CN117362694B - Physical-chemical composite crosslinking high oil absorption resin and preparation method and application thereof - Google Patents
Physical-chemical composite crosslinking high oil absorption resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN117362694B CN117362694B CN202311668491.2A CN202311668491A CN117362694B CN 117362694 B CN117362694 B CN 117362694B CN 202311668491 A CN202311668491 A CN 202311668491A CN 117362694 B CN117362694 B CN 117362694B
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- Prior art keywords
- oil absorption
- parts
- resin
- initiator
- high oil
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- 229920005989 resin Polymers 0.000 title claims abstract description 132
- 239000011347 resin Substances 0.000 title claims abstract description 132
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000004132 cross linking Methods 0.000 title abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000003999 initiator Substances 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 34
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- -1 perfluoroalkyl alcohol Chemical compound 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 230000008961 swelling Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 17
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 6
- 229940057995 liquid paraffin Drugs 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- QXJCOPITNGTALI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F QXJCOPITNGTALI-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 4
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 claims description 3
- HMGDEQANNRNNKX-UHFFFAOYSA-N 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononan-1-ol Chemical compound OCCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HMGDEQANNRNNKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 119
- 239000012071 phase Substances 0.000 description 28
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- 238000010382 chemical cross-linking Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-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
- LNUDZOHDUVPVPO-UHFFFAOYSA-N 3,3-difluoro-2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C(F)F)C(F)(F)F LNUDZOHDUVPVPO-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The embodiment of the invention discloses a physical-chemical composite crosslinking high oil absorption resin and a preparation method and application thereof. The method comprises the following steps: carrying out suspension polymerization on styrene and divinylbenzene in the presence of a pore-forming agent, an initiator, a stabilizer and deionized water to obtain skeleton resin; carrying out polymerization reaction on perfluoroalkyl alcohol and alkyl alkenoic acid ester in the presence of an alkaline catalyst and an organic solvent to obtain a fluorinated modified monomer, and carrying out free radical polymerization on the fluorinated modified monomer in the presence of an initiator to obtain a linear fluorine-containing alkyl alkenoic acid ester polymer; swelling the skeleton resin and the linear fluorine-containing alkyl vinyl ester polymer respectively, and carrying out polymerization reaction in the presence of an initiator to obtain the high oil absorption resin. The high oil absorption resin prepared by the invention has good hydrophobicity and thermal stability, large oil absorption, high oil absorption rate, good oil retention performance, easy regeneration of the resin after use, recycling, secondary pollution avoidance and good application prospect in deep oil removal of oily sewage.
Description
Technical Field
The embodiment of the invention relates to the technical field of functional polymer materials, in particular to a physical-chemical composite crosslinking high oil absorption resin and a preparation method and application thereof.
Background
The oil substances carried in the wastewater or the feed liquid are divided into suspension oil, dispersion oil, emulsified oil and dissolved oil according to the existing forms, and the main technical difficulty of oil removal is deep removal of the dissolved oil. Physical adsorption is a relatively mature dissolved oil removal process, and impurities are not additionally introduced in the adsorption process, but deep oil removal level (oil content is less than 1 mg/L) is difficult to achieve.
The high oil absorption resin is a novel functional polymer material developed based on the traditional oil absorption material, and is characterized by moderate crosslinking in microcosmic form, wherein the crosslinking mode mainly comprises chemical crosslinking, physical crosslinking and ionic bond chemical crosslinking. Chemical crosslinking is that long-chain macromolecules are combined together through covalent bonds with larger bond energy to form a stable space three-dimensional network structure. For single chemical crosslinking resin, the chemical crosslinking effect is covalent bond effect, so that the energy is large, the molecular chain is strongly bound by crosslinking, the steric hindrance is large, and the oil-retaining effect is good, but the deep oil removal is difficult.
Physical crosslinking mainly uses intermolecular force, a long-chain macromolecule has hydroxyl or other polar groups to attract each other to form hydrogen bond binding force; the other is the weaker van der Waals forces between the segments of the macromolecules. The ionic bond chemical crosslinking is that polymer chain segments are connected together through ionic bonds, so that a network structure is formed. Polymers formed by physical crosslinking and ionic bond chemical crosslinking have poor thermal stability and limited application.
The theory that the thermal reversibility and the relaxation property of the physical crosslinking can solve the defects of low oil absorption multiplying power and poor oil absorption and release reversibility of the resin and coordinate the functional relationship of adsorption, oil preservation and desorption is considered by a learner to introduce physical crosslinking into the chemically crosslinked oil absorption resin. Compared with single chemical crosslinking, physical crosslinking increases the viscosity of the three-dimensional molecular net and the viscosity coefficient of organic oil molecules diffused in the material, improves the elastic modulus of the material, and forms the three-dimensional molecular net with better rebound resilience. Butadiene rubber and nylon-12 are commonly used physical cross-linking agents. Shan Guorong and the like, a single chemical crosslinking and a physical-chemical compound crosslinking polyacrylate high oil absorption resin taking cis Ding Shengjiao as a physical crosslinking agent are synthesized by adopting a suspension polymerization method, and the research on the adsorption/desorption properties of the two resins shows that the introduction of the physical crosslinking accelerates the oil absorption rate of the resin and improves the oil absorption capacity of the low-lipophilicity monomer resin, and meanwhile, the partial physical crosslinking oil absorption resin is found to have an optimal chemical crosslinking agent content area, but the thermodynamic property and the stress property of the physical-chemical compound crosslinking resin are not deeply studied.
In view of this, the present invention is specifically proposed.
Disclosure of Invention
The present invention has been made based on the following findings of the inventors:
fluorine is used as an element with the strongest electronegativity, and a fluorine carbon bond with extremely high bond energy in the fluorine-containing polymer endows the polymer with the stability of a main chain framework, and the chemical inertness, durability and liquid handling property of the fluorine-containing polymer are the first choice materials for many industrial and commercial applications. It has been found that fluoropolymers containing C-F bonds have many excellent physicochemical properties, such as excellent dielectric properties, very low coefficient of friction, low refractive index, good light transmission, chemical resistance, high and low temperature resistance, low surface tension, good biocompatibility, gas permeability, etc. For example, a porous form of flexible fluoropolymer material (PHFBA-co-PDVB) can separate a variety of organic oils from water and still have excellent thermal stability at 340 ℃. Wan et al prepared porous poly (trifluoroethyl methacrylate-divinylbenzene) P (TFEMA-DVB) material with trifluoroethyl methacrylate (TFEMA) fluoromonomer as oil phase, divinylbenzene (DVB) as cross-linking agent, calcium chloride aqueous solution as water phase, block copolymer Hypermer B246 of polyhydroxy stearic acid and polyethylene glycol as emulsifier, azodiisobutyronitrile (AIBN) as initiator, and the prepared fluorine-containing polymer has good hydrophobicity and acid and alkali corrosion resistance, and can rapidly adsorb organic oil from water surface or bottom, which shows that fluorine-containing polymer has great potential in terms of cleaning spilled oil. Therefore, the inventor introduces the fluorine-containing polymer into a crosslinking system, and conducts intensive research on the thermal stability and oil absorption performance of a crosslinking product, so as to seek oil absorption resin with excellent performance and further meet the actual requirements of oily sewage treatment.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
according to a first aspect of embodiments of the present invention, the present invention provides a method for preparing a physical-chemical composite crosslinked high oil absorption resin, the method comprising the steps of:
(1) Carrying out suspension polymerization on styrene and divinylbenzene in the presence of a pore-forming agent, an initiator, a stabilizer and deionized water to obtain skeleton resin;
(2) Carrying out polymerization reaction on perfluoroalkyl alcohol and alkyl alkenoic acid ester in the presence of an alkaline catalyst and an organic solvent to obtain a fluorinated modified monomer, and carrying out free radical polymerization on the fluorinated modified monomer in the presence of an initiator to obtain a linear fluorine-containing alkyl alkenoic acid ester polymer;
(3) Swelling the skeleton resin and the linear fluorine-containing alkyl vinyl ester polymer respectively, and carrying out polymerization reaction in the presence of an initiator to obtain the high oil absorption resin.
The invention introduces the fluorinated modified linear alkyl olefine acid ester polymer into the chemically crosslinked skeleton resin in a physical crosslinking mode to obtain the physical-chemical composite crosslinking high oil absorption resin material. The physical crosslinking is introduced, so that the steric hindrance of a single chemically crosslinked molecular chain can be improved, the functional relationship of adsorption, oil retention and desorption is coordinated, the modified flexible macromolecular chain is used as a physical crosslinking agent to be introduced into the skeleton resin, a loose three-dimensional molecular network structure with high crosslinking degree and low crosslinking density can be obtained, the oil absorption multiplying power and the oil absorption and release reversibility of the resin are improved, in addition, the linear fluoroalkyl olefine acid ester polymer is polymerized after the alkyl olefine acid ester is fluorinated and modified, the hydrophobicity and the thermal stability of the polymer are improved, and the thermal stability, the oil absorption rate, the oil retention and the desorption performance of the high oil absorption resin are all optimized after the modified polymer is swelled into the skeleton resin. Compared with the traditional deoiling resin, the physical-chemical composite crosslinking high oil absorption resin prepared by the invention has optimized heat stability, oil absorption rate, oil retention and desorption performance, can adsorb and remove dissolved oil under acidic, weak acidic and neutral conditions, and is suitable for wide pH value; the deep oil removal effect on the effluent oil content is less than 1mg/L is obvious; no impurity is introduced; a proper eluent can be selected according to the adsorption condition and the actual field requirement; the resin is easy to regenerate and has long service life; has great popularization and application value.
Further, in the step (1), the preparation method of the skeleton resin includes:
uniformly mixing 100 parts of styrene, 12-36 parts of divinylbenzene, 0-15 parts of pore-forming agent and 0.05-0.8 part of initiator to obtain an oil phase;
1-5 parts of stabilizer are dissolved in 50-230 parts of deionized water to obtain a water phase;
and after the oil phase and the water phase are mixed, heating to 40-60 ℃ under the stirring condition, preserving heat for 2-4 hours, continuously heating to 60-85 ℃, preserving heat for 0.5-3 hours, obtaining yellowish spherical particles, and washing and drying to obtain the skeleton resin.
Further, the pore-forming agent is dichloroethane, toluene, isooctane, n-heptane, n-hexane, isoamyl alcohol or liquid paraffin, preferably, the pore-forming agent consists of any one of toluene, isooctane or isoamyl alcohol and liquid paraffin according to the volume ratio of 3:1;
the initiator is an oil-soluble initiator, it being understood that oil-soluble initiators include organic peroxide initiators: such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, and the like; azo initiator: such as azobisisobutyronitrile, azobisisoheptonitrile, preferably the oil-soluble initiator is azobisisobutyronitrile, t-butyl hydroperoxide or benzoyl peroxide;
the stabilizer is polyvinylpyrrolidone, gelatin, cetyl trimethyl ammonium bromide or polyvinyl ethyl ether, and preferably the stabilizer is polyvinylpyrrolidone or cetyl trimethyl ammonium bromide.
Further, in some specific embodiments, the washing step is: and (3) performing centrifugal washing by using an organic solvent and deionized water, wherein the organic solvent is methanol, ethanol, n-propanol, isopropanol and the like. The drying conditions are as follows: and (5) vacuum drying at 40-60 ℃ for 4-12 h.
Further, in the step (2), the preparation method of the linear fluoroalkyl enoate polymer comprises the following steps:
adding the organic solvent with the molar ratio of 1: 0.4-1: 0.01-0.1 of perfluoroalkyl alcohol, alkyl alkenoic acid ester and alkaline catalyst, stirring for 4-8 hours at 50-110 ℃, cooling to room temperature, washing, and removing water to obtain a mixture containing fluorinated modified monomers;
and (3) adding an initiator into the mixture containing the fluorinated modified monomer in an inert gas atmosphere, stirring for 3-6 hours at 40-70 ℃, and then performing reduced pressure rotary evaporation, washing and drying to obtain the linear fluorine-containing alkyl vinyl ester polymer, wherein the addition amount of the initiator is 0.1-1.5 parts by 100 parts of the fluorinated modified monomer.
Further, the perfluoroalkyl alcohol is perfluoro-n-butanol, 3- (perfluoro-n-hexyl) propanol or tetrafluoropropanol, and preferably, the perfluoroalkyl alcohol is perfluoro-n-butanol;
the alkyl vinyl acid ester is acrylic ester, vinyl acid ester or butenyl acid ester, preferably, the alkyl vinyl acid ester is methyl methacrylate, ethyl methacrylate or methyl vinyl acetate;
the alkaline catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide or calcium hydroxide, and preferably, the alkaline catalyst is sodium hydroxide or potassium hydroxide;
the organic solvent is n-butanol, n-amyl alcohol or isoamyl alcohol;
the initiator is an oil-soluble initiator, and preferably the oil-soluble initiator is azobisisobutyronitrile or di-tert-butyl peroxide.
Further, in some specific embodiments, in the step of preparing the mixture comprising the fluorinated modifying monomer, washing is performed using an alkaline saturated solution and deionized water, wherein the alkaline solute of the alkaline saturated solution is sodium hydroxide, sodium carbonate, potassium hydroxide, sodium bicarbonate or potassium bicarbonate, preferably sodium carbonate. Adding a drying agent for removing water, wherein the drying agent is anhydrous sodium sulfate, anhydrous magnesium sulfate, anhydrous calcium sulfate, silica gel or anhydrous calcium chloride, and preferably anhydrous sodium sulfate or anhydrous calcium chloride.
Further, in the step (3), the preparation method of the high oil absorption resin comprises the following steps:
stirring and emulsifying 0-10 parts of pore-forming agent, 0.5-15 parts of emulsifier and 350-500 parts of deionized water, adding 150-300 parts of skeleton resin, and stirring and swelling for 3-12 hours at the rotating speed of 50-250 r/min to obtain a first mixed solution;
stirring and emulsifying 20-50 parts of an organic solvent, 0.5-15 parts of an emulsifying agent and 200-350 parts of an inorganic salt water solution, adding 100 parts of the linear fluorine-containing alkyl acrylate polymer, and stirring and swelling for 3-12 hours at the rotating speed of 50-250 r/min to obtain a second mixed solution;
and (3) stirring 0.1-1 part of the first mixed solution, the second mixed solution and the initiator at 60-90 ℃ for 6-15 hours in an inert gas atmosphere, cooling the system to room temperature, washing, and drying to obtain the high oil absorption resin.
Further, the pore-forming agent is one or more of dichloroethane, toluene, isooctane, tetrachloroethylene, n-heptane, n-hexane, isoamyl alcohol and liquid paraffin, and preferably, the pore-forming agent is dichloroethane or tetrachloroethylene;
the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, polyoxyethylene ether, polyoxypropylene ether or polyvinyl alcohol, and preferably, the emulsifier is sodium dodecyl sulfate or polyvinyl alcohol;
the inorganic salt water solution is 1-10% of sodium chloride water solution, calcium chloride water solution or magnesium chloride water solution, preferably sodium chloride water solution;
the initiator is an inorganic peroxide initiator, comprising potassium persulfate, sodium persulfate or ammonium persulfate, and preferably, the initiator is ammonium persulfate;
the organic solvent is methanol or ethanol.
Further, in some specific embodiments, the washing step is: washing with alcohol organic solvent for 2-3 times and washing with deionized water for 3-5 times. The drying step is as follows: and drying for 4-12 hours at the temperature of 40-60 ℃ in a vacuum drying oven.
According to a second aspect of embodiments of the present invention, there is provided a physical-chemical composite crosslinked high oil absorption resin made by the method as described in any one of the above.
According to a third aspect of embodiments of the present invention, the present invention provides an application of the above-described physical-chemical composite crosslinked high oil absorption resin in treatment of oily wastewater or feed liquid.
According to a fourth aspect of embodiments of the present invention, there is provided a method of degreasing oily wastewater or feed liquid, the method comprising the steps of:
(1) Filtering the oily wastewater or feed liquid to remove suspended matters;
(2) Loading the high oil absorption resin as described above into an adsorption column;
(3) The oily wastewater or feed liquid after suspended matters are removed in the step (1) enters an adsorption column in the step (2) from bottom to top, and top water is discharged after oil removal;
(4) When the oil content of the effluent does not meet the requirement, the high oil absorption resin reaches the penetrating adsorption capacity, and the resin needs to be regenerated.
The pH range of the oil-containing feed liquid/wastewater treated by the resin is 2-7, the highest applicable temperature is 120 ℃, the normal operation temperature is 10-80 ℃, the filling height is 0.8-2.2 m, and the expansion rate is 20-50%. According to specific adsorption conditions and actual production requirements, the eluent can be selected from ethanol, 40-60 ℃ sodium hydroxide solution (5-30 wt%) and 50-70 ℃ hot water. The eluent consumption is 3 BV-8 BV, and the regeneration flow rate is 1 BV/h-5 BV/h; after regeneration, the rinsing rate of clean water is 2 m/h-15 m/h, and the rinsing time is 60 min-120 min.
The preparation mechanism of the high oil absorption resin is as follows:
(1) Preparing skeleton resin by suspension polymerization of styrene-divinylbenzene: polymerization of styrene and divinylbenzene involves the formation and consumption of dangling double bonds during the copolymerization. For mono-ene (styrene) -diene (divinylbenzene) radical cross-linking copolymerization, the introduction of diene monomers forms dangling double bonds on the base chain. When styrene is polymerized with divinylbenzene, after one vinyl group of the divinylbenzene reacts, the reactivity of the second vinyl group is significantly reduced and a portion of the copolymer retains dangling double bonds therein.
(2) Preparation of a linear fluoroalkyl enoate polymer: reacting alkyl olefine acid ester with perfluoroalkyl alcohol for fluorination modification to generate alkyl olefine acid perfluoro ester, and then initiating free radical polymerization by an initiator to obtain the linear fluorine-containing olefine acid polymer. Taking ethyl methacrylate and perfluoro-n-butanol to obtain perfluoro-methacrylate as an example, and obtaining the poly-perfluoro-methacrylate after polymerization.
(3) Preparing physical-chemical composite crosslinking high oil absorption resin by a swelling method: (1) stirring and emulsifying a pore-forming agent, an emulsifying agent and deionized water, adding a skeleton resin, and swelling; (2) stirring and emulsifying an organic solvent, an emulsifying agent and deionized water, adding a linear fluorine-containing alkyl acrylate polymer, and swelling; (3) mixing the swelled materials (1) and (2), adding an initiator, and gradually heating and polymerizing under the inert gas atmosphere. And refining the reactant to obtain the physical-chemical composite cross-linked high oil absorption resin.
The embodiment of the invention has the following advantages:
the invention is mainly aimed at innovatively optimizing the preparation method of the high oil absorption resin capable of deeply removing oil. From the standpoint of polymer molecular design, (1) perfluoroalkyl alcohol modified alkyl alkenoate, introducing perfluoro group; (2) controlling the polymerization degree of the monomer after the fluorination modification to obtain a linear fluorine-containing vinyl acid ester polymer; (3) preparing 'skeleton' resin by chemical cross-linking polymerization of styrene and divinylbenzene; (4) the high oil absorption resin containing physical-chemical compound crosslinking is obtained by a swelling polymerization method of 'skeleton' resin and linear fluorine-containing alkyl olefine acid ester copolymer. The high oil absorption resin prepared by the invention has good hydrophobicity and thermal stability, large oil absorption, high oil absorption rate, good oil retention performance, easy regeneration of the resin after use, recycling, secondary pollution avoidance and good application prospect in deep oil removal of oily sewage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
FIG. 1 is a graph showing the variation of sample mass with temperature or time according to the present invention;
fig. 2 shows the change of the oil absorption rate of the sample with time.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following, unless otherwise specified, "parts" means "parts by weight".
Example 1
The embodiment provides a preparation method of a physical-chemical composite cross-linked high oil absorption resin, which comprises the following steps:
(1) Preparation of backbone resin
Mixing 100 parts of styrene, 25 parts of divinylbenzene and 0.1 part of azodiisobutyronitrile, uniformly stirring, adding 15 parts of isooctane, and continuously stirring to uniformly disperse all the components to obtain an oil phase;
adding 5 parts of cetyl trimethyl ammonium bromide into 120 parts of deionized water, and uniformly stirring to obtain a water phase;
mixing the oil phase and the water phase, stirring and heating to 60 ℃, keeping for 2 hours, continuously heating to 75 ℃, keeping the temperature for 1.5 hours to obtain yellowish spherical particles, washing the solid by ethanol and deionized water, and carrying out vacuum drying for 10 hours at 50 ℃ to obtain the resin microsphere taking styrene-divinylbenzene as a framework.
(2) Preparation of linear fluoroalkylacrylate copolymers
To 135ml of butanol, 0.5mol of perfluoro-n-butanol, 0.25mol of ethyl methacrylate and 0.03mol of sodium hydroxide were added, and the mixture was stirred and heated to 55℃and kept at the temperature for 1 hour, and the temperature was further raised to 95℃and kept at the temperature for 7 hours. Cooling to room temperature, washing the organic phase with saturated sodium carbonate solution, washing with deionized water to neutrality, adding anhydrous sodium sulfate to the oil phase for dewatering, and filtering to obtain mixture containing fluoridated modified monomer.
Adding azodiisobutyronitrile into the mixture containing the fluorinated modified monomer, adding 0.1 part of azodiisobutyronitrile based on 100 parts of the fluorinated modified monomer, carrying out polymerization reaction for 6 hours at 60 ℃ in an inert gas atmosphere, and removing the solvent in the oil phase by rotary evaporation under reduced pressure after the reaction is finished. Washing the crude product with a proper amount of ethanol for 2-3 times, washing with deionized water for 2-3 times, and drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain the linear fluorine-containing butyl methacrylate polymer.
(3) Preparation of composite cross-linked high oil absorption resin
Stirring and emulsifying 5 parts of dichloroethane, 1 part of sodium dodecyl sulfate and 350 parts of deionized water, adding 200 parts of the skeleton resin prepared in the step (1), and stirring at room temperature (80-150 r/min) to swell for 12h to obtain a first mixed solution;
stirring and emulsifying 20 parts of ethanol, 3 parts of sodium dodecyl sulfate and 200 parts of 5% sodium chloride aqueous solution, adding 100 parts of the linear fluorine-containing butyl methacrylate polymer prepared in the step (2), and stirring at room temperature (80 r/min-100 r/min) to swell for 10 hours to obtain a second mixed solution;
and adding the first mixed solution, the second mixed solution and 0.2 part of ammonium persulfate into a reactor with a temperature control, stirring and condensation reflux system, and reacting at 85 ℃ for 10 hours in an inert gas atmosphere. And (3) after the system is cooled to room temperature, washing with ethanol for 2-3 times, washing with deionized water for 3-5 times, and drying in a vacuum drying oven at 40 ℃ for 6 hours to obtain the composite cross-linked high oil absorption resin, which is denoted as ORZ-C1.
Example 2
The embodiment provides a preparation method of a physical-chemical composite cross-linked high oil absorption resin, which comprises the following steps:
(1) Preparation of backbone resin
Mixing 100 parts of styrene, 35 parts of divinylbenzene and 0.2 part of benzoyl peroxide, uniformly stirring, adding 12 parts of a mixture of isoamyl alcohol and liquid paraffin in a volume ratio of 3:1, and continuously stirring to uniformly disperse all the components to obtain an oil phase;
adding 3 parts of polyvinylpyrrolidone into 150 parts of deionized water, and uniformly stirring to obtain a water phase;
mixing the oil phase and the water phase, stirring and heating to 50 ℃, preserving heat for 1h, continuously heating to 80 ℃, preserving heat for 3h to obtain yellowish spherical particles, washing solids with diethyl ether and deionized water, and vacuum drying at 40 ℃ for 12h to obtain the resin microsphere taking styrene-divinylbenzene as a framework.
(2) Preparation of linear fluoroalkylacrylate copolymers
To 110ml of isobutanol, 1.0mol of tetrafluoropropanol, 0.55mol of methyl methacrylate and 0.03mol of potassium hydroxide were added, and the mixture was stirred and heated to 55℃and kept at that temperature for 1 hour, and then the temperature was further raised to 100℃and kept at that temperature for 6 hours. Cooling to room temperature, washing an organic phase with saturated sodium carbonate solution, washing with a proper amount of deionized water to be neutral, adding a proper amount of anhydrous calcium chloride into an oil phase for dewatering, and filtering to obtain a mixture containing fluorinated modified monomers;
and adding di-tert-butyl peroxide into the mixture containing the fluorinated modified monomer, adding 0.2 part of di-tert-butyl peroxide based on 100 parts of the fluorinated modified monomer, carrying out polymerization reaction for 5-6 hours at 70 ℃ in an inert gas atmosphere, and removing the solvent in the oil phase by rotary evaporation under reduced pressure after the reaction is finished. Washing the crude product with a proper amount of ethanol for 2-3 times, washing with deionized water for 2-3 times, and drying in a vacuum drying oven at 50 ℃ for 10 hours to obtain the linear fluorine-containing propyl methacrylate polymer.
(3) Preparation of composite cross-linked high oil absorption resin
Stirring and emulsifying 5 parts of dichloroethane, 6 parts of sodium dodecyl sulfonate and 350 parts of deionized water, adding 240 parts of the resin microspheres prepared in the step (1), and stirring at room temperature (80-110 r/min) to swell for 12 hours to obtain a first mixed solution;
30 parts of methanol, 3 parts of polyvinyl alcohol and 250 parts of 8% magnesium chloride solution are stirred and emulsified at 95 ℃, cooled to 45 ℃, 100 parts of linear fluorine-containing propyl methacrylate polymer prepared in the step (2) is added, and stirred (100 r/min-110 r/min) and swelled for 8 hours to obtain a second mixed solution;
and adding the first mixed solution, the second mixed solution and 0.2 part of ammonium persulfate into a reactor with a temperature control, stirring and condensation reflux system, keeping the temperature at 60 ℃ for 2 hours under an inert gas atmosphere, continuously heating to 80 ℃ and keeping the temperature for 10 hours, cooling the system to room temperature, washing with ethanol for 2-3 times, washing with deionized water for 3-5 times, and drying in a vacuum drying oven at 40 ℃ for 6 hours to obtain the composite cross-linked high oil absorption resin, which is denoted as ORZ-C2.
Example 3
The embodiment provides a preparation method of a physical-chemical composite cross-linked high oil absorption resin, which comprises the following steps:
(1) Preparation of backbone resin
Mixing 100 parts of styrene, 15 parts of divinylbenzene and 0.15 part of benzoyl peroxide, uniformly stirring, adding 10 parts of toluene, and continuously stirring to uniformly disperse all the components to obtain an oil phase;
adding 2 parts of cetyl trimethyl ammonium bromide into 120 parts of deionized water, and uniformly stirring to obtain a water phase;
mixing the oil phase and the water phase, stirring and heating to 50 ℃, preserving heat for 1h, continuously heating to 75 ℃, preserving heat for 3h to obtain yellowish spherical particles, washing solid with ethanol and deionized water, and vacuum drying at 55 ℃ for 6h to obtain the resin microsphere taking styrene-divinylbenzene as a framework.
(2) Preparation of linear fluoroalkylacrylate copolymers
Adding 0.6mol of 3- (perfluoro-n-hexyl) propanol, 0.2mol of methyl vinyl acetate and 0.05mol of sodium hydroxide into 95ml of isobutanol, stirring and heating to 65 ℃, keeping the temperature for 1h, continuously heating to 110 ℃, keeping the temperature for 7h, cooling to room temperature, washing an organic phase with saturated sodium carbonate solution, washing a proper amount of deionized water to be neutral, adding a proper amount of anhydrous magnesium sulfate into an oil phase for dewatering, and filtering to obtain a mixture containing fluorinated modified monomers;
adding azodiisobutyronitrile into the mixture containing the fluorinated modified monomer, adding 0.3 part of azodiisobutylcyanide based on 100 parts of the fluorinated modified monomer, carrying out polymerization reaction for 6 hours at 70 ℃ in an inert gas atmosphere, after the reaction is finished, removing the solvent in the oil phase by reduced pressure rotary evaporation, washing the crude product with a proper amount of ethanol for 2-3 times, washing with deionized water for 2-3 times, and drying for 10 hours at 50 ℃ in a vacuum drying oven to obtain the linear fluorine-containing methyl vinyl (perfluoro-n-hexyl) propyl ester polymer.
(3) Preparation of composite cross-linked high oil absorption resin
Stirring and emulsifying 2 parts of tetrachloroethylene, 6 parts of sodium dodecyl sulfate and 350 parts of deionized water, adding 200 parts of the resin microspheres prepared in the step (1), and stirring at room temperature (80-100 r/min) to swell for 12 hours to obtain a first mixed solution;
adding 30 parts of ethanol, 8 parts of sodium dodecyl sulfate and 200 parts of 3% sodium chloride solution into 100 parts of linear fluorine-containing methyl vinyl (perfluoro-n-hexyl) propyl ester polymer prepared in the step (2), and stirring (90 r/min-110 r/min) to swell for 12h to obtain a second mixed solution;
and adding the first mixed solution, the second mixed solution and 0.3 part of ammonium persulfate into a reactor with a temperature control, stirring and condensation reflux system, keeping the temperature at 60 ℃ for 4 hours under the inert gas atmosphere, continuously heating to 90 ℃ and keeping the temperature for 10 hours. And (3) after the system is cooled to room temperature, washing with ethanol for 2-3 times, washing with deionized water for 3-5 times, and drying in a vacuum drying oven at 50 ℃ for 10 hours to obtain the composite cross-linked high oil absorption resin, which is denoted as ORZ-C3.
Comparative example 1
The comparative example provides a physical-chemical composite crosslinking high oil absorption resin with cis Ding Shengjiao as a physical crosslinking agent and butyl methacrylate as a chemical crosslinking agent, and the preparation method comprises the following steps:
uniformly mixing 30 parts of butyl methacrylate and 10 parts of cis Ding Shengjiao to obtain a mixture A;
uniformly mixing 100 parts of styrene, 80 parts of butyl methacrylate, 3.5 parts of azobisisobutyronitrile and 2 parts of polyvinyl alcohol to obtain a mixture B;
adding the mixture B into a reaction kettle, adding 200 parts of deionized water into the reaction kettle, heating to 60 ℃, preserving heat for 3 hours, adding the mixture A into the reaction kettle, continuously heating to 80 ℃, preserving heat for 3 hours, washing solids with ethanol and deionized water, and vacuum-drying at 45 ℃ for 6 hours to obtain the composite cross-linked oil absorption resin, namely resin No. 1.
Comparative example 2
The comparative example provides an oil-absorbing resin using ethylene glycol diacrylate as a chemical cross-linking agent, and the preparation method comprises the following steps:
mixing 100 parts of styrene, 35 parts of ethylene glycol diacrylate and 0.25 part of benzoyl peroxide uniformly by stirring, adding 10 parts of toluene, and continuously stirring to uniformly disperse all the components to obtain an oil phase;
adding 1.5 parts of hydroxypropyl methylcellulose into 180 parts of deionized water, and uniformly stirring to obtain a water phase;
mixing the oil phase and the water phase, stirring and heating to 60 ℃, preserving heat for 1h, continuously heating to 80 ℃, preserving heat for 2.5h, washing the solid by ethanol and deionized water, and vacuum drying at 45 ℃ for 6h to obtain the oil-absorbing resin, namely resin No. 2.
Test example 1 thermal stability test
Before thermogravimetric analysis test, the sample is placed in a vacuum oven, the adsorbed moisture or impurities in the sample are removed by treatment for 10 hours at 120 ℃, the sample to be measured of 10 mg is placed in a crucible, the temperature is increased at 10 ℃/min in the air atmosphere, and the temperature test range is 25-700 ℃. During the test, the thermal stability of the resin samples was analyzed based on the change in sample mass with temperature or time.
As shown in FIG. 1, the quality of the three samples is kept better at 50-100 ℃ in the air atmosphere. Resin 1# began to lose weight at 102 ℃, and severe loss of weight was manifested as: the first severe weightlessness stage is 105-265 ℃ and the second severe weightlessness stage is 270-420 ℃; resin 2# began to lose weight at 204 ℃, with severe loss of weight expressed as: the first severe weightlessness stage is 250-350 ℃ and the second severe weightlessness stage is 430-615 ℃; ORZ-C1 resins exhibit significant weight loss at 225℃as evidenced by: the first severe weightlessness stage is 265-430 ℃ and the second severe weightlessness stage is 445-600 ℃. The comparative analysis of the three resins shows that the oil-absorbing resin prepared by the invention has higher thermal stability.
Test example 2 oil absorption test
The oil absorption multiplying power is the ratio of the oil absorption quantity in unit time to the mass of the resin, and is an important index for measuring the oil absorption capacity of the resin. The oil absorption multiplying power is measured by a weighing method. Weighing a certain amount of dry resin, placing into a non-woven fabric pouch, immersing into a beaker filled with an oil product to be measured (such as benzene or trichloroethylene), taking out the pouch after a certain period of time, dripping at room temperature for about 1min, taking out the oil absorption resin, and rapidly weighing. The oil absorption multiplying power (W) is calculated as follows:
W=(G 2 -G 1 )/G 1
wherein: g 1 -the weight of the resin before oil absorption; g 2 -the weight of the resin after oil absorption.
And (3) measuring the relation between the oil absorption multiplying power and the time of the resin 1#, the resin 2#, and the ORZ-C1 resin, analyzing the oil absorption capacity and the saturation time of the three resins, and evaluating the resin performance.
As shown in fig. 2, the oil absorption multiplying power of resin 1# is 10.4g/g, and the adsorption equilibrium is reached for 5 hours; the oil absorption rate of the resin No. 2 is 12.2g/g, the oil absorption rate is reduced after 2 hours, and the adsorption equilibrium is reached after 5 hours; the oil absorption rate of the ORZ-C1 is 14.9g/g, the oil absorption rate is reduced after 3 hours, and the adsorption equilibrium is reached after 4 hours. Therefore, the oil absorption resin prepared by the invention has higher oil absorption multiplying power, can quickly reach adsorption balance, and has better oil-retaining effect after saturation.
Test example 3 application of high oil absorption resin
The material liquid to be treated is a nickel sulfate material liquid, the dissolved oil content is 350-600 mg/L, the pH value is 5-7, the material liquid temperature is 40-60 ℃, and the oil content of the material liquid effluent is less than 0.5mg/L under the premise of not introducing impurities. The concentration, pH and temperature of the dissolved oil of the nickel sulfate feed liquid are all fluctuated under the influence of the upstream process and seasonal temperature. Other ions are not introduced, namely the deoiling adsorption process does not support the adjustment of the pH value of the feed liquid to be acidic (the pH value is about 2-4).
ORZ-C1 was packed into a resin column (for laboratory use) at a packing height of 1.0m, a packing volume of about 400ml, a liquid inlet and outlet in the lower direction at a flow rate of 4BV/h, when the water content is 362BV, the oil content of the effluent is 0.516mg/L, the resin penetration needs to be regenerated, and the volume expansion rate of the resin is 31.2%. Hot water at 65 ℃ is selected as eluent in the regeneration stage, the dosage is 7.5BV, the flow rate is 2BV/h, then clean water is used for leaching, the rate is 3m/h, and the leaching time is 60min.
The pH of the nickel sulfate feed liquid is adjusted to about 3. The resin No. 1 is filled into a resin column (for laboratory use) with a filling height of 1.0m and a filling quantity of about 385ml, and is fed in and fed out in a liquid feeding mode at a flow rate of 3BV/h, when the water treatment amount is 324BV, the oil content of the effluent is 0.530mg/L, the resin penetration needs to be regenerated, and the volume expansion rate of the resin is 36.7%. Ethanol is used as eluent in the regeneration stage, the dosage is 8BV, the flow rate is 2BV/h, then the eluent is leached by clean water, the rate is 2.5m/h, and the leaching time is 100min.
And adjusting the pH value of the nickel sulfate feed liquid to 3-4. The resin No. 2 is filled into a resin column (for laboratory use) with the filling height of 1.0m, the filling quantity of about 392ml, the inlet and outlet of the resin column are realized in a liquid inlet mode, the flow speed is 4BV/h, when the water quantity is 349BV, the oil content of the outlet water is 0.528mg/L, the resin penetration is required to be regenerated, and the volume expansion rate of the resin is 28.4%. Ethanol is used as eluent in the regeneration stage, the dosage is 8BV, the flow rate is 2BV/h, then the eluent is leached by clean water, the rate is 2.5m/h, and the leaching time is 100min.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the physical-chemical composite cross-linked high oil absorption resin is characterized by comprising the following steps of:
(1) Carrying out suspension polymerization on styrene and divinylbenzene in the presence of a pore-forming agent, an initiator, a stabilizer and deionized water to obtain skeleton resin;
(2) Carrying out polymerization reaction on perfluoroalkyl alcohol and alkyl alkenoic acid ester in the presence of an alkaline catalyst and an organic solvent to obtain a fluorinated modified monomer, and carrying out free radical polymerization on the fluorinated modified monomer in the presence of an initiator to obtain a linear fluorine-containing alkyl alkenoic acid ester polymer;
(3) Swelling the skeleton resin and the linear fluorine-containing alkyl vinyl ester polymer respectively, and carrying out polymerization reaction in the presence of an initiator to obtain the high oil absorption resin.
2. The method for preparing a physical-chemical composite cross-linked high oil absorption resin according to claim 1, wherein in the step (1), the method for preparing the skeleton resin comprises:
100 parts of styrene, 12-36 parts of divinylbenzene, more than or equal to 0 and less than or equal to 15 parts of pore-forming agent and 0.05-0.8 part of initiator are uniformly mixed to obtain an oil phase;
1-5 parts of stabilizer are dissolved in 50-230 parts of deionized water to obtain a water phase;
and after the oil phase and the water phase are mixed, heating to 40-60 ℃ under the stirring condition, preserving heat for 2-4 hours, continuously heating to 60-85 ℃, preserving heat for 0.5-3 hours, obtaining yellowish spherical particles, and washing and drying to obtain the skeleton resin.
3. The method for preparing a physical-chemical composite cross-linked high oil absorption resin according to claim 2, wherein, in the step (1),
the pore-forming agent is dichloroethane, toluene, isooctane, n-heptane, n-hexane, isoamyl alcohol or liquid paraffin;
the initiator is an oil-soluble initiator;
the stabilizer is polyvinylpyrrolidone, gelatin, cetyl trimethyl ammonium bromide or polyvinyl ethyl ether.
4. The method for preparing a physical-chemical composite cross-linked high oil absorption resin according to claim 1, wherein in the step (2), the method for preparing the linear fluorine-containing alkyl acrylate polymer comprises:
adding the organic solvent with the molar ratio of 1: 0.4-1: 0.01-0.1 of perfluoroalkyl alcohol, alkyl alkenoic acid ester and alkaline catalyst, stirring for 4-8 hours at 50-110 ℃, cooling to room temperature, washing, and removing water to obtain a mixture containing fluorinated modified monomers;
and (3) adding an initiator into the mixture containing the fluorinated modified monomer in an inert gas atmosphere, stirring for 3-6 hours at 40-70 ℃, and then performing reduced pressure rotary evaporation, washing and drying to obtain the linear fluorine-containing alkyl vinyl ester polymer, wherein the addition amount of the initiator is 0.1-1.5 parts by 100 parts of the fluorinated modified monomer.
5. The method for preparing a physical-chemical composite cross-linked high oil absorption resin according to claim 4, wherein,
the perfluoroalkyl alcohol is perfluoro-n-butanol, 3- (perfluoro-n-hexyl) propanol or tetrafluoropropanol;
the alkyl olefine acid ester is acrylic ester or butenoic acid ester;
the alkaline catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide or calcium hydroxide;
the organic solvent is n-butanol, n-amyl alcohol or isoamyl alcohol;
the initiator is an oil-soluble initiator.
6. The method for preparing a physical-chemical composite cross-linked high oil absorption resin according to claim 1, wherein in the step (3), the method for preparing the high oil absorption resin comprises:
stirring and emulsifying more than 0 and less than or equal to 10 parts of pore-forming agent, 0.5-15 parts of emulsifying agent and 350-500 parts of deionized water, adding 150-300 parts of skeleton resin, and stirring and swelling for 3-12 hours at the rotating speed of 50-250 r/min to obtain a first mixed solution;
stirring and emulsifying 20-50 parts of an organic solvent, 0.5-15 parts of an emulsifying agent and 200-350 parts of an inorganic salt water solution, adding 100 parts of the linear fluorine-containing alkyl acrylate polymer, and stirring and swelling for 3-12 hours at the rotating speed of 50-250 r/min to obtain a second mixed solution;
and (3) stirring 0.1-1 part of the first mixed solution, the second mixed solution and the initiator at 60-90 ℃ for 6-15 hours in an inert gas atmosphere, cooling the system to room temperature, washing, and drying to obtain the high oil absorption resin.
7. The method for preparing a physical-chemical composite cross-linked high oil absorption resin according to claim 6, wherein in the step (3),
the pore-forming agent is dichloroethane, toluene, isooctane, tetrachloroethylene, n-heptane, n-hexane, isoamyl alcohol or liquid paraffin;
the emulsifier is sodium dodecyl sulfate, sodium dodecyl sulfonate, polyoxyethylene ether, polyoxypropylene ether or polyvinyl alcohol;
the organic solvent is methanol or ethanol;
the inorganic salt water solution is 1-10% of sodium chloride water solution, calcium chloride water solution or magnesium chloride water solution by mass percent;
the initiator is an inorganic peroxide initiator.
8. A physico-chemical composite crosslinked high oil absorption resin, characterized in that it is made by the method of any one of claims 1-7.
9. The use of the physical-chemical composite cross-linked high oil absorption resin as claimed in claim 8 in oil removal treatment of oily wastewater or feed liquid.
10. A method for removing oil from oily wastewater or feed liquid, the method comprising the steps of:
(1) Filtering the oily wastewater or feed liquid to remove suspended matters;
(2) Loading the high oil absorption resin as set forth in claim 8 into an adsorption column;
(3) The oily wastewater or feed liquid after suspended matters are removed in the step (1) enters an adsorption column in the step (2) from bottom to top, and top water is discharged after oil removal;
(4) When the oil content of the effluent does not meet the requirement, the high oil absorption resin reaches the penetrating adsorption capacity, and the resin needs to be regenerated.
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