CN103159966B - Cross-linking formulations for forming quaternary ammonium salts - Google Patents
Cross-linking formulations for forming quaternary ammonium salts Download PDFInfo
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- CN103159966B CN103159966B CN201210096355.6A CN201210096355A CN103159966B CN 103159966 B CN103159966 B CN 103159966B CN 201210096355 A CN201210096355 A CN 201210096355A CN 103159966 B CN103159966 B CN 103159966B
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- quaternary ammonium
- ammonium salt
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- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000009472 formulation Methods 0.000 title claims abstract description 26
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 23
- 238000004132 cross linking Methods 0.000 title description 24
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- -1 ether glycols Chemical class 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229960001701 chloroform Drugs 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960000655 ensulizole Drugs 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 239000004971 Cross linker Substances 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 125000001453 quaternary ammonium group Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 238000010612 desalination reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000036632 reaction speed Effects 0.000 description 7
- JTYUIAOHIYZBPB-UHFFFAOYSA-N 1-bromo-6-chlorohexane Chemical compound ClCCCCCCBr JTYUIAOHIYZBPB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- JJMIAJGBZGZNHA-UHFFFAOYSA-N sodium;styrene Chemical compound [Na].C=CC1=CC=CC=C1 JJMIAJGBZGZNHA-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- FXLJHFCTYDFUER-UHFFFAOYSA-N 1-bromoprop-2-enylbenzene Chemical compound C=CC(Br)C1=CC=CC=C1 FXLJHFCTYDFUER-UHFFFAOYSA-N 0.000 description 1
- CIEWGZJDEDBECJ-UHFFFAOYSA-N 1-chloro-4-methylbenzene Chemical compound [CH2]C1=CC=C(Cl)C=C1 CIEWGZJDEDBECJ-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 1
- FEMVWXUMIWVIQK-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C(=C)C1=CC=NC=C1.C(=C)C1=CC=NC=C1 FEMVWXUMIWVIQK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- SYUYDTGNTUKQQM-UHFFFAOYSA-N OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)O Chemical compound OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)O SYUYDTGNTUKQQM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- MZNDIOURMFYZLE-UHFFFAOYSA-N butan-1-ol Chemical compound CCCCO.CCCCO MZNDIOURMFYZLE-UHFFFAOYSA-N 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- WNJYIHGQTOOFER-UHFFFAOYSA-L disodium;styrene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.C=CC1=CC=CC=C1 WNJYIHGQTOOFER-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N para-chlorotoluene Natural products CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a quaternary ammonium salt-forming cross-linked formulation comprising: a swellable polymer having an amino group; a crosslinker, wherein the crosslinker has at least two halogen substituents, and the halogen substituents are not the same; and a solution, wherein the solution includes a solvent dissolving the swellable polymer having the amino group.
Description
[technical field]
The present invention relates to a kind of cross-linked formulations, and particularly relate to a kind of cross-linked formulations that forms quaternary ammonium salt.
[prior art]
The various filtration material for desalinations that are applied to seawater, process water and waste water of Ge great factory of world active development, filtration material for desalination can be processed in water salt expeditiously except wanting, more wish to reduce working pressure, thereby reduce clean water treatment cost because of low power consuming.
There is research using ionic polymer as filtration material for desalination; this material can under low pressure still have high-throughput; but; in order to strengthen the physical strength of filtration material for desalination; conventionally can add linking agent and ionic polymer is cross-linked; but the speed of the kind of linking agent and crosslinking reaction speed all can affect stability and the quality of filtration material for desalination.
In order further to improve the quality of filtration material for desalination, the present invention proposes a kind of cross-linked formulations, this cross-linked formulations comprises that the quaternary ammonium salt that the crosslinking reaction of being undertaken by this cross-linked formulations obtains can be used as filtration material for desalination with amino swellable polymer, linking agent and solution.
[summary of the invention]
The invention provides a kind of cross-linked formulations that forms quaternary ammonium salt, comprising: with amino swellable polymer; Linking agent, wherein this linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And solution, wherein this solution comprises that dissolving is with the high molecular solvent of amino swellable.
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularly go out preferred embodiment, and coordinate accompanying drawing, be described in detail below:
[brief description of the drawings]
Figure 1A-1D is a series of Fourier transform infrared spectroscopy figure (FT-IR), in order to the crosslinking degree of the embodiment of the present invention to be described.
[embodiment]
The invention provides a kind of cross-linked formulations that forms quaternary ammonium salt, comprising: with amino swellable polymer; Linking agent, wherein linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And solution, wherein solution comprises that dissolving is with the high molecular solvent of amino swellable, protonic solvent (protic solvent), non-solvent or above-mentioned combination.So-called " swellable (water-swellable) polymer " means polymer itself and can expand by absorbing water herein, and this polymer can absorb large quantity of moisture and can not cause it in water, to dissolve.
Above-mentionedly formed by following chemical formula (I-1), chemical formula (I-2) and the monomer polymerization of chemical formula (I-3) with amino swellable polymer:
wherein R
1be selected from phenylbenzimidazole sulfonic acid base or alkyl group sulfonic group;
wherein R
2be selected from
wherein R
3be selected from
and chemical formula (I-1), chemical formula (I-2) are about 0.1-50: 1-99: 0.1-50 with the mol ratio of chemical formula (I-3).
Above-mentioned linking agent is selected from many haloalkanes, phenyl polyhalide, many halogenated heterocyclics or many halos polymer, the compound of for example chemical formula (II), chemical formula (III) or chemical formula (IV),
Wherein A is selected from C
1-C
25alkylidene group (alkylene), C
6-C
25arylidene (arylene) or C
7-C
25sub-aralkyl (aralkylene); R
1, R
2be selected from independently of one another Cl, Br or I, and R
1≠ R
2.
Wherein R
3, R
4, R
5be selected from independently of one another and replace or unsubstituted aryl (aryl) or acryl series (acrylic) structure, as
r
6, R
9be selected from independently of one another H or CH
3; R
7, R
8be selected from independently of one another CH
2cl, CH
2br, CH
2i; R
10, R
11be selected from independently of one another H, CH
3, CH
2cl, CH
2br, CH
2i, wherein R
7≠ R
10, R
8≠ R
11, the number that wherein a, b, c are repeating unit, and a, b, c are 1～1000 integer independently of one another.
Wherein R
12, R
13be selected from independently of one another Cl, Br or I, and R
12≠ R
13, the number that wherein d, e are repeating unit, and d, e are 1～1000 integer independently of one another.
Linking agent and be 0.01-10 with the part by weight between amino swellable polymer, but the ratio of linking agent is not as limit, those skilled in the art can adjust according to the demand of practical application.In the time that linking agent ratio is higher, can obtain the comparatively fine and close quaternary ammonium salt of structure, in the time that linking agent ratio is lower, can obtain the quaternary ammonium salt that structure is comparatively loose.
Should be noted, the quaternary ammonium salt making by cross-linked formulations of the present invention can further form fiber (fiber) by spinning step, because the spinning time may need several hours, if so when rate of crosslinking is too fast, can cause viscosity (viscosity) to rise rapidly, make quaternary ammonium salt cannot carry out spinning step, therefore, the present invention is by the not identical speed that slows down crosslinking reaction of those halogenic substituents in linking agent.
In addition, the quaternary ammonium salt making by cross-linked formulations of the present invention can further be formed in carrier layer by coating (coating) step, to be made into filtration material for desalination, but, if rate of crosslinking when too fast, can cause viscosity (viscosity) to rise rapidly, can make that the thickness of coating is too thick or thickness is wayward, therefore, the present invention by those halogenic substituents in linking agent not identical regulate and control the speed of crosslinking reaction.
In one embodiment, use the identical polymer different linking agent of arranging in pairs or groups, experimental result is found at ambient temperature, use the bromo-6 chlorohexane (1-bromo-6-chloro-hexane of 1-, BCH) rate of crosslinking is slower than 1, 6-dibromo-hexane (1, 6-dibromo hexane, DBH), this is because bromine atoms and chlorine atom are while carrying out crosslinking reaction, bromine atoms is easier and high molecular weight reactive Cheng Jian than chlorine atom, therefore, both sides are that the rate of crosslinking of the linking agent of bromine atoms can be faster than one side bromine linking agent of chlorine on one side, hence one can see that, the linking agent that uses both sides to have different halogens can slow down the speed of crosslinking reaction really, therefore, those skilled in the art can be according to the needs of actual procedure (spinning process or coating process), add dissimilar linking agent, with the speed of regulation and control crosslinking reaction.
Above-mentioned dissolving is high polar solvent with the high molecular solvent of amino swellable, for example N, N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (Dimethylformamide, DMF), methyl-sulphoxide (Dimethyl sulfoxide, DMSO), alcohols, N-Methyl pyrrolidone (N-methyl pyrrolidinone, NMP) etc.
Above-mentioned protonic solvent comprises water, acid or alcohols.Acids comprises formic acid (formic acid), acetic acid (acetic acid), citric acid (citric acid), succsinic acid (succinic acid), hydrochloric acid (hydrochloric acid) or above-mentioned combination.
Alcohols can be monohydroxy-alcohol or polyvalent alcohol, for example methyl alcohol of monohydroxy-alcohol (methanol), ethanol (ethanol), n-propyl alcohol (n-propanol), Virahol (isopropanol), propyl carbinol (n-butanol) or Pentyl alcohol (n-pentanol).
Polyvalent alcohol comprises glycols, many alcohols, ether glycols or above-mentioned combination.Glycols is ethylene glycol such as, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexanediol, cyclohexyl dimethanol (Cyclohexyldimethanol, CHDM), ethohexadiol, neopentyl glycol (Neopentyl glycol, NPG), neopentyl glycol (Trimethylpentanediol, TMPD), xylyl alcohol, dihydroxy-benzene, cresorcin or dihydroxyphenyl propane (Bisphenol-A), poly adipate succinic acid ester [Poly (butanediol-co-adipate) glycol, PBA], polytetramethylene ether diol (Polytetramethylene glycol, PTMEG), polypropylene glycol (Polypropylene glycol, PPG), polyoxyethylene glycol (Polyethylene glycol, PEG).
Many alcohols comprise polyester polyol, polyether glycol, polycarbonate polyol, polycaprolactone polyol, polyacrylate polyol, for example glycerol, trimethylammonium alcohol propane (Trimethylolpropane), tetramethylolmethane (Pentaerythritol), benzenetriol.
Ether glycols for example comprises Diethylene Glycol, triethylene glycol, dipropylene glycol, tripropylene glycol.
Above-mentioned non-solvent refers to and the immiscible solvent of swellable polymer with amino, because the swellable polymer with amino is ionic polymer, therefore non-solvent is low polar solvent, non-solvent comprises tetrahydrofuran (THF) (Tetrahydrofuran, THF), methylene dichloride (dichloromethane, DCM), trichloromethane (chloroform), straight or branched alkanes (pentane, hexane (hexane), heptane (heptane)), benzene (benzene), toluene (toluene) or acetone (acetone) etc.
Above-mentioned dissolving is with the high molecular solvent of amino swellable: the part by weight of protonic solvent or non-solvent is about 9/1-5/5.
In one embodiment, dissolving is N,N-dimethylacetamide (DMAc) with the high molecular solvent of amino swellable, and protonic solvent is ethanol (ethanol), and the mixed weight ratio of the former with the latter is 9: 1.
In another embodiment, dissolving is N,N-dimethylacetamide (DMAc) with the high molecular solvent of amino swellable, and non-solvent is tetrahydrofuran (THF) (Tetrahydrofuran, THF), the mixed weight ratio of the former with the latter is 5: 5.
Should be noted, protonic solvent and with between amino swellable polymer can form hydrogen bond, this hydrogen bond can slow down crosslinking reaction speed.In addition,, because non-solvent can not dissolve each other with swellable polymer, therefore, the existence of non-solvent can reduce the chance of linking agent and the collision of swellable polymer, and then reduces crosslinking reaction speed.Hence one can see that, and those skilled in the art can, according to the needs of actual procedure, mix one or more protonic solvents or non-solvent, to regulate and control required crosslinking reaction speed.
Moreover in one embodiment, cross-linked formulations provided by the present invention at room temperature (20-25 DEG C) starts to carry out part crosslinking reaction, can help by heating steps the carrying out of crosslinking reaction.In another embodiment, cross-linked formulations provided by the present invention need just can be carried out crosslinking reaction by heating steps.
In sum, cross-linked formulations provided by the present invention can be in order to regulate and control crosslinking reaction speed, (for example spinning forms fiber to be beneficial to follow-up ion Process Technology of Polymer process, or coat in carrier layer, form coating layer), and the fiber of subsequent process gained or coating layer can pass through heating steps again, make polymer and linking agent completely crosslinked, the material of last gained can be used as filtration material for desalination.
[embodiment]
Embodiment 1 synthetic cross-linking agent chemical structure (III): Poly (styrene-co-vinylbenzylhalide) copolymer
Get respectively 2g/1g/1g vinylbenzene (Styrene)/1-chloro-4-methyl-benzene (vinylbenzylchloride)/brooethyl vinylbenzene (vinylbenzylbromide) (each monomer ratio is determined by demand), and add 20ml tetrahydrofuran (THF) (THF), under nitrogen, react, temperature is risen to 70 DEG C again, then add initiator benzoyl peroxide (benzoperoxide, BPO) solution (BPO solution: 0.04g/5ml THF) reacts 3 hours at 70 DEG C.Again by product with methyl alcohol sedimentation, filter after draining and can obtain Poly (styrene-co-vinylbenzylhalide) copolymer.
Embodiment 2 synthetic cross-linking agent chemical structures (IV): Halide-methylated Polysulfone (PSF-X)
3 grams of polysulfones (polysulfone) (molecular weight 35,000) are mixed with 80ml chloroform (chloroform), under nitrogen, be heated to 50 DEG C it is dissolved completely, to form mixing solutions.
By 2g formaldehyde (P-formaldehyde), 0.35g tin tetrachloride (SnCl
4), 4.3g trimethylchlorosilane (trimethylsilylchloride, SiMe
3cl) with 5.9g bromotrimethylsilane (trimethylsilylbromide, SiMe
3br) (SiMe
3cl and SiMe
3the ratio of Br is depending on actual needs adjustment) be jointly dissolved in 30ml chloroform (chloroform), more above-mentioned solution is added in polysulfones solution and is mixed together, with 50 DEG C of reflux 48 hours.After reaction finishes, add methyl alcohol that product is precipitated, finally can obtain white solid Halide-methylated Polysulfone (PSF-X).
The swollen polymer Poly of embodiment 3 synthesis of soluble (sodium styrene sulfate-co-4-vinylpyridine-co-styrene)
Get 230g Sodium styrene sulfonate (sodium styrene sulfate), 460g 4-vinylpyridine (4-vinylpyridine), 230g vinylbenzene (styrene) (each monomer ratio can optionally be adjusted), 1150ml deionized water, 1150ml Virahol (IPA) stirring and dissolving, pass into nitrogen, at 70 DEG C of constant temperature, react 30 minutes, to form mixing solutions.
Get 9.2g Potassium Persulphate (potassium persulfate, KPS) and be dissolved in 230ml deionized water, more slowly splash in above-mentioned mixing solutions, react and complete for 3 hours.The macromolecular solution having reacted, with salt solution sedimentation, can obtain Off-white solid Poly (sodium styrene sulfate-co-4-vinylpyridine-co-styrene) after drying, washing purifying.
The synthetic quaternary ammonium salt of embodiment 4
The polymer of embodiment 3 is formulated in to N, in N-N,N-DIMETHYLACETAMIDE (DMAc) solvent, solid content is 20wt%, proportionally add bromo-6 chlorohexanes (1-bromo-6-chloro-hexane, BCH) of linking agent 1-of 0.3 times (0.3 equivalent) being equivalent to macromolecular chain pyridine (pyridine) molar content.
Get above-mentioned appropriate sample and on viscosity apparatus, carry out viscosity monitoring, viscosity measurement and temperature of reaction are all at room temperature carried out, and every set time record viscosity numerical value change, experimental result is as shown in table 1.
Table 1
Comparative example 1
Experimental procedure, material, measuring method and implementation condition are with embodiment 4, and linking agent changes 1,6-dibromo-hexane (1,6-dibromo hexane, DBH) into by BCH only, and linking agent equivalents still maintains 0.3 equivalent.Experimental result is as shown in table 2.
Can be learnt by table 1 and the experimental result of table 2, than DBH, BCH viscosity under same experimental conditions rises slowly many.
Table 2
Embodiment 5 utilizes protonic solvent or non-solvent control crosslinking reaction speed
The polymer of embodiment 3 is formulated in respectively in the solvent that is shown in table 3 and (is respectively N, N-N,N-DIMETHYLACETAMIDE (DMAc), N, mixed solvent and the N of N-N,N-DIMETHYLACETAMIDE and tetrahydrofuran (THF) (THF), the mixed solvent of N-N,N-DIMETHYLACETAMIDE and alcohol), wherein solution solid content is fixed on 23.5wt%.
Above-mentioned each batch of solution is proportionally added respectively to the bromo-6 chlorohexane (1-bromo-6-chloro-hexane of 1-that are equivalent to macromolecular chain pyridine (pyridine) 0.3 equivalent, BCH) linking agent, get appropriate sample and on viscosity apparatus, carry out online viscosity monitoring, Temperature Setting is at 25 DEG C, change in time, every 0.5 hour record viscosity numerical value change, experimental result is as shown in table 3.
Data by table 3 can be learnt, add protonic solvent (as alcohol) or non-solvent (as tetrahydrofuran (THF)), really can slow down crosslinking reaction speed.
Table 3
Embodiment 6
The swellable molecule of embodiment 3 is mixed to (75: 25,60: 40,50: 50 and 40: 60) by weight proportion with the polymer of embodiment 1 (linking agent), be formulated in respectively N, in N-dimethylacetamide solvent, macromolecular solid content is 20wt%.
After above-mentioned solution is fully mixed, then by solution coat on glass baseplate, after 130 DEG C of crosslinked sclerosis, then confirm with FT-IR, experimental result is if table 5 is with as shown in Figure 1A-1D, by 1638cm
-1fT-IR charateristic avsorption band can determine that mixing solutions has carried out crosslinking reaction.
Table 5
| The weight blending ratio of embodiment 3: embodiment 1 | Accompanying drawing |
| 75∶25 | 1A |
| 60∶40 | 1B |
| 50∶50 | 1C |
| 40∶60 | 1D |
Embodiment 7
Implementation step is with embodiment 6, and difference is that macromolecular material changes swellable polymer and the embodiment 2 (linking agent) of embodiment 3 into, and blending ratio is respectively 70: 30,63: 37 and 37: 63, by 1638cm
-1fT-IR charateristic avsorption band can determine that mixing solutions has carried out crosslinking reaction.
Although the present invention discloses as above with several preferred embodiments; but it is not in order to limit the present invention; under any, in technical field, there is the technician of common knowledge; without departing from the spirit and scope of the present invention; when changing arbitrarily and modify, therefore protection scope of the present invention is when being as the criterion depending on claims person of defining.
Claims (11)
1. a cross-linked formulations that forms quaternary ammonium salt, comprising:
With amino swellable polymer, wherein should be formed with the monomer polymerization of chemical formula (I-3) by following chemical formula (I-1), chemical formula (I-2) with amino swellable polymer:
wherein R
1be selected from phenylbenzimidazole sulfonic acid base or alkyl group sulfonic group;
wherein R
2be selected from
wherein R
3be selected from
and chemical formula (I-1), chemical formula (I-2) are 0.1-50: 1-99: 0.1-50 with the mol ratio of chemical formula (I-3);
Linking agent, wherein this linking agent has at least two halogenic substituents, and these halogenic substituents are not identical; And
Solution, wherein this solution comprises that dissolving is with the high molecular solvent of amino swellable.
2. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this linking agent is selected from chemical formula (II), chemical formula (III) or chemical formula (IV),
Wherein A is selected from C
1-C
25alkylidene group (alkylene), C
6-C
25arylidene (arylene) or C
7-C
25sub-aralkyl (aralkylene); R
1, R
2be selected from independently of one another Cl, Br or I, and R
1≠ R
2;
Wherein R
3, R
4, R
5be selected from independently of one another
R
6, R
9be selected from independently of one another H or CH
3;
R
7, R
8be selected from independently of one another CH
2cl, CH
2br, CH
2i;
R
10, R
11be selected from independently of one another H, CH
3, CH
2cl, CH
2br, CH
2i, wherein R
7≠ R
10, R
8≠ R
11, the number that wherein a, b, c are repeating unit, and a, b, c are 1～1000 integer independently of one another;
Wherein R
12, R
13be selected from independently of one another Cl, Br or I, and R
12≠ R
13, the number that wherein d, e are repeating unit, and d, e are 1～1000 integer independently of one another.
3. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 1, wherein this solution also comprises protonic solvent or non-solvent.
4. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 3, wherein this dissolving is with the high molecular solvent of amino swellable: the part by weight of protonic solvent or non-solvent is 9/1-5/5.
5. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 3, wherein this protonic solvent comprises water, acids or alcohols.
6. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 5, wherein this acids comprises formic acid, acetic acid, citric acid, succsinic acid, hydrochloric acid or above-mentioned combination.
7. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 5, wherein this alcohols comprises monohydroxy-alcohol or polyvalent alcohol.
8. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 7, wherein this monohydroxy-alcohol comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or above-mentioned combination.
9. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 7, wherein this polyvalent alcohol comprises many alcohols, ether glycols or above-mentioned combination.
10. the cross-linked formulations of formation quaternary ammonium salt as claimed in claim 3, wherein this non-solvent comprises tetrahydrofuran (THF), methylene dichloride, trichloromethane, straight or branched alkanes, benzene, toluene, acetone or above-mentioned combination.
The cross-linked formulations of 11. formation quaternary ammonium salts as claimed in claim 1, wherein this linking agent account for this with the high molecular part by weight of amino swellable be 0.01-10 doubly.
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| 马光辉."化学交联法制备聚(4-乙烯基吡啶)纳米凝胶微球".《过程工程学报》.2002,第2卷(第4期), * |
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