CN105884956A - Ultrahigh crosslinked resin and preparation method and application thereof - Google Patents
Ultrahigh crosslinked resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN105884956A CN105884956A CN201610488995.XA CN201610488995A CN105884956A CN 105884956 A CN105884956 A CN 105884956A CN 201610488995 A CN201610488995 A CN 201610488995A CN 105884956 A CN105884956 A CN 105884956A
- Authority
- CN
- China
- Prior art keywords
- preparation
- divinylbenzene
- benzene
- chloro
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 239000011347 resin Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 230000008961 swelling Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002952 polymeric resin Substances 0.000 claims description 26
- 229920003002 synthetic resin Polymers 0.000 claims description 26
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000008346 aqueous phase Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004005 microsphere Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- UCCJUQNDECTTOL-UHFFFAOYSA-N C(=C)C1=C(C=CC=C1)C=C.ClC1=CC=C(C=C1)C Chemical compound C(=C)C1=C(C=CC=C1)C=C.ClC1=CC=C(C=C1)C UCCJUQNDECTTOL-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003361 porogen Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical group ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 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 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- -1 polydimethylsiloxane Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims 1
- 230000001186 cumulative effect Effects 0.000 claims 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 13
- 238000004042 decolorization Methods 0.000 abstract description 11
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 3
- 238000007265 chloromethylation reaction Methods 0.000 abstract description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003183 carcinogenic agent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010557 suspension polymerization reaction Methods 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 39
- 238000002835 absorbance Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- 238000000855 fermentation Methods 0.000 description 12
- 230000004151 fermentation Effects 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000000049 pigment Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000469 ethanolic extract Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 1
- 241001455226 Sauria Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C08F212/00—Copolymers 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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers 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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a super-high cross-linking resin, which is prepared by taking chloromethyl styrene and divinylbenzene as raw materials, changing the cross-linking degree or adding different pore-forming agents, preparing gel type and pore type precursor resins with controllable pore diameter through suspension polymerization, and carrying out Friedel-Crafts reaction on the precursor resins under the action of a catalyst in a swelling state to obtain the super-high cross-linking resin with high specific surface area and large pore volume and controllable pore diameter. The invention also discloses a preparation method and application of the ultrahigh crosslinked resin. Compared with the prior art, the preparation method is simple, the chloromethylation of the carcinogenic substance chloromethyl ether is avoided, the cost is low, the industrial production can be realized, and the obtained ultrahigh crosslinked resin has a good decolorization effect on organic acid.
Description
Technical field
The invention belongs to Polymer Synthesizing field, be specifically related to a kind of hypercrosslinked polymeric resin and preparation method and application.
Background technology
Linear polystyrene or low cross-linking are gathered by Friedel-Crafts reaction by Davankov in late 1990s
Benzene second is dilute uses outside electrophilic reagent to introduce new crosslinking, because its degree of cross linking is the highest, commonly referred to superhigh cross-linking polyphenyl
The dilute resin of second.Such Polystyrene resin has that specific surface area is big, average pore size is little, pore-size distribution is narrow, machine
The architectural features such as tool intensity is good, Polystyrene resin network structure can stop resin after solvent desorbing simultaneously
Expand, so it is good to have swellability, fine heat-resisting performance, use the advantages such as cycle length.
Current industrial synthesizing styrene system hypercrosslinked polymeric resin be by chloromethyl ether carry out chloromethylation obtain chloromethyl gather
Styrene-divinyl benzene resin, by introducing-CH2Cl adds catalyst in the swollen state, and to carry out Friedel-Crafts anti-
Should, by-CH2-the phenyl ring remote with the phenyl ring of another chain or the gathering of same chain is connected, and improves cross-linkage of resin,
Obtaining hypercrosslinked polymeric resin, but the method exists complex operation, chloromethyl ether used is severe toxicity carcinogenecity material and on phenyl ring
Random distribution cross-links internal structure heterogeneity after making, and needs to find a kind of simple to operate and comparatively safe method synthesis superelevation
Crosslinked resin.
Sherrington etc. at the beginning of 21 century enter polymer by merging the third monomer p-chloromethyl styrene (VBC)
Chain has finally given the resin of diapsid distribution, has expanded the preparation thinking of hypercrosslinked polymeric resin, has investigated Louis simultaneously
Acid catalyst, the response time, the impact on hypercrosslinked polymeric resin of the p-chloromethyl styrene content.But preparing superhigh cross-linking
In resin process, simple and effective technical controlling pore structure remains a difficult problem, it is therefore desirable to applicable method pin
The aperture of resin is adjusted by the molecular size of adsorbate.
Because typically can be along with substantial amounts of pigment in organic acid, owing to the existence of pigment have impact on the quality of product with outer
See, simultaneously may be to human body, bad environmental, so decolorizing effect directly affects quality and the life of whole technique of product
Producing cost, the pigment in organic acid effectively can be removed so needing to seek a kind of resin.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hypercrosslinked polymeric resin, to solve the internal junction that prior art exists
The problems such as structure heterogeneity, Porosity control difficulty and decolorizing effect are the best.
The present invention also to solve the technical problem that the preparation method being to provide above-mentioned hypercrosslinked polymeric resin.
The present invention finally to solve the technical problem that the application being to provide above-mentioned hypercrosslinked polymeric resin.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows:
A kind of hypercrosslinked polymeric resin, it has a following construction unit:
The skeleton of this resin is polystyrene, and mean diameter is 100～500 μm, and average specific surface area is 250～1600m2/ g,
Average pore volume is 0.32～0.95cm3/g。
The preparation method of above-mentioned hypercrosslinked polymeric resin, it comprises the steps:
(1) by after soluble in water to stabilizer, sodium chloride and aqueous phase polymerization inhibitor, with 1-chloro-4-methyl-benzene, divinylbenzene,
Initiator and porogen mixing, after ultrasonic dissolution and floating polyreaction, be cooled to room temperature；
(2) after the deionized water (70～90 DEG C) after the mixed system of gained is heated in step (1) rinses 3 times,
After carrying out solidifying and rinse 3 times with methanol, then carrying out soxhlet extraction with ethanol, gained solid portion obtains chloromethane after drying
Base styrene-divinylbenzene microsphere；
(3) 1-chloro-4-methyl-benzene-divinylbenzene microspheres the most swelling 2～12h that will prepare in step (2)
After, temperature reaction, it is cooled to room temperature after having reacted；
(4) mixed system of gained in step (3) immersed in the mixed liquor of aqueous hydrochloric acid solution and ethanol and stir, then
Carrying out soxhlet extraction with ethanol, gained solid portion is washed through deionization, is dried, and obtains hypercrosslinked polymeric resin.
In step (1), described stabilizer is polyvinyl alcohol, methylcellulose, gelatin, magnesium hydroxide and hydroxyl phosphorus
Any one or a few combination in acid calcium；Described aqueous phase polymerization inhibitor is methylene blue, the molten melanin of aqueous, sulfuration
Sodium, thiourea, sodium sulfate, ammonium thiocyanate, the salt (preferably sulfuric acid copper or copper chloride) of copper, picric acid, phenol and
Any one or a few combination in hydroquinone；Described initiator be dilauroyl peroxide, dibenzoyl peroxide,
Any one or a few combination in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) and hydrogen peroxide；Described porogen is
Any one or a few combination in normal hexane, toluene, Hexalin, polypropylene glycol and polydimethylsiloxane.
In step (1), 1-chloro-4-methyl-benzene quality accounts for 1-chloro-4-methyl-benzene and the 85 of divinylbenzene gross mass～99%；Surely
Determine agent the quality that quality is water 0.2～2%, preferably 2%；The quality of aqueous phase polymerization inhibitor is the 0.1～0.5% of the quality of water,
Preferably 0.16%；The quality of sodium chloride is the 3.3% of the quality of water；The quality of initiator is p-chloromethyl styrene and diethyl
The 0.5～2% of alkene benzene gross mass, preferably 1%；The volume of porogen is that 1-chloro-4-methyl-benzene, divinylbenzene and cross-linking agent are total
The 50～100% of volume, preferably 80%；The gross mass of deionized water, stabilizer and sodium chloride and 1-chloro-4-methyl-benzene, two
The ratio of Ethenylbenzene and cross-linking agent gross mass is 5～10:1.
In step (1), the condition of floating polyreaction is under 70～90 DEG C (preferably 80～85 DEG C) after reaction 16～24h,
1～3h is reacted again under 100～150 DEG C (preferably 110～120 DEG C).
In step (2), curing operation refers to products therefrom washing by soaking 3-4 time in methanol aqueous solution.
In step (2), the described method being dried is: (excellent less than-0.09mbar and 40～60 DEG C at relative vacuum degree
Select 45 DEG C) under, dry 10～16h.
In step (3), described solvent is dichloromethane, dichloroethanes, Nitrobenzol, chlorobenzene or o-dichlorohenzene；Its
In, the mass ratio of 1-chloro-4-methyl-benzene-divinylbenzene microspheres and solvent is 1:10～20, preferably 1:10.
In step (3), the condition of temperature reaction is under nitrogen protection, reacts 8～12h under 80～120 DEG C (preferably 85 DEG C),
Used catalyst is any one or a few the combination in lewis acid and halogenation boron.
Wherein, described lewis acid is FeCl3、AlCl3、SnCl4Or ZnCl2, described halogenation boron Cl3Or BBr3。
In step (3), in catalyst and 1-chloro-4-methyl-benzene-divinylbenzene microspheres, the mol ratio of chlorine is 1～3:1, preferably
1:1.
In step (4), the concentration of described aqueous hydrochloric acid solution is the amount ratio of 0.1mol/L, aqueous hydrochloric acid solution and ethanol
For 1:10～20.
The reaction equation of the present invention is as follows:
The application in organic acid decolours of the above-mentioned hypercrosslinked polymeric resin is also within protection scope of the present invention.
Wherein, described organic acid decolouring refers to remove pigment from citric acid fermentation broth.
Beneficial effect: compared with prior art, the present invention has the advantage that
1, the present invention prepares 1-chloro-4-methyl-benzene-diethyl by 1-chloro-4-methyl-benzene, divinylbenzene by suspension polymerisation
Alkene benzene resin, thus simplify production method, and avoid tradition chloromethyl ether used by chloromethylation.
2, the aperture of precursor resin can be adjusted by the present invention according to the molecular size of adsorbate, obtains suitable aperture and divides
The hypercrosslinked polymeric resin of cloth.Gel type precursor resin can by adjust p-chloromethyl styrene, divinylbenzene ratio to front
The aperture of body resin regulates and controls within the specific limits；Optimum porogen can well be dissolved in one with polymer network
Rise, just can be separated when monomer conversion height, carry out polymerization further and understand the shape that is bound up by polymer network
Micropore in one-tenth；Non-benign porogen is the best with polymer network compatibility, occurs when monomer conversion is low to be separated, enters
Filling small hole is formed macropore while being bound up by polymer network by one-step polymerization.
3, the hypercrosslinked polymeric resin prepared contains bigger specific surface area (specific surface area is up to 1000～1700m2/ g) and relatively
(pore volume is up to 0.8～1.3cm for big pore volume3/ g), the good decolorizing effect to pigment, pigment analysis uses wavelength to be 260nm
Place's absorbance represents the content of pigment in citric acid fermentation broth, and this superhigh cross-linking degree resin is to pigment in citric acid fermentation broth
Clearance has reached 97%.
Accompanying drawing explanation
Fig. 1 is infrared comparison diagram before and after crosslinking after 1-chloro-4-methyl-benzene-divinylbenzene resins；
Fig. 2 is internal structure scanning electron microscope (SEM) figure after crosslinking after 1-chloro-4-methyl-benzene-divinylbenzene resins；
Fig. 3 is 1-chloro-4-methyl-benzene-divinylbenzene resins macrograph；
Fig. 4 is hypercrosslinked polymeric resin nitrogen Adsorption and desorption isotherms prepared by the present invention；
Fig. 5 is the pore-size distribution of hypercrosslinked polymeric resin prepared by the present invention.
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that reality
Execute the content described by example and be merely to illustrate the present invention, and should be also without limitation on not described in detail in claims
The present invention.
The preparation method of embodiment 1:2% degree of cross linking 1-chloro-4-methyl-benzene-divinylbenzene gel type resin, specifically includes following step
Rapid:
(1) water-oil factor=8:1, aqueous phase consist of deionized water 50ml, polyvinyl alcohol 0.1g, sodium chloride 1.65g, to benzene
Diphenol 0.08g；Oil phase consists of p-chloromethyl styrene 6.34g, divinylbenzene 0.129g, azodiisobutyronitrile 0.0646g；
Before adding aqueous phase, lead to argon 30min in advance, at 50 DEG C, oil phase is added aqueous phase mixing 1h, be warming up to 80 DEG C of reactions
20h, reaction the later stage be warming up to 110 DEG C carry out ripening 2h after naturally cool to room temperature.
(2) products therefrom use be heated to the deionized water of 80 DEG C repeatedly in wash 3 times, solidify with methanol and wash
After 3 times, ethanol carries out surname extraction 8h, at relative vacuum degree less than-0.09mbar, is dried 12h under temperature 45 C.
(3) microsphere (such as Fig. 2) obtained in step 2 is taken out 5g addition 50g dichloroethanes swelling overnight, add in advance
Enter 1g anhydrous ferric chloride mixing 1h, reaction temperature 85 DEG C, response time 8h, naturally cool to room temperature.
(4) microsphere in step 3 is detached mother solution, with 0.1% hydrochloric acid and ethanol mixing, washing, carry out Soxhlet with ethanol
Extract 8h, at relative vacuum degree less than-0.09mbar, under temperature 45 C, be dried 12h.
(5) experiment display, the hypercrosslinked polymeric resin (internal structure SEM is schemed such as Fig. 2) of this enforcement preparation, citric acid is sent out
Ferment liquid measures the solution absorbance under 260nm after diluting 50 times be this resin of 0.36,0.2g and 10ml citric acid fermentation broth
Carrying out static shaking flask absorption, in 120min, internal adsorption basically reaches saturated, dilutes the solution of 50 times at 260nm after absorption
Lower absorbance is 0.014, and absorbance before percent of decolourization=(absorbance after absorbance-decolouring before decolouring)/decolouring
* 100%, can draw according to Fig. 4 nitrogen adsorption desorption curve, the specific surface area of adsorbent is 1569m2/ g, pore volume
0.938cm3/ g, percent of decolourization is 96%.Can be seen that micropore occupies leading position with mesoporous according to Fig. 5 graph of pore diameter distribution.
Embodiment 2: the preparation method of pass chloromethyl styrene resin, specifically includes following steps:
(1) water-oil factor=8:1, aqueous phase consist of deionized water 50ml, polyvinyl alcohol 0.1g, sodium chloride 1.65g, to benzene
Diphenol 0.08g；Oil phase consist of 1-chloro-4-methyl-benzene 5.498g, divinylbenzene 0.97g, azodiisobutyronitrile 0.0646g,
Toluene 6.1ml；Before adding aqueous phase, lead to argon 30min in advance, at 50 DEG C, oil phase is added aqueous phase mixing 1h, heat up
To 80 DEG C reaction 20h, reaction the later stage be warming up to 110 DEG C carry out ripening 2h after naturally cool to room temperature.
(2) products therefrom use be heated to the deionized water of 80 DEG C repeatedly in wash 3 times, solidify with methanol and wash
After 3 times, acetone carries out surname extraction 8h removing porogen, at relative vacuum degree less than-0.09mbar, dry under temperature 45 C
Dry 12h.
(3) microsphere that obtains in step 2 takes out 5g, and to add 50g dichloroethanes swelling overnight, add in advance 1g without
Water iron chloride mixing 1h, reaction temperature 85 DEG C, response time 8h, naturally cool to room temperature.
(4) microsphere in step 3 is detached mother solution, with 0.1% hydrochloric acid and ethanol mixing, washing, carry out Soxhlet with ethanol
Extract 8h, at relative vacuum degree less than-0.09mbar, under temperature 45 C, be dried 12h.
(5) experiment display, the hypercrosslinked polymeric resin of this enforcement preparation, measure after citric acid fermentation broth is diluted 50 times
Solution absorbance under 260nm is 0.38, and this resin of 0.2g and 10ml citric acid fermentation broth carry out static shaking flask absorption,
In 120min, internal adsorption basically reaches saturated, and the solution absorbance under 260nm diluting 50 times after absorption is 0.068,
And absorbance * 100% before percent of decolourization=(absorbance after absorbance-decolouring before decolouring)/decolouring, the specific surface of adsorbent
Amass as 801m2/ g, pore volume 0.52cm3/ g, percent of decolourization is 82%.
The preparation method of embodiment 3:10% degree of cross linking 1-chloro-4-methyl-benzene-divinylbenzene resins, specifically includes following steps:
(1) water-oil factor=8:1, aqueous phase consists of deionized water 50ml, magnesium hydroxide 0.1g, sodium chloride 1.65g, methylene
Base indigo plant 0.08g；Oil phase consists of p-chloromethyl styrene 5.821g, divinylbenzene 0.647g, dibenzoyl peroxide
0.0646g；Before adding aqueous phase, lead to argon 30min in advance, at 50 DEG C, oil phase is added aqueous phase mixing 1h, be warming up to
60 DEG C reaction 20h, reaction the later stage be warming up to 110 DEG C carry out ripening 2h after naturally cool to room temperature.
(2) products therefrom use be heated to the deionized water of 80 DEG C repeatedly in wash 3 times, solidify with methanol and wash
After 3 times, ethanol carries out surname extraction 8h, at relative vacuum degree less than-0.09mbar, is dried 12h under temperature 45 C.
(3) microsphere (such as Fig. 2) obtained in step 2 is taken out 5g addition 50g Nitrobenzol swelling overnight, add in advance
1g anhydrous Aluminum chloride mixing 1h, reaction temperature 115 DEG C, response time 8h, naturally cool to room temperature.
(4) microsphere in step 3 is detached mother solution, with 0.1% hydrochloric acid and ethanol mixing, washing, carry out Soxhlet with ethanol
Extract 8h, at relative vacuum degree less than-0.09mbar, under temperature 45 C, be dried 12h.
(5) experiment display, the hypercrosslinked polymeric resin of this enforcement preparation, measure after citric acid fermentation broth is diluted 50 times
Solution absorbance under 260nm is 0.35, and this resin of 0.2g and 10ml citric acid fermentation broth carry out static shaking flask absorption,
In 120min, internal adsorption basically reaches saturated, and the solution absorbance under 260nm diluting 50 times after absorption is 0.035,
And absorbance * 100% before percent of decolourization=(absorbance after absorbance-decolouring before decolouring)/decolouring, the specific surface of adsorbent
Amass as 950m2/ g, pore volume 0.623cm3/ g, percent of decolourization is 90%.
Embodiment 4: the preparation method of pass 1-chloro-4-methyl-benzene-divinylbenzene gel type resin, specifically includes following steps:
(1) water-oil factor=8:1, aqueous phase consists of deionized water 50ml, magnesium hydroxide 0.1g, sodium chloride 1.65g, methylene
Base indigo plant 0.08g；Oil phase consist of p-chloromethyl styrene 5.498g, divinylbenzene 0.97g, dibenzoyl peroxide 0.646g,
Polypropylene glycol 6.1ml；Before adding aqueous phase, lead to argon 30min in advance, at 50 DEG C, oil phase added aqueous phase and mix 1h,
Be warming up to 60 DEG C reaction 20h, reaction the later stage be warming up to 110 DEG C carry out ripening 2h after naturally cool to room temperature.
(2) products therefrom use be heated to the deionized water of 80 DEG C repeatedly in wash 3 times, solidify with methanol and wash
After 3 times, acetone carries out surname extraction 8h removing porogen, at relative vacuum degree less than-0.09mbar, dry under temperature 45 C
Dry 12h.
(3) microsphere (such as Fig. 2) obtained in step 2 is taken out 5g addition 50g Nitrobenzol swelling overnight, add in advance
1g anhydrous Aluminum chloride mixing 1h, reaction temperature 115 DEG C, response time 8h, naturally cool to room temperature.
(4) microsphere in step 3 is detached mother solution, with 0.1% hydrochloric acid and ethanol mixing, washing, carry out Soxhlet with ethanol
Extract 8h, at relative vacuum degree less than-0.09mbar, under temperature 45 C, be dried 12h.
(5) experiment display, the hypercrosslinked polymeric resin of this enforcement preparation, measure after citric acid fermentation broth is diluted 50 times
Solution absorbance under 260nm is 0.38, and this resin of 0.2g and 10ml citric acid fermentation broth carry out static shaking flask absorption,
In 120min, internal adsorption basically reaches saturated, and the solution absorbance under 260nm diluting 50 times after absorption is 0.089,
And absorbance * 100% before percent of decolourization=(absorbance after absorbance-decolouring before decolouring)/decolouring, the specific surface of adsorbent
Amass as 615m2/ g, pore volume 0.43cm3/ g, percent of decolourization is 76.6%.
Embodiment 5: the preparation method of pass 1-chloro-4-methyl-benzene-divinylbenzene resins, specifically includes following steps:
(1) water-oil factor=8:1, aqueous phase consists of deionized water 50ml, magnesium hydroxide 0.1g, sodium chloride 1.65g, methylene
Base indigo plant 0.08g；Oil phase consist of p-chloromethyl styrene 5.498g, divinylbenzene 0.97g, dibenzoyl peroxide 0.646g,
Toluene 3ml, two kinds of porogen mixing of Hexalin 3ml；Argon 30min was led in advance before adding aqueous phase, will at 50 DEG C
Oil phase adds aqueous phase mixing 1h, is warming up to 60 DEG C of reaction 20h, the reaction later stage be warming up to 110 DEG C carry out after ripening 2h from
So it is cooled to room temperature.
(2) products therefrom use be heated to the deionized water of 80 DEG C repeatedly in wash 3 times, solidify with methanol and wash
After 3 times, acetone carries out surname extraction 8h removing porogen, at relative vacuum degree less than-0.09mbar, dry under temperature 45 C
Dry 12h.
(3) microsphere (such as Fig. 2) obtained in step 2 is taken out 5g addition 50g chlorobenzene swelling overnight, add 1g in advance
Anhydrous zinc chloride mixing 1h, reaction temperature 90 DEG C, response time 8h, naturally cool to room temperature.
(4) microsphere in step 3 is detached mother solution, with 0.1% hydrochloric acid and ethanol mixing, washing, carry out Soxhlet with ethanol
Extract 8h, at relative vacuum degree less than-0.09mbar, under temperature 45 C, be dried 12h.
(5) experiment display, the hypercrosslinked polymeric resin of this enforcement preparation, measure after citric acid fermentation broth is diluted 50 times
Solution absorbance under 260nm is 0.36, and this resin of 0.2g and 10ml citric acid fermentation broth carry out static shaking flask absorption,
In 120min, internal adsorption basically reaches saturated, and the solution absorbance under 260nm diluting 50 times after absorption is 0.245,
And absorbance * 100% before percent of decolourization=(absorbance after absorbance-decolouring before decolouring)/decolouring, the specific surface of adsorbent
Amass as 254.59m2/ g, pore volume 0.387cm3/ g, percent of decolourization is 32%.
Claims (10)
1. a hypercrosslinked polymeric resin, it is characterised in that it has a following construction unit:
The skeleton of this resin is polystyrene, and mean diameter is 100～500 μm, and average specific surface area is 250～1600m2/ g,
Average pore volume is 0.32～0.95cm3/g。
2. the preparation method of the hypercrosslinked polymeric resin described in claim 1, it is characterised in that it comprises the steps:
(1) by after soluble in water to stabilizer, sodium chloride and aqueous phase polymerization inhibitor, with 1-chloro-4-methyl-benzene, divinylbenzene,
Initiator and porogen mixing, after ultrasonic dissolution and floating polyreaction, be cooled to room temperature；
(2) in step (1), the mixed system of gained after washing, after carrying out solidifying and washing with methanol, then uses ethanol
Carrying out soxhlet extraction, gained solid portion obtains 1-chloro-4-methyl-benzene-divinylbenzene microspheres after drying；
(3) by after the most swelling for 1-chloro-4-methyl-benzene-divinylbenzene microspheres of preparing in step (2), rise
Temperature reaction, is cooled to room temperature after having reacted；
(4) mixed system of gained in step (3) immersed in the mixed liquor of aqueous hydrochloric acid solution and ethanol and stir, then
Carrying out soxhlet extraction with ethanol, gained solid portion, through washing, being dried, obtains hypercrosslinked polymeric resin.
Preparation method the most according to claim 2, it is characterised in that in step (1), described stabilizer is
Any one or a few combination in polyvinyl alcohol, methylcellulose, gelatin, magnesium hydroxide and calcium hydroxy phosphate；Institute
The aqueous phase polymerization inhibitor stated is methylene blue, water-soluble black element, sodium sulfide, thiourea, sodium sulfate, ammonium thiocyanate, copper
Any one or a few combination in salt, picric acid, phenol and hydroquinone；Described initiator is peroxidating
In lauroyl, dibenzoyl peroxide, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) and hydrogen peroxide any one or several
The combination planted；Described porogen is appointing in normal hexane, toluene, Hexalin, polypropylene glycol and polydimethylsiloxane
Anticipate one or more combination.
Preparation method the most according to claim 2, it is characterised in that in step (1), 1-chloro-4-methyl-benzene matter
Amount accounts for 1-chloro-4-methyl-benzene and the 85 of divinylbenzene gross mass～99%；The quality of stabilizer is the 0.2～2% of the quality of water,
The quality of aqueous phase polymerization inhibitor is the 0.1～0.5% of the quality of water, and the quality of sodium chloride is the 3.3% of the quality of water；Initiator
Quality is p-chloromethyl styrene and divinylbenzene gross mass 0.5～2%, the volume of porogen be 1-chloro-4-methyl-benzene,
Divinylbenzene and the 50 of cross-linking agent cumulative volume～100%；Deionized water, stabilizer, sodium chloride, total matter of aqueous phase polymerization inhibitor
Amount is 5～10:1 with 1-chloro-4-methyl-benzene, divinylbenzene, the ratio of initiator gross mass.
Preparation method the most according to claim 2, it is characterised in that in step (1), the bar of floating polyreaction
Part is at 70～90 DEG C after reaction 16～24h, then reacts 1～3h at 100～150 DEG C.
Preparation method the most according to claim 2, it is characterised in that in step (3), described solvent is two
Chloromethanes, dichloroethanes, Nitrobenzol, chlorobenzene or o-dichlorohenzene；Wherein, 1-chloro-4-methyl-benzene-divinylbenzene microspheres and
The mass ratio of solvent is 1:10～20.
Preparation method the most according to claim 2, it is characterised in that in step (3), the condition of temperature reaction
For under nitrogen protection, reacting 8～12h at 80～120 DEG C, used catalyst is any one in lewis acid and halogenation boron
Kind or several combinations.
Preparation method the most according to claim 7, it is characterised in that in step (3), catalyst and chloromethyl
In styrene-divinylbenzene microsphere, the mol ratio of chlorine is 1～3:1.
Preparation method the most according to claim 2, it is characterised in that in step (4), described hydrochloric acid is water-soluble
The concentration of liquid be the amount ratio of 0.1mol/L, aqueous hydrochloric acid solution and ethanol be 1:10～20.
10. the application in organic acid decolours of the hypercrosslinked polymeric resin described in claim 1.
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| CN108485569A (en) * | 2018-03-28 | 2018-09-04 | 方建波 | A kind of preparation method of retardation setting type building structure glue material |
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