethenoxy ether, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerol diglycidylether,, one contracting two propanetriol-diglycidyl-ethers, vinyl alcohol diglycidylether, epoxy chloropropane, quadrol, diethylenetriamine, triethylene tetramine, aluminum chloride, magnesium chloride, calcium chloride, Tai-Ace S 150, magnesium sulfate, calcium sulfate etc.In order to obtain good surface-crosslinked effect, at least one of preferred alcohol of the present invention, propylene glycol, glycerol, Virahol, vinyl alcohol diglycidylether.
The consumption of surface crosslinking agent, is used 0.5～30 part with respect to the resin of 100 parts of quality, preferably 1～20 part.The amount of surface crosslinking agent is less than 0.5 part, and cross-linking effect is not obvious; The amount of surface crosslinking agent is higher than 30 parts, and High hydrophilous resin forms fine and close upper layer, and water-retaining capacity declines.
Surface-crosslinked temperature is generally determined according to the surface crosslinking agent using.The surface crosslinking agent using according to the present invention, general 70～200 ℃ of surface-crosslinked temperature, preferably 80～150 ℃.The surface-crosslinked time is generally 0.5～1 hour.
The method of preparing super absorbent resin by inverse suspension polymerization of the present invention, the High hydrophilous resin median size making is 100～200 μ m.Resin 1min absorption salt ratio is more than 45g/g, and rate of liquid aspiration is in 20s.
The testing method of High hydrophilous resin of the present invention is as follows:
(1) median size
By JIS standard sieve by upper beginning according to 830 μ m(20 orders), 550 μ m(30 orders), 270 μ m(50 orders), 180 μ m(80 orders) 150 μ m(100 orders), 106 μ m(150 orders), 75 μ m(200 orders) sequential combination, on the sieve of the superiors, put into High hydrophilous resin 100g left and right, use laboratory sifter screening 20 minutes.Then, the High hydrophilous resin in 6 screen clothes of the 2nd screen cloth to the is counted to heavy (particles above due to 830 μ m and below 106 μ m are less and using value is not high, therefore not at the row of statistics), its weight is respectively A
2, A
3, A
4, A
5, A
6.Calculate according to the following formula the median size of High hydrophilous resin:
(2) water-intake rate
In the beaker of 2L, pour the deionized water of 1000mL into.Accurately take 0.2g High hydrophilous resin, pack into after Nylon Bag, be soaked in deionized water.After 1 hour, Nylon Bag is hung to liquid level, naturally drip 10 minutes, claim that now total mass is M
1.Use does not have the Nylon Bag of sample to carry out blank assay simultaneously, and the quality that takes blank Nylon Bag is M
2.Water-intake rate is calculated as follows:
(3) absorption salt ratio
In 1000ml beaker, pour the physiological saline of 500ml0.9% into.Accurately take 0.2g High hydrophilous resin, pack into after tea-bag, be soaked in 0.9% physiological saline.After 30 minutes, the tea-bag that sample is housed is brought out, under stationary state, drip 10 minutes, claim that now total mass is W
1.Use does not have the tea-bag of sample to carry out blank assay simultaneously, and the quality that takes blank tea-bag is W
2.Absorption salt ratio is calculated as follows:
(4) 1 minutes absorption salt ratios
In 1000ml beaker, pour the physiological saline of 500ml0.9% into.Accurately take 0.2g High hydrophilous resin, pack into after tea-bag, be soaked in 0.9% physiological saline.After 1 minute, the tea-bag that sample is housed is brought out, under stationary state, drip 10 minutes, claim that now total mass is W
1.Use does not have the tea-bag of sample to carry out blank assay simultaneously, and the quality that takes blank tea-bag is W
2.1 minute absorption salt ratio is pressed absorption salt ratio formula and is calculated.
(5) rate of liquid aspiration
In the 100mL beaker with rotor, pack 0.9% physiological saline 50g into, beaker is placed on magnetic stirrer, with the speed of 600 revs/min, stirs, accurately take the polymer of 2.0g, put in whirlpool, with stopwatch, start timing, when whirlpool disappears, when liquid level becomes horizontality simultaneously, as terminal, record its time.
More than test is all carried out in the time of 25 ℃.
Embodiment
Embodiment 1: 342.5g normal heptane is joined in five mouthfuls of round-bottomed flasks of 1L that agitator, reflux exchanger, dropping funnel, thermometer and nitrogen inlet tube are housed.Add wherein 0.75g Tripolyglycerol monostearates and 0.85g sorbitan tristearate, be warming up to 50 ℃, with the stirring velocity of 350rpm, make it dispersed.
By 130 g mass concentrations, be 75%(wt%) acrylic acid aqueous solution join in 500 ml erlenmeyer flasks.130.2g32 wt% aqueous sodium hydroxide solution is added drop-wise in this erlenmeyer flask.Then, add wherein 0.5g Potassium Persulphate, 0.2g propylene glycol diglycidylether, 0.12g Natvosol, obtains the Acrylic Acid Monomer aqueous solution.
This Acrylic Acid Monomer aqueous solution is joined in above-mentioned five mouthfuls of round-bottomed flasks, pass into while stirring nitrogen 30～60 minutes.Then by warming-in-water to 75 ℃, react 3 hours.After reaction finishes, temperature continues to rise to 92 ℃ and carries out azeotropic dehydration, removes altogether 110g water.Temperature is cooled to 50 ℃ and filters, use absolute ethanol washing, at 60～80 ℃, be dried 30～60 minutes.
4.4g ethanol, 3.2g Virahol, 0.4g vinyl alcohol diglycidylether are mixed, be sprayed onto uniformly the above-mentioned resin surface of 100g, in the baking oven of 140 ℃, surface-crosslinked processing is 50 minutes, obtains the High hydrophilous resin of white granular.
Embodiment 2: except changing the consumption of Tripolyglycerol monostearates and sorbitan tristearate into 0.9g and 0.7g, stirring velocity are adjusted into 380rpm, other operate with embodiment 1.
Embodiment 3: 380g hexanaphthene is joined in five mouthfuls of round-bottomed flasks of 1L that agitator, reflux exchanger, dropping funnel, thermometer and nitrogen inlet tube are housed.Add wherein 0.7g Tripolyglycerol monostearates and 0.7g sorbitan tristearate, be warming up to 50 ℃, with the stirring velocity of 320rpm, make it dispersed.
The acrylic acid aqueous solution of 130 g 75wt% is joined in 500 ml erlenmeyer flasks.130.2g32 wt% aqueous sodium hydroxide solution is added drop-wise in this erlenmeyer flask.Then, add wherein 0.45g Potassium Persulphate, 0.015g propylene glycol diglycidylether, 0.1g Natvosol, obtains the Acrylic Acid Monomer aqueous solution.
This Acrylic Acid Monomer aqueous solution is joined in above-mentioned five mouthfuls of round-bottomed flasks, pass into while stirring nitrogen 30～60 minutes.Then by warming-in-water to 70 ℃, react 3.5 hours.After reaction finishes, temperature continues to rise to 88 ℃ and carries out azeotropic dehydration, removes altogether 110g water.Temperature is cooled to 50 ℃ and filters, use absolute ethanol washing, at 60～80 ℃, be dried 30～60 minutes.
4.4g ethanol, 3.2g Virahol, 0.4g vinyl alcohol diglycidylether are mixed, be sprayed onto uniformly the above-mentioned resin surface of 100g, in the baking oven of 140 ℃, surface-crosslinked processing is 50 minutes, obtains the High hydrophilous resin of white granular.
Embodiment 4: except changing the consumption of Tripolyglycerol monostearates and sorbitan tristearate into 0.85g and 0.55g, stirring velocity are adjusted into 360rpm, other operate with embodiment 3.
Embodiment 5: 342.5g normal heptane is joined in five mouthfuls of round-bottomed flasks of 1L that agitator, reflux exchanger, dropping funnel, thermometer and nitrogen inlet tube are housed.Add wherein 0.7g Tripolyglycerol monostearates and 0.9g sorbitan tristearate, be warming up to 50 ℃, with the stirring velocity of 400rpm, make it dispersed.
The acrylic acid aqueous solution of 130 g 75wt% is joined in 500 ml erlenmeyer flasks.130.2g32 wt% aqueous sodium hydroxide solution is added drop-wise in this erlenmeyer flask.Then, 0.5g Potassium Persulphate, 0.2g propylene glycol diglycidylether wherein, 0.1g Walocel MT 20.000PV, obtains the Acrylic Acid Monomer aqueous solution.
This Acrylic Acid Monomer aqueous solution is joined in above-mentioned five mouthfuls of round-bottomed flasks, pass into while stirring nitrogen 30～60 minutes.Then by warming-in-water to 76 ℃, react 2.5 hours.After reaction finishes, temperature continues to rise to 92 ℃ and carries out azeotropic dehydration, removes altogether 110g water.Temperature is cooled to 50 ℃ and filters, use absolute ethanol washing, at 60～80 ℃, be dried 30～60 minutes.
4.4g ethanol, 1.2g propylene glycol, 0.6g glycerol, 0.4g vinyl alcohol diglycidylether are mixed, be sprayed onto uniformly the above-mentioned resin surface of 100g, in the baking oven of 150 ℃, surface-crosslinked processing is 40 minutes, obtains the High hydrophilous resin of micro-yellow particle shape.
Embodiment 6: 380g hexanaphthene is joined in five mouthfuls of round-bottomed flasks of 1L that agitator, reflux exchanger, dropping funnel, thermometer and nitrogen inlet tube are housed.Add wherein 0.8g Tripolyglycerol monostearates and 0.8g sorbitan tristearate, be warming up to 50 ℃, with the stirring velocity of 390rpm, make it dispersed.
The acrylic acid aqueous solution of 130 g 75wt% is joined in 500 ml erlenmeyer flasks.130.2g32 wt% aqueous sodium hydroxide solution is added drop-wise in this erlenmeyer flask.Then, add wherein 0.5g Potassium Persulphate, 0.02g propylene glycol diglycidylether, 0.1g Walocel MT 20.000PV, obtains the Acrylic Acid Monomer aqueous solution.
This Acrylic Acid Monomer aqueous solution is joined in above-mentioned five mouthfuls of round-bottomed flasks, pass into while stirring nitrogen 30～60 minutes.Then by warming-in-water to 72 ℃, react 3 hours.After reaction finishes, temperature continues to rise to 88 ℃ and carries out azeotropic dehydration, removes altogether 110g water.Temperature is cooled to 50 ℃ and filters, use absolute ethanol washing, at 60～80 ℃, be dried 30～60 minutes.
4.4g ethanol, 1.2g propylene glycol, 0.6g glycerol, 0.4g vinyl alcohol diglycidylether are mixed, be sprayed onto uniformly the above-mentioned resin surface of 100g, in the baking oven of 150 ℃, surface-crosslinked processing is 40 minutes, obtains the High hydrophilous resin of micro-yellow particle shape.
Comparative example 1: except only using 1.5g sorbitan tristearate as dispersion agent, other operate with embodiment 1.Obtain white oarse-grained High hydrophilous resin.
Comparative example 2: except not adding Natvosol, other operate with embodiment 1, obtain the High hydrophilous resin of white powder.
The performance test of the High hydrophilous resin obtaining in table 1 embodiment and comparative example
| ? | Outward appearance | Median size (μ m) | Water-intake rate (g/g) | Absorption salt ratio (g/g) | 1 minute absorption salt ratio (g/g) | Rate of liquid aspiration (s) |
| Embodiment 1 | White particle | 290 | 360 | 58 | 48 | 18 |
| Embodiment 2 | White particle | 230 | 345 | 54 | 45 | 14 |
| Embodiment 3 | White particle | 274 | 420 | 60 | 46 | 16 |
| Embodiment 4 | White particle | 216 | 380 | 58 | 45 | 12 |
| Embodiment 5 | Micro-yellow particle | 180 | 330 | 56 | 48 | 8 |
| Embodiment 6 | Micro-yellow particle | 168 | 345 | 56 | 50 | 7 |
| Comparative example 1 | White particle | 500 | 280 | 52 | 21 | 65 |
| Comparative example 2 | White powder | 90 | 250 | 43 | 40 | 5 |
From the test result of table 1, the High hydrophilous resin obtaining in embodiment 1-6, median size, between 150-300 μ m, has moderate water-intake rate and absorption salt ratio, faster rate of liquid aspiration.On the other hand, only use sorbitan tristearate to make dispersion agent, grain diameter is thicker, and rate of liquid aspiration is slow; Do not use thickening material, particle diameter is partially thin, affects its use value.
Claims (9)
1. a method for preparing super absorbent resin by inverse suspension polymerization, is characterized in that
1) take hydrophobic lipophilicity organism is solvent, and the 0.1%-10% dispersion agent that is Acrylic Acid Monomer quality by consumption adds in solvent, in 40～60 ℃ of heating for dissolving;
2) add quantitative vinylformic acid, in ice-water bath, with sodium hydroxide solution neutralization, after neutralization, adding consumption is 0.01%～5% thickening material, linking agent and the water soluble starter of Acrylic Acid Monomer quality, obtains Acrylic Acid Monomer solution;
3) Acrylic Acid Monomer solution is added in solvent, pass into while stirring nitrogen 30～60 minutes, temperature is increased to 60～80 ℃, react 2～5 hours;
4) after reaction finishes, temperature is increased to 85～95 ℃, carries out azeotropic dehydration;
5) after dehydration finishes, be cooled to 40～60 ℃ and filter, use afterwards absolute ethanol washing, then at 60～80 ℃, be dried 30～60 minutes;
6) use surface crosslinking agent to carry out surface-crosslinked processing, finally obtain super absorbent resin;
Described dispersion agent be take Tripolyglycerol monostearates and the sorbitan tristearate that ratio is 1: 2～2: 1 and is formed;
Described thickening material is selected from one or more of Natvosol, hydroxypropylcellulose, methylcellulose gum and carboxymethyl cellulose.
2. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, it is characterized in that described solvent is selected from Skellysolve A, normal hexane, normal heptane, octane, hexanaphthene, cyclooctane and methylcyclohexane one or more, consumption is the 50%-600% of described Acrylic Acid Monomer quality.
3. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, is characterized in that described water soluble starter is Potassium Persulphate, and consumption is 0.05～3% of Acrylic Acid Monomer quality.
4. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, it is characterized in that described linking agent is selected from ethylene glycol, propylene glycol, glycerol, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propanetriol-diglycidyl-ether, one contracting two propanetriol-diglycidyl-ethers, sorbyl alcohol glycidyl ether, N.N '-methylene-bisacrylamide, N hydroxymethyl acrylamide, EDIA, polyethylene glycol acrylate, one or more of propylene glycol acrylate and triallylamine, consumption is 0.01～3% of Acrylic Acid Monomer quality.
5. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, is characterized in that described inverse suspension polymerization temperature of reaction is 60～80 ℃, and the time is 2-5 hour.
6. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, it is characterized in that described surface crosslinking agent is selected from ethanol, ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, glycerol, polyglycerol, Virahol, 1, 4-butyleneglycol, diethanolamine, trolamine, polyethenoxy ether, ethylene glycol diglycidylether, epoxy chloropropane, quadrol, diethylenetriamine, triethylene tetramine, aluminum chloride, magnesium chloride, calcium chloride, Tai-Ace S 150, one or more of magnesium sulfate and calcium sulfate, consumption is used 0.5～30 part with respect to the resin of 100 parts of quality.
7. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, is characterized in that 70～200 ℃ of described surface-crosslinked temperature, and the time is 0.5-1 hour.
8. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, the described High hydrophilous resin median size making is 100～200 μ m.
9. the method for preparing super absorbent resin by inverse suspension polymerization according to claim 1, the described High hydrophilous resin 1min absorption salt ratio making is more than 45g/g, and rate of liquid aspiration is in 20s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110307721.3A CN102408505B (en) | 2011-10-12 | 2011-10-12 | Method for preparing super absorbent resin by inverse suspension polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110307721.3A CN102408505B (en) | 2011-10-12 | 2011-10-12 | Method for preparing super absorbent resin by inverse suspension polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408505A CN102408505A (en) | 2012-04-11 |
| CN102408505B true CN102408505B (en) | 2014-04-23 |
Family
ID=45910887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110307721.3A Active CN102408505B (en) | 2011-10-12 | 2011-10-12 | Method for preparing super absorbent resin by inverse suspension polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408505B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492069B (en) * | 2011-12-19 | 2013-08-14 | 江苏大学 | Water-absorbing resin dry glue powder and application thereof in demulsification of oil-water emulsion |
| CN103421134B (en) * | 2012-05-17 | 2016-03-09 | 浙江卫星石化股份有限公司 | The preparation method of a kind of cable or optical cable High hydrophilous resin |
| CN103145887B (en) * | 2013-03-07 | 2015-02-25 | 中国石油大学(华东) | Method and device for preparing microballoons by bi-dispersible inverse suspension polymerization |
| CN103215023B (en) * | 2013-04-26 | 2015-08-05 | 浙江师范大学 | A kind of water-ol type hydraulic liquid thickening material and its preparation method and application |
| CN103554331A (en) * | 2013-11-05 | 2014-02-05 | 中海油能源发展股份有限公司惠州石化分公司 | Method for preparing polyacrylic acid high-water-absorptivity resin microspheres by reversed phase suspension polymerization |
| CN103601834A (en) * | 2013-11-19 | 2014-02-26 | 宜兴丹森科技有限公司 | Method for preparing super absorbent resin through reverse suspension polymerization |
| CN104918964B (en) * | 2014-07-11 | 2017-07-18 | 住友精化株式会社 | The manufacture method of water-absorbing resins |
| JP5719078B1 (en) | 2014-07-11 | 2015-05-13 | 住友精化株式会社 | Method for producing water absorbent resin |
| KR102086050B1 (en) | 2016-12-20 | 2020-03-06 | 주식회사 엘지화학 | Super absorbent polymer and preparation method thereof |
| CN108822730B (en) * | 2018-06-05 | 2020-08-04 | 山东科技大学 | Thin spray material for roadway reinforcement dust adhesion and preparation method thereof |
| CN108745323B (en) * | 2018-06-07 | 2021-04-09 | 干霸干燥剂(深圳)有限公司 | Fiber-based super absorbent resin calcium chloride composite gel drying agent and preparation method thereof |
| CN112705266A (en) * | 2021-01-26 | 2021-04-27 | 丹东明珠特种树脂有限公司 | Catalyst for preparing methyl methacrylate, preparation method and esterification preparation process thereof |
| CN113897010B (en) * | 2021-10-25 | 2023-03-31 | 湖南俏妃卫生用品有限公司 | Preparation method of super absorbent resin |
| CN114149529A (en) * | 2021-12-31 | 2022-03-08 | 南京紫鸿生物科技有限公司 | Partially neutralized sodium polyacrylate and its preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165152A (en) * | 1997-04-22 | 1997-11-19 | 梅秀泉 | Polyacrylate type high water absorption resin |
| JP2000128907A (en) * | 1998-10-22 | 2000-05-09 | Mitsubishi Chemicals Corp | Production of water-absorbing polymer |
| JP2002105125A (en) * | 2000-09-27 | 2002-04-10 | Sumitomo Seika Chem Co Ltd | Method for producing water-absorbing resin |
| CN1834122A (en) * | 2006-04-11 | 2006-09-20 | 浙江大学 | Method of preparing high water absorbing resin by process of reversed phase suspension polymerizing polypropylene |
| CN1903893A (en) * | 2006-07-19 | 2007-01-31 | 浙江大学 | Antisticking agent in preparation of reversed phase suspension polymerization polypropylene high water absorption resin |
| CN101225132A (en) * | 2007-12-20 | 2008-07-23 | 中国科学院长春应用化学研究所 | Preparation method of reverse phase suspension polymerization polymethacrylic acid hygroscopic resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06345819A (en) * | 1993-06-08 | 1994-12-20 | Nippon Synthetic Chem Ind Co Ltd:The | Production of highly water absorbing resin |
-
2011
- 2011-10-12 CN CN201110307721.3A patent/CN102408505B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165152A (en) * | 1997-04-22 | 1997-11-19 | 梅秀泉 | Polyacrylate type high water absorption resin |
| JP2000128907A (en) * | 1998-10-22 | 2000-05-09 | Mitsubishi Chemicals Corp | Production of water-absorbing polymer |
| JP2002105125A (en) * | 2000-09-27 | 2002-04-10 | Sumitomo Seika Chem Co Ltd | Method for producing water-absorbing resin |
| CN1834122A (en) * | 2006-04-11 | 2006-09-20 | 浙江大学 | Method of preparing high water absorbing resin by process of reversed phase suspension polymerizing polypropylene |
| CN1903893A (en) * | 2006-07-19 | 2007-01-31 | 浙江大学 | Antisticking agent in preparation of reversed phase suspension polymerization polypropylene high water absorption resin |
| CN101225132A (en) * | 2007-12-20 | 2008-07-23 | 中国科学院长春应用化学研究所 | Preparation method of reverse phase suspension polymerization polymethacrylic acid hygroscopic resin |
Non-Patent Citations (1)
| Title |
|---|
| 高吸水性树脂表面交联改性的研究进展;张春晓等;《2009中国功能材料科技与产业高层论坛论文集》;20091231;第565-567页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408505A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408505B (en) | Method for preparing super absorbent resin by inverse suspension polymerization | |
| CN103910896B (en) | A kind ofly lowly return the preparation method of oozing hydroscopic high-molecular resin | |
| CN100398573C (en) | Method for preparing high absorptive resin in acrylic acid type | |
| CN103665411B (en) | A kind of high hydroscopic resin and preparation method thereof of high salt tolerant high water absorption multiplying power | |
| CN102153693B (en) | Salt-tolerant acrylic absorbent resin and method for preparing same | |
| US20080119626A1 (en) | Polyacrylic Acid (Salt) Water-Absorbent Resin, Production Process Thereof, and Acrylic Acid Used in Polymerization for Production of Water-Absorbent Resin | |
| CN105837725B (en) | Water-absorbing resins and preparation method thereof | |
| CN1733815A (en) | Preparation method of high-strength water-absorbing material | |
| CN109608666A (en) | A kind of surface-crosslinked technique of the water-absorbing resins comprising special feed way | |
| CN107722163A (en) | The water-absorbing resins and its application of acrylic water-absorbent resin and low soluble component | |
| JPH03195713A (en) | Production of polymer having high water absorption | |
| CN107522991A (en) | A kind of super absorbent resin prepared using a step inverse suspension polymerization and preparation method thereof | |
| JPS63270741A (en) | Production of water-absorptive polyacrylic acid resin | |
| CN105297428B (en) | A kind of preparation method of high-hydroscopicity complex | |
| CN109535307A (en) | A kind of inverse suspension polymerization preparation process of water-absorbing resins | |
| CN104177556B (en) | Plastic stabilizer and preparation method thereof | |
| CN103421134B (en) | The preparation method of a kind of cable or optical cable High hydrophilous resin | |
| KR100258017B1 (en) | Superabsorbent polymer | |
| JP2012207139A (en) | Method for producing absorbent resin, and the absorbent resin | |
| TW201427726A (en) | Odour-and colour-stable water-absorbing composition | |
| JPH02194010A (en) | Production of polymetal acrylate | |
| CN103087252A (en) | Preparation method of high-absorption composite | |
| CN100443553C (en) | Preparation method of superabsorbent and water-retaining composite material containing amorphous silicate mineral | |
| CN101333261B (en) | A kind of manufacturing method of superabsorbent resin | |
| CN1817916A (en) | Composite materials with high water absorbing and retaining performances containing diatomite and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161214 Address after: 314000 Jiaxing City, South Lake District, Zhejiang Bridge Town, step by step Coke Road, No. 565 Patentee after: Zhejiang satellite Mstar Technology Ltd Address before: 314000 Jiaxing Industrial Park, Jiaxing, step by step Coke Road, No. 1, No. Patentee before: Zhejiang Satellite Petro Chemical Co., Ltd. |