CN114989336B - 一种小分子交联剂超吸水树脂材料及其制备方法 - Google Patents
一种小分子交联剂超吸水树脂材料及其制备方法 Download PDFInfo
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- CN114989336B CN114989336B CN202210693251.7A CN202210693251A CN114989336B CN 114989336 B CN114989336 B CN 114989336B CN 202210693251 A CN202210693251 A CN 202210693251A CN 114989336 B CN114989336 B CN 114989336B
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- resin material
- absorbent resin
- super absorbent
- tungstate
- linking agent
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- 239000011347 resin Substances 0.000 title claims abstract description 88
- 229920005989 resin Polymers 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000002250 absorbent Substances 0.000 title claims abstract description 76
- 230000002745 absorbent Effects 0.000 title claims abstract description 70
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims abstract description 4
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 claims abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 150000003384 small molecules Chemical class 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
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- 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
- 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 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 53
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- IGWIEYXEWVUGCK-UHFFFAOYSA-N 4-aminobenzenesulfonic acid;sodium Chemical compound [Na].NC1=CC=C(S(O)(=O)=O)C=C1 IGWIEYXEWVUGCK-UHFFFAOYSA-N 0.000 abstract description 3
- 229950000244 sulfanilic acid Drugs 0.000 abstract description 3
- 229920002125 Sokalan® Polymers 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 21
- 238000012360 testing method Methods 0.000 description 17
- 230000008961 swelling Effects 0.000 description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 239000004202 carbamide Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 10
- 238000010998 test method Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
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- 238000004065 wastewater treatment Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
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- 229960005070 ascorbic acid Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 239000000017 hydrogel Substances 0.000 description 1
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- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- -1 sodium tungstate small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
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- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
本发明公开了一种小分子交联剂超吸水树脂材料及其制备方法,由聚合物基体和小分子交联剂组成,所述小分子交联剂包括钨酸钠、钨酸钾、钨酸钙、钨酸铵、对氨基苯磺酸、对氨基苯磺酸钠、钨酸钴、钨酸亚铁、钨酸铵、钨酸锌中的一种或多种。本发明得到具有优异吸水保水性能的超吸水树脂材料,小分子交联剂具有廉价、低生物毒性、易得等优势。
Description
技术领域
本发明属于功能性高分子材料技术领域,具体涉及到一种小分子交联剂超吸水树脂材料及其制备方法。
背景技术
超吸水树脂(SAPs)是一种功能性高分子材料,由于其独特的三维亲水交联网络,可以吸收和保持高达自身重量数百至数千倍的大量水分。目前,SAPs在农业、生物医学、日化和废水处理等领域得到了快速发展。目前,人们已经深入研究了单体对SAPs吸水性能的影响,证明了单体在决定吸水性方面起着关键作用。同时,除了各种单体外,交联剂对合成SAPs的吸水能力也有很大影响,因为SAPs的结构稳定性主要由交联剂决定。事实上,SAPs独特的吸水能力来源于其亲水基团和适当的交联结构,其中交联是实现稳定SAPs的关键过程。因此,SAPs的吸水行为与交联剂高度相关。例如,Hu等(J.Mater.Chem.A,2020,8,12613)发现引入氢氧化钙纳米颗粒(CNS)作为物理交联剂有利于形成绒毛状结构,从而进一步显著提高制备SAPs的吸水能力。然而,这种CNS是通过硅酸三钙的水化过程产生,而水化温度也应固定在0℃左右,因为纳米颗粒的大小受温度控制。此外,这种绒毛状SAPs的合成温度必须控制在0℃左右,以确保CNS不会失效。因此,尽管可以显著提高溶胀率,但CNS及其相应SAPs的生产将消耗大量能量;Chen等(RSC Adv.,2020,10,41022)使用改性二氧化硅纳米颗粒(VSNPs)作为交联剂来提高SAPs的吸水能力,其溶胀率可达到5000g/g。然而,VSNPs的生产也存在一些缺点,如制造工艺复杂、能耗高。此外,作为最常用的交联剂,虽然N,N'-亚甲基双丙烯酰胺(MBA)可以有效提高SAPs的结构稳定性,但MBA对生物仍有一定的毒性,其对应的SAPs也表现出相对较低的吸水能力。
因此,迫切需要寻找廉价、低生物毒性、易得、低能耗的新型交联剂。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊,而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题,提出了本发明。
本发明的其中一个目的是提供一种小分子交联剂超吸水树脂材料。
为解决上述技术问题,本发明提供了如下技术方案:一种小分子交联剂超吸水树脂材料,由聚合物基体和小分子交联剂组成;
所述聚合物基体由高分子单体聚合而成,所述高分子单体包括丙烯酸及其盐或酯/脂、丙烯酰胺、甲基丙烯酰胺、(3-丙烯酰胺丙基)三甲基氯化铵、N-异丙基丙烯酰胺、2-丙烯酰胺-2-甲基丙磺酸及其盐类、二甲基二烯丙基氯化铵、甲基丙烯酸、丙烯酸-2-羟乙脂、甲基丙烯酸酯、N-羟甲基丙烯酰胺、二甲胺基丙基丙烯酰胺、甲基丙烯酸-2-羟乙脂中的一种或多种;
所述小分子交联剂包括钨酸钠、钨酸钾、钨酸钙、钨酸铵、对氨基苯磺酸、对氨基苯磺酸钠、钨酸钴、钨酸亚铁、钨酸铵、钨酸锌中的一种或多种。
作为本发明小分子交联剂超吸水树脂材料的一种优选方案,其中:所述小分子交联剂用量为所述高分子单体用量的0.1~40wt%。
本发明的另一个目的是提供如上述所述的小分子交联剂超吸水树脂材料的制备方法,包括,
将中和剂至于去离子水中溶解,搅拌均匀得到中和剂溶液;
将高分子单体加入到中和剂溶液,搅拌均匀得到混合液A;
将小分子交联剂加入混合液A,搅拌均匀得到混合液B;
将引发剂、催化剂加入上述混合液B,搅拌均匀,静置得到超吸水树脂材料。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:所述述中和剂包括氢氧化钠、氢氧化钾、氢氧化铵、三乙醇胺、氨甲基丙醇、氨丁三醇、2-氨基-2-羟甲基-1,3-丙二醇、四羟丙基乙二胺中的一种或多种。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:所述混合液A的pH为1~13。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:所述中和剂用量为所述高分子单体用量的0~90wt%。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:所述引发剂为水溶性单体,所述水溶性单体选自过硫酸铵、过硫酸钾或2,2'-偶氮二异丁基脒二盐酸盐。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:所述催化剂包括N,N,N',N'-四甲基乙二胺、过硫酸钠、硫代硫酸钠、L-抗坏血酸中的一种或多种。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:所述引发剂用量为所述高分子单体用量的0.1~25wt%,所述催化剂用量为所述高分子单体用量的0.1~25wt%。
作为本发明小分子交联剂超吸水树脂材料的制备方法的一种优选方案,其中:反应温度为-20~120℃。
与现有技术相比,本发明具有如下有益效果:
本发明通过钨酸钠小分子交联丙烯酸等高分子单体得到具有优异吸水保水性能的超吸水树脂材料。小分子交联剂具有廉价、低生物毒性、易得等优势。尤其重要的是,合成的超吸水树脂具有卓越的吸水保水性能。制备的超吸水树脂材料可广泛应用于农业、园艺、卫生产品、废水处理等各个领域。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中:
图1为本发明实施例1所得聚丙烯酸/钨酸钠(PAA/ST)超吸水树脂材料在去离子水、0.9wt%NaCl溶液、3wt%尿素溶液里的吸水能力;
图2为本发明实施例1所得聚丙烯酸/钨酸钠(PAA/ST)超吸水树脂材料在不同pH溶液里溶胀能力;
图3为本发明实施例1所得聚丙烯酸/钨酸钠(PAA/ST)超吸水树脂材料在不同温度去离子水溶液里溶胀能力;
图4为本发明实施例1所得聚丙烯酸/钨酸钠(PAA/ST)超吸水树脂材料在土壤里的保水性能。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
其次,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
如无特别说明,实施例中所采用的原料均为商业购买。
实施例1
在室温中,将3g氢氧化钠至于15ml去离子水中溶解,搅拌均匀得到中和剂溶液。接着将6ml丙烯酸加入上述中和剂溶液,搅拌均匀得到混合溶液。接着加入0.1g钨酸钠,搅拌均匀。随后加入0.12g过硫酸铵和60μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PAA/ST超吸水树脂材料。
将得到的PAA/ST超吸水树脂材料进行吸水能力测试,测试方法为:将干燥的吸水树脂材料分别置于去离子水、0.9wt%NaCl溶液、3wt%尿素溶液里,待溶胀平衡后,记录干燥时样品的重量(M0)和溶胀后样品的重量(M1),由二者的相对比率{M1-M0)/M0}计算得到吸水树脂产品的吸水率(g/g)。
测试结果如图1所示,可以看出PAA/ST超吸水树脂材料在去离子水中的吸水率为2370g/g,在0.9wt%NaCl溶液中的吸水率为95g/g,在3wt%尿素溶液中的吸水率为2210g/g。
研究PAA/ST超吸水树脂材料在不同pH溶液里溶胀能力,测试方法为:采用HCl或NaOH调节水溶液的pH值至设定值3~11。随后将干燥的吸水树脂材料至于不同pH值的水溶液,待溶胀平衡后,记录干燥时样品的重量(M0)和溶胀后样品的重量(M1),由二者的相对比率{M1-M0)/M0}计算得到吸水树脂产品在不同pH时的吸水率(g/g)。
PAA/ST超吸水树脂材料在不同pH溶液里溶胀能力见图2。可以看出,在酸性条件下,该超吸水树脂材料的吸水能力较差;在中性及碱性条件下,该超吸水树脂材料的具有较好的吸水能力。
研究PAA/ST超吸水树脂材料在不同温度去离子水溶液里溶胀能力,测试方法为:利用鼓风干燥箱调节去离子水的温度分别至25,45和65℃。然后将干燥的吸水树脂材料至于不同温度的水溶液,待溶胀平衡后,记录干燥时样品的重量(M0)和溶胀后样品的重量(M1),由二者的相对比率{M1-M0)/M0}计算得到吸水树脂产品在不同温度时的吸水率(g/g)。
PAA/ST超吸水树脂材料在不同温度去离子水溶液里溶胀能力见图3。可见,在25~65℃水溶液里,该超吸水树脂材料的吸水能力不受影响。
将得到的PAA/ST超吸水树脂材料用于吸附水溶液里的亚甲基蓝,测试方法为:在室温25℃和pH=7条件下,将该超吸水树脂样品浸泡在100ml不同浓度的亚甲基蓝(25,50,100,200,300和400mg/l)溶液里,研究水凝胶对亚甲基蓝的吸附去除能力。测试结果显示,PAA/ST超吸水树脂材料对亚甲基蓝的吸附去除能力超过90%。
将得到的PAA/ST超吸水树脂材料用于土壤保水剂,测试方法为:在室温25℃下,将0.1g该超吸水树脂材料、40g水和60g泥土至于烧杯中,观察水的浸出情况;空白对照例则仅将40g水和60g泥土至于烧杯中。
两者的对比结果如图4所示,可见PAA/ST超吸水树脂材料可以把水分固定在土壤里(图4b),而未加入PAA/ST超吸水树脂材料的烧杯里有大量水浸出(图4a)。
实施例2
本实施例2与实施例1基本相同,区别在于所用的小分子交联剂材料及用量不同,按照实施例1的方法测试吸水能力,测试结果如表1所示。
表1
由表1中数据可以看出,采用水杨酸钠、木糖醇、无水肌酸、草酸铵、氨基磺酸、肌醇等作为小分子交联剂材料交联丙烯酸单体无法获得超吸水树脂材料;而采用钨酸钠、钨酸钾、对氨基苯磺酸、对氨基苯磺酸钠等作为小分子交联剂材料交联丙烯酸单体则能够获得具有卓越的吸水保水性能的超吸水树脂材料。
实施例3
本实施例3与实施例1基本相同,区别在于所用的引发剂材料及用量不同,按照实施例1的方法测试吸水能力,测试结果如表2所示。
表2
由表2中数据可以看出,在相同的反应条件下,采用偶氮二异庚腈、硝酸铈铵等作为引发剂,无法获得超吸水树脂材料;而采用过硫酸铵、过硫酸钾、2,2'-偶氮二异丁基脒二盐酸盐等作为引发剂则能够获得具有卓越的吸水保水性能的超吸水树脂材料。
实施例4
本实施例4与实施例1基本相同,区别在于所用的催化剂材料及用量不同,按照实施例1的方法测试吸水能力,测试结果如表3所示。
表3
由表3中数据可以看出,在相同的反应条件下,采用亚硫酸钠、L-抗坏血酸等作为催化剂,无法获得超吸水树脂材料;而采用N,N,N',N'-四甲基乙二胺(TEMED)、过硫酸钠等作为催化剂则能够获得具有卓越的吸水保水性能的超吸水树脂材料。
实施例5
本实施例5与实施例1基本相同,区别在于反应温度和pH不同,按照实施例1的方法测试吸水能力,测试结果如表4所示。
表4
由表4中数据可以看出,反应温度过高达到140℃时,无法获得超吸水树脂材料,因此合适的反应温度为-20~120℃。反应的pH过高或过低都无法获得超吸水树脂材料,因此合适的反应pH为1~13。
实施例6
在60℃下,将5g丙烯酰胺加入20ml去离子水中,搅拌均匀得到混合溶液。接着加入0.1g钨酸钠,搅拌均匀。随后加入0.2g过硫酸铵和40μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PAM/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PAM/ST超吸水树脂材料的吸水能力,测试结果显示,PAM/ST超吸水树脂材料在去离子水中的吸水率为205g/g,在0.9wt%NaCl溶液中的吸水率为23g/g,在3wt%尿素溶液中的吸水率为230g/g。
实施例7
在50℃下,将2.5g氢氧化钾至于25ml去离子水中溶解,搅拌均匀得到中和剂溶液。接着将6ml丙烯酸和2g丙烯酰胺加入上述中和剂溶液,搅拌均匀得到混合溶液。接着加入0.1g钨酸钠,搅拌均匀。随后加入0.3g过硫酸铵和100μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PAA/PAM/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PAA/PAM/ST超吸水树脂材料的吸水能力,测试结果显示,PAA/PAM/ST超吸水树脂材料在去离子水中的吸水率为1470g/g,在0.9wt%NaCl溶液中的吸水率为65g/g,在3wt%尿素溶液中的吸水率为1320g/g。
实施例8
在0℃下,将6g丙烯酸钠(AAS)至于18ml去离子水中溶解,接着加入0.5g钨酸钠(ST),搅拌均匀。随后加入0.13g过硫酸铵和85μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PAAS/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PAAS/ST超吸水树脂材料的吸水能力,测试结果显示,PAAS/ST超吸水树脂材料在去离子水中的吸水率为3580g/g,在0.9wt%NaCl溶液中的吸水率为85g/g,在3wt%尿素溶液中的吸水率为2460g/g。
实施例9
在25℃下,将8g丙烯酸钾(PA)至于18ml去离子水中溶解,接着加入0.35g钨酸钠(ST),搅拌均匀。随后加入0.23g过硫酸铵和55μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PPA/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PPA/ST超吸水树脂材料的吸水能力,测试结果显示,PPA/ST超吸水树脂材料在去离子水中的吸水率为2950g/g,在0.9wt%NaCl溶液中的吸水率为116g/g,在3wt%尿素溶液中的吸水率为2350g/g。
实施例10
在80℃下,将5gN-异丙基丙烯酰胺(NIPAM)至于20ml去离子水中溶解,接着加入0.4g钨酸钠(ST),搅拌均匀。随后加入0.25g过硫酸铵和15μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PNIPAM/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PNIPAM/ST超吸水树脂材料的吸水能力,测试结果显示,PNIPAM/ST超吸水树脂材料在去离子水中的吸水率为1560g/g,在0.9wt%NaCl溶液中的吸水率为56g/g,在3wt%尿素溶液中的吸水率为1130g/g。
实施例11
在50℃下,将7.5g丙烯酸羟乙酯(HA)至于20ml去离子水中溶解,接着加入0.25g钨酸钠(ST),搅拌均匀。随后加入0.35g过硫酸铵和40μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PHA/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PHA/ST超吸水树脂材料的吸水能力,测试结果显示,PHA/ST超吸水树脂材料在去离子水中的吸水率为2510g/g,在0.9wt%NaCl溶液中的吸水率为83g/g,在3wt%尿素溶液中的吸水率为2130g/g。
实施例12
在0℃下,将2.5g氢氧化钠至于20ml去离子水中溶解,搅拌均匀得到中和剂溶液。接着将6g2-丙烯酰胺-2-甲基丙磺酸(AMPS)至于上述中和剂溶液,搅拌均匀。随后加入0.32g钨酸钠(ST),搅拌均匀。最后加入0.3g过硫酸铵和40μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PAMPS/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PAMPS/ST超吸水树脂材料的吸水能力,测试结果显示,PAMPS/ST超吸水树脂材料在去离子水中的吸水率为4750g/g,在0.9wt%NaCl溶液中的吸水率为132g/g,在3wt%尿素溶液中的吸水率为3930g/g。
实施例13
在60℃下,将5g二甲基二烯丙基氯化铵(DDAC)至于20ml去离子水中,接着加入0.25g钨酸钠(ST),搅拌均匀。随后加入0.35g过硫酸铵和80μl N,N,N',N'-四甲基乙二胺,搅拌均匀,反应得到PDDAC/ST超吸水树脂材料。
按照实施例1中记载的测试方法测试PDDAC/ST超吸水树脂材料的吸水能力,测试结果显示,该超吸水树脂材料在去离子水中的吸水率为1820g/g,在0.9wt%NaCl溶液中的吸水率为58g/g,在3wt%尿素溶液中的吸水率为1370g/g。
本发明提供了一种小分子交联剂制备超吸水树脂材料及其制备方法。通过钨酸钠等小分子交联丙烯酸等高分子单体得到具有优异吸水保水性能的超吸水树脂材料。小分子交联剂具有廉价、低生物毒性、易得等优势。尤其重要的是,合成的超吸水树脂具有卓越的吸水保水性能。制备的超吸水树脂材料可广泛应用于农业、园艺、卫生产品、废水处理等各个领域。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (2)
1.一种小分子交联剂超吸水树脂材料的制备方法,其特征在于:所述小分子交联剂超吸水树脂材料由聚合物基体和小分子交联剂组成,所述聚合物基体由高分子单体聚合而成;
所述制备方法包括,
将中和剂置于去离子水中溶解,搅拌均匀得到中和剂溶液;所述中和剂用量为所述高分子单体用量的0~90wt%;
将高分子单体加入到中和剂溶液,搅拌均匀得到混合液A;所述混合液A的pH为5~9;所述高分子单体包括丙烯酸及其盐、丙烯酰胺、甲基丙烯酰胺、(3-丙烯酰胺丙基)三甲基氯化铵、N-异丙基丙烯酰胺、2-丙烯酰胺-2-甲基丙磺酸及其盐类、二甲基二烯丙基氯化铵、甲基丙烯酸、丙烯酸-2-羟乙酯、N-羟甲基丙烯酰胺、二甲胺基丙基丙烯酰胺、甲基丙烯酸-2-羟乙酯中的一种或多种;
将小分子交联剂加入混合液A,搅拌均匀得到混合液B;所述小分子交联剂用量为所述高分子单体用量的2~8.33 wt%;所述小分子交联剂包括钨酸钠、钨酸钾、钨酸钙、钨酸铵、钨酸钴、钨酸亚铁、钨酸锌中的一种或多种;
将引发剂、催化剂加入上述混合液B,搅拌均匀,静置得到超吸水树脂材料;
所述引发剂选自过硫酸铵、过硫酸钾或2,2'-偶氮二异丁基脒二盐酸盐;所述引发剂用量为所述高分子单体用量的2.17~7 wt %;
所述催化剂为N,N,N',N'-四甲基乙二胺;
反应温度为-20~120℃。
2.如权利要求1所述的小分子交联剂超吸水树脂材料的制备方法,其特征在于:所述述中和剂包括氢氧化钠、氢氧化钾、氢氧化铵、三乙醇胺、氨甲基丙醇、氨丁三醇、2-氨基-2-羟甲基-1,3-丙二醇、四羟丙基乙二胺中的一种或多种。
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